WO2015042013A1 - Stable linear polymers - Google Patents

Abstract

This disclosed technology relates to a polymer additive for use in a composition and/or process for personal care, home care, Industrial and Institutional (I&I) care and health care applications. The examples provide a multifunctional polymer additive made up of units derived from a unique mixture of monomers that can function as a rheology modifier, a fixative, a detergent builder, and an emulsifier. The polymer also has good high temperature stability and effectiveness over a wide pH range.

Description

STABLE LINEAR POLYMERS

[0001] This disclosed technology relates to a polymer additive for use in a compo- sition and/or process for personal care, home care, Industrial and Institutional (I&I) care and health care applications. The examples provide a multifunctional polymer additive made up of units derived from a unique mixture of monomers that can function as a rheology modifier, a fixative, a detergent builder, and an emulsifier. The polymer also has good high temperature stability and effectiveness over a wide pH range.

BACKGROUND

[0002] In general, the rheology of products in the personal care, home care and I&I care areas is part of the criteria for a useful end product. Desirable rheology modifiers will provide adequate thickening over a wide pH range and in small doses, without altering other desirable properties of a product. For instance, aqueous formulations in personal care and industrial cleansing products typically contain thickeners to vis- cosify the composition sufficiently to enable convenient delivery and handling of the formulated product.

[0003] Known thickeners comprise a number of polymeric materials of various chemical types. A list of them can be found in Gottschalk, T., Breslawec, H.P., International Cosmetic Ingredient Dictionary and Handbook, Personal Care Products Council Publisher, 14th Ed, Washington, DC, USA, (2012), 3974-3 977. Common thickeners are, for example, polymers based on polyacrylic acid, e.g. Carbopols™, carbomers, ammonium polyacrylates or sodium acrylates copolymers. Also suitable are cellulose ethers, cellulose derivatives (e.g. carboxymethylcellulose, hydroxyeth- ylcellulose), gelatins, starch and starch derivatives, sodium alginates, fatty acid polyethylene glycol esters, agar agar, tragacanth or dextrins. Also suitable are polyvinyl alcohols, polyacrylamides, polyvinylpyrrolidone, polyvinyl methyl ether, polyethylene oxides, copolymers of maleic anhydride and vinyl methyl ether, and mixtures thereof.

[0004] (Meth)acrylate monomers functionalized with long alkyl chains and poly(ethyleneoxide)s (PEG), have been used as associative monomers to improve the feel & sensory properties, for example, in personal care formulations, as taught for instance in US Patent No. 7,399,478 to Loftier et al, issued Jul. 15, 2008 and US Patent No. 7,566,763 to Loffler et al, issued Jul. 28, 2009. However, the ethyleneox- ide chemistry is being phased out by the personal care industry due to the potential presence of dioxane byproducts. Furthermore, the solubility of poly ethers in water decreases as temperature increases, which presents issues when formulating products. In addition, the ester based PEG containing long alkyl chain (meth)acrylate monomer is prone to hydrolysis at high temperatures.

[0005] Ionic rheology modifiers for aqueous systems can lose performance at low pH, or in the presence of a large amount of electrolytes. Lightly crosslinked AMPS™ based polymers have been used as rheology modifiers at broad pH and electrolyte concentration ranges, for instance, as shown in US Patent No. 7,932,337 to Benetti et al., issued Apr. 26, 201 1. Similarly, US Patent No. 4,975,482 to Peiffer, issued Dec. 4, 1990, describes a linear poly(acrylamide-co-Ci₂AMPS) to thicken a salt solution by hydrophobic associative thickening.

[0006] Improved and alternative thickening systems for low pH systems or systems with a high concentration of electrolytes, without the use of PEG would be desireable.

[0007] In addition, particularly in the home care and I&I care fields, but also in the personal care area, new and effective polymer "builders" would be desirable.

[0008] Builders are used in detergent cleaners and are typically surfactant containing systems utilized to extend and improve the detergent cleaner's cleaning properties. The function of the builder is to remove calcium and other undesirable metal ions from washing solutions by sequestration or precipitation.

[0009] In addition, builders can chelate ions of hardness, and provide a pH buffering function and some anti-redeposition functionality that can enhance cleaning performance. Inorganic sodium tripolyphosphate (STPP) is a conventional builder that has historically been used in detergent cleaners. However, there are perceived environmental issues associated with STPP and its use has been reduced or eliminated from many detergent products, such as, for example, dishwashing detergents. The loss of STPP as a builder has created immediate product performance issues in the dishwashing detergent market, particularly in relation to a lack of cleaning efficiency and film formation due to a failure to remove metal ion residue. [0010] A new copolymer of a unique mixture of monomers has been developed that can act as a thickener and as a builder in personal care, home care, and I&I care systems.

SUMMARY

[0011] The disclosed technology provides a polymer that includes units derived from: (A) a first monomer composition including an ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomer, where the monomer includes at least one alkyl group containing 5 to 30 carbon atoms, or salts thereof; and (B) a second monomer composition including one or more ethylenically unsaturated polymerizable monomers, or salts thereof; wherein the second monomer composition (B) is different from the first monomer composition (A).

[0012] The disclosed technology provides for embodiments where (B), the second monomer composition, comprises at least one of: (i) one or more ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomers where the monomers of free of any alkyl groups containing more than 4 carbon atoms or salts thereof; (ii) one or more carboxylic acid monomers or partial esters, or salts thereof; (iii) one or more amide monomers; (iv) one or more alkoxylated hydrophobically modified associative monomers; (v) one or more phosphonic acid monomers or partial esters, or salts thereof; (vi) one or more vinyl monomers; or (vii) any combination thereof.

[0013] The disclosed technology provides for embodiments where (B) comprises one or more ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomers where the monomers are free of any alkyl groups containing more than 4 carbon atoms.

[0014] The disclosed technology provides for embodiments where (B) comprises a compound having the structure:

where R⁴ is an alkyl group containing 1 to 4 carbon atoms; R⁵ is hydrogen or an alkyl group containing from 1 to 4 carbon atoms; and R⁶ is an alkyl group containing 1 to 4 carbon atoms; and R⁷ is hydrogen or a methyl group; and the sulfonic acid goup may be present as the acid, a metal salt, an ammonium salt, or an alkylamine salt thereof.

[0015] The sulfonic acid group in the structure of (B) above may be present as the acid as shown, or it can be a metal salt, an ammonium salt, or an alkylamine salt thereof. In other words, the disclosed technology provides for embodiments where (B) comprises 2-acrylamido-2-methylpropane-l -sulfonic acid, a mono or multivalent metal of one or more thereof, an ammonium salt of one or more thereof, an alkylamine salt of one or more thereof or a combination thereof.

[0016] The disclosed technology provides for embodiments where (B) comprises 2-acrylamido-2-methypropane-l -sulfonic acid, a mono or multivalent metal of one or more thereof, an ammonium salt or one or more thereof, an alkylamine salt of one or more thereof or a combination thereof.

[0017] The disclosed technology provides for embodiments where (B) comprises one or more ethylenically unsaturated polymerizable carboxylic acid monomers, or salts and/or esters or partial esters thereof.

[0018] The disclosed technology provides for embodiments where (B) comprises acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid or salts and/or esters or partial esters thereof.

[0019] The disclosed technology provides for embodiments where (B) comprises one or more acrylamide monomers.

[0020] The disclosed technology provides for embodiments where (B) comprises one or more ethylenically unsaturated amido functional monomers selected from acrylamide, methyl acrylamide, methyl methacrylamide, N-alkylmethacrylamide, Ν,Ν-dialkylmethacrylamide, N-alkylacrylamide, and N,N-dialkylacrylamide.

[0021] The disclosed technology provides for embodiments where the polymer further comprises units derived from: (C) a third monomer composition comprising one or more monomers that include an alkyl group containing 1 to 18 carbon atoms comprising a simple ester, a vinyl ester, an mono-allyl ether, or salts thereof, or any combination thereof.

[0022] The disclosed technology provides for embodiments where (A) comprises a compound having the structure:

where R 1 is an alkyl group containing from 5 to 30 carbon atoms; R 2 is hydrogen or an alkyl group containing from 1 to 30 carbon atoms; and R is an alkyl group containing 1 to 4 carbon atoms; and R⁷ is hydrogen or a methyl group; and the sulfonic group can be present as the acid, as shown, or a metal, ammonium, or alkylamine salt thereof.

[0023] The disclosed technology provides for embodiments where (A) 2- acrylamidododecane-1 -sulfonic acid, 2-acrylamidohexadecane-l -sulfonic acid, 2- acrylamidooctadecane-1 -sulfonic acid, 2-acrylamidodecane-l -sulfonic acid, 2- acrylamidooctane-1 -sulfonic acid, 2-acrylamido-2,4,4-trimethylpentane-l -sulfonic acid, 2- acrylamidoheptadecane-1 -sulfonic acid, 2-acrylamidopentadecane-l -sulfonic acid, 2- acrylamido-2-octyldecane-l -sulfonic acid, 2-methacrylamidododecane-l -sulfonic acid, 2- methacrylamidohexadecane-1 -sulfonic acid, 2-methacrylamidooctadecane-l -sulfonic acid, 2-methacrylamidodecane-l -sulfonic acid, 2-methacrylamidooctane-l -sulfonic acid, 2- methacrylamido-2,4,4-trimethylpentane- 1 -sulfonic acid, 2-methacrylamidoheptadecane- 1 - sulfonic acid, 2-methacrylamidopentadecane-l -sulfonic acid, 2-methacrylamido-2- octyldecane-1 -sulfonic acid, an alkali metal of one or more thereof, an ammonium salt or one or more thereof, an alkylamine salt of one or more thereof, or a combination thereof.

[0024] The disclosed technology provides for embodiments where the polymer is made up of: 0.1 to 50, or 0.1 to 30, or even 0.1 to 10 percent by weight of monomer units derived from (A); and 1 to 99.9 or 50 to 99.9, or 70 to 99.9, or even 90 to 99.9 percent by weight of monomer units derived from (B).

[0025] The disclosed technology provides for embodiments where the polymer is made up of: 0.1 to 50, or 0.1 to 30, or even 0.1 to 10 percent of monomer units derived from (A); 1 to 98.9 or 50 to 98.9, or 70 to 98.9, or even 90 to 98.9 percent by weight units derived from (B); and 1 to 49 percent by weight units derived from (C).

[0026] The disclosed technology provides for embodiments where the polymer is free of units derived from an alkylene glycol monomer.

[0027] The disclosed technology provides for embodiments where the polymer units derived from the compounds of (A) have the following structures:

R¹ -R²

R³

SO3H

wherein: R 1 is an alkyl group containing from 5 to 24 carbon atoms; R 2 is hydrogen or an alkyl group containing from 1 to 10 carbon atoms; R is an alkyl group containing 1 to 4 carbon atoms; R⁷ is hydrogen or a hydrocarbyl group; and the sulfonic group can be present as an acid, as shown, or in the form of an alkali metal or ammonium salt thereof.

[0028] The disclosed technology provides for a process of making a polymer comprising the steps of: (I) reacting: (A) a first monomer composition comprising an ethyleni- cally unsaturated hydrocarbylamidoalkanesulfonic acid monomer, where the monomer includes at least one alkyl group containing 5 to 30 carbon atoms, or salts thereof; (B) a second monomer composition comprising one or more ethylenically unsaturated polymer- izable monomers, or salts thereof; wherein the second monomer composition (B) is different from the first monomer composition (A). The disclosed technology provides for embodiments where the process is a solution polymerization, a precipitation polymerization, a gel polymerization, emulsion polymerization, or an inverse emulsion polymeriza- tion.

[0029] The disclosed technology provides for embodiments where step (I) of the process further comprises reacting: (C) a third monomer composition comprising one or more monomers that include an alkyl group containing 1 to 18 carbon atoms comprising a simple ester, a vinyl ester, an mono-allyl ether, or any combination thereof; with (A) and (B).

[0030] The disclosed technology provides for the use of the described polymer as a builder in detergent cleaners.

[0031] The disclosed technology provides for methods that include the use of the described polymer as a builder in detergent cleaners. [0032] The disclosed technology provides for the use of the described polymer as a thickener in aqueous and/or non-aqueous formulations and aqueous and/or non-aqueous surfactant compositions.

[0033] The disclosed technology provides for methods that include the use of the described polymer as a thickener in aqueous formulations and aqueous surfactant compositions.

DETAILED DESCRIPTION

[0034] Various preferred features and embodiments will be described below by way of non-limiting illustration.

[0035] The term "personal care" as used herein includes, without being limited thereto, includes cosmetics, toiletries, cosmeceuticals, beauty aids, insect repellents, personal hygiene and cleansing products applied to the body, including the skin, hair, scalp, and nails of humans and animals.

[0036] The term "home care products" as used herein includes, without being limited thereto, products employed in a domestic household for surface cleaning or maintaining sanitary conditions, such as in the kitchen and bathroom (e.g., hard surface cleaners, hand and automatic dish care, toilet bowl cleaners and disinfectants), and laundry products for fabric care and cleaning (e.g., detergents, fabric conditioners, pre-treatment stain removers), and the like.

[0037] The term "health care products" as used herein includes, without being limited thereto, pharmaceuticals (controlled release pharmaceuticals), pharmacosmet- ics, oral care (mouth and teeth) products, such as oral suspensions, mouthwashes, toothpastes, dentifrices, and the like, and over-the-counter products and appliances (topical and transdermal), such as patches, plasters and the like, externally applied to the body, including the skin, scalp, nails and mucous membranes of humans and animals, for ameliorating a health-related or medical condition, for generally maintaining hygiene or well-being, and the like.

[0038] The term "institutional and industrial care" ("I&I") as used herein includes, without being limited thereto, products employed for surface cleaning or maintaining sanitary conditions in institutional and industrial environments, textile treatments (e.g., textile conditioners, carpet and upholstery cleaners), automobile care (e.g., hand and automatic car wash detergents, tire shines, leather conditioners, liquid car polishes, plastic polishes and conditioners), paints and coatings, and the like.

[0039] As used herein, the term "rheological properties" and grammatical variations thereof, includes, without limitation such properties as Brookfield viscosity, increase or decrease in viscosity in response to shear stress, flow characteristics, gel properties such as stiffness, resilience, flowability, and the like, foam properties such as foam stability, foam density, ability to hold a peak, and the like, suspension properties such as yield value, and aerosol properties such as ability to form aerosol droplets when dispensed from propellant based or mechanical pump type aerosol dispensers.

[0040] The term "aesthetic property" and grammatical variations thereof as applied to compositions refers to visual and tactile psychosensory product properties, such as color, clarity, smoothness, tack, lubricity, texture, conditioning and feel, and the like.

[0041] Here, as well as elsewhere in the specification and claims, individual numerical values (including carbon atom numerical values), or limits, can be combined to form additional non-disclosed and/or non-stated ranges.

[0042] The headings provided herein serve to illustrate, but not to limit the claims in any way or manner.

[0043] The disclosed technology provides a polymer including units derived from: (A) a first monomer composition comprising an ethylenically unsaturated hydro- carbylamidoalkanesulfonic acid monomer, where the monomer includes at least one alkyl group containing 5 to 30 carbon atoms, or salts thereof; and (B) a second monomer composition comprising one or more ethylenically unsaturated polymeriza- ble monomers, or salts thereof; wherein the second monomer composition (B) is different from the first monomer composition (A).

[0044] In some embodiments (A) and (B) differ in that the monomers of (B) do not contain a pendant alkyl group that includes more than 4 carbon atoms, while the monomers of (A) must include a pendant alkyl group containing from 5 to 30 carbon atoms.

[0045] In some embodiments (A) and (B) differ in that the monomers of (A) have a higher number average molecular weight than the monomers of (B). [0046] In some embodiments (A) and (B) differ in that the monomers of (A) have the specific structure defined below for it, and the monomers of (B) have the specific structure defined below for it. In other embodiments the monomer of (B) are eth- ylenically unsaturated amidoalkanesulfonic acids, partial esters thereof, or full esters thereof.

[0047] In some embodiments more than 50%, on a molar basis, of the monomers that become part of the described polymers are ionic. In other words, in some embodiments the described polymer is made up of units where more than 50% of the units are ionic, such that the polymer may be described as ionic.

[0048] The monomers of (A) may include ethylenically unsaturated, water- soluble sulfonic acid monomers that have been hydrophobically modified and include polymerizable sulfonic acids such as unsaturated hydrocarbylamidoalkanesulfonic acids that have been hydrophobically modified, for example, acrylamido- or methac- rylamidosulfonic acids hydrophobically modified by the addition of a long hydro- carbyl or alkyl subsitient group. In one embodiment, the ethylenically unsaturated water-soluble polymerizable sulfonic acid can be an unsaturated-hydrocarbylamido- alkanesulfonic acid.

[0049] In some embodiment the monomers of (A) may include a compound having the structure:

where R 1 is an alkyl group containing from 5 to 30 carbon atoms; R 2 is hydrogen or an alkyl group containing from 1 to 30 carbon atoms; and R is an alkyl group containing 1 to 4 carbon atoms; and R⁷ is hydrogen or a methyl group; or a metal, ammonium, or alkyla- mine salt thereof. In some embodiments R¹ is an alkyl group containing from 5 to 30 carbon atoms, or from 5 to 24, or from 6 to 24, or from 8 to 22, or from 6 to 18, or from 10 to 16 carbon atoms, or even 10, 14 or 15 carbon atoms. In some embodiments R is hydrogen or an alkyl group containing from 1 to 30 carbon atoms, or even from 1 to 10, 1 to 8 or even 1 or 8 carbon atoms. In some embodiments R is an alkyl group containing 1 to 4 carbon atoms, or even just 1 carbon atom. In some embodiments R⁷ is hydrogen or a methyl group.

[0050] Suitable examples for the monomers of (A) include 2- acrylamidododecane-1 -sulfonic acid, 2-acrylamidohexadecane-l -sulfonic acid, 2- acrylamidooctadecane-1 -sulfonic acid, 2-acrylamidodecane-l -sulfonic acid, 2- acrylamidooctane-1 -sulfonic acid, 2-acrylamido-2,4,4-trimethylpentane-l -sulfonic acid, 2-acrylamidoheptadecane-l -sulfonic acid, 2-acrylamidopentadecane-l -sulfonic acid, 2-acrylamido-2-octyldecane-l -sulfonic acid, 2-methacrylamidododecane-l - sulfonic acid, 2-methacrylamidohexadecane-l -sulfonic acid, 2- methacrylamidooctadecane-1 -sulfonic acid, 2-methacrylamidodecane-l -sulfonic acid, 2-methacrylamidooctane-l -sulfonic acid, 2-methacrylamido-2,4,4- trimethylpentane-1 -sulfonic acid, 2-methacrylamidoheptadecane-l -sulfonic acid, 2- methacrylamidopentadecane-1 -sulfonic acid, 2-methacrylamido-2-octyldecane-l - sulfonic acid, an alkali metal of one or more thereof, an ammonium salt or one or more thereof, an alkylamine salt of one or more thereof, or a combination thereof.

[0051] The monomers of (B) may include one or more various monomers that differ from the monomers of (A).

[0052] The monomers of (B) may include at least one of: (i) one or more eth- ylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomers where the monomers are free of any alkyl groups containing more than 4 carbon atoms or salts thereof; (ii) one or more carboxylic acid monomers or partial esters, or salts thereof; (iii) one or more amide monomers; (iv) one or more alkoxylated hydrophobically modified associative monomers; (v) one or more phosphonic acid monomers or partial esters, or salts thereof; (vi) one or more vinyl monomers; or (vii) any combi- nation thereof.

[0053] In some embodiments the monomers of (B) include: (i) one or more ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomers where the monomers of free of any alkyl groups containing more than 4 carbon atoms or salts thereof.

[0054] In such embodiments the monomers of (B) may include ethylenically unsaturated, water-soluble sulfonic acid monomers and include polymerizable sulfonic acids such as unsaturated hydrocarbylamidoalkanesulfonic acids, for example, acrylamido- or methacrylami do sulfonic acids, where the monomers are free of any alkyl groups containing more than 4 carbon atoms.

[0055] In one embodiment, the monomers of (B) may include ethylenically unsaturated, water-soluble sulfonic acid monomers and include polymerizable sulfonic acids such as unsaturated hydrocarbylamidoalkanesulfonic acids, for example, acrylamido- or methacrylamidosulfonic acids. In one embodiment, the ethylenically unsaturated water-soluble polymerizable sulfonic acid can be an unsaturated- hydrocarbylamido-alkanesulfonic acid. The pendent group can also include phenyl groups, alkyl substituted phenyl groups and cycloaliphatic groups.

[0056] In one embodiment, the monomers of (B) may include a compound having the structure:

where R⁴ is an alkyl group containing 1 to 4 carbon atoms; R⁵ is hydrogen or an alkyl group containing from 1 to 4 carbon atoms; and R⁶ is an alkyl group containing 1 to 4 carbon atoms; and R⁷ is hydrogen or a methyl group; or a metal, ammonium, or alkyla- mine salt thereof. In some embodiments R⁴ is an alkyl group containing less than 4 carbon atoms, 1 to 4 carbon atoms, or even just 1 carbon atom. In some embodiments R⁵ is hydrogen or an alkyl group containing less than 4 catrbon atoms, from 1 to 4 carbon atoms or even just 1 carbon atoms. In some embodiments R5 is hydrogen or a methyl group. In some embodiments R⁶ is an alkyl group containing 1 to 4 carbon atoms or even just 1 carbon atom. In some embodiments R⁷ is hydrogen or a methyl group. Any of these embodiments may also include a metal, ammonium, or alkylamine salt of the sulfonic acid thereof.

[0057] In embodiments where the monomers of (B) include a metal salt of compound described above, suitable metals include either alkali or alkaline metals. In some embodiments the metal is calcium.

[0058] In embodiments where the monomers of (B) include an alkylamine salt of compound described above, suitable alkylamines include lipophilic amines and/or lipophilic amine salts. The amine ion, that is, the amine in its cationic form, can be represented by:

r8_r9r10_r11_n+ where R⁸, R⁹, R¹⁰ and R¹¹ are independently hydrogen or hydrocarbyl groups, provid- ed that at least one of R⁸, R⁹, R¹⁰ and R¹¹ is a hydrocarbyl group of sufficient length suitable to impart lipophilic properties. The term "amine salt" or "amine ions" includes ions or salts, where up to three of the R groups are hydrocarbyl groups, and quaternary amine ions or salts, where each of the R groups is a hydrocarbyl group. In order to provide suitable lipophilic character, the total carbon atoms in the amine ion should be at least 6, and in one embodiment at least 10, or at least 14. In certain embodiments, the total number of carbon atoms in an amine cation does not exceed 36 carbon atoms; thus the total number of carbon atoms may be, e. g., 6 to 36. Examples of suitable amines include N,N-dimethyl-n-dodecylamine, 2- ethylhexylamine, tri-n-butylamine, triisobutylamine, triisooctylamine, tripropyla- mine, trihexyl amine, trioctylamine, decylamine, dodecylamine, tridecylamine, tridodecylamine, hexadecylamine, octadecylamine, oleylamine, higher tert-alkyl primary amines such as Primene 81R™ and Primene JMT™ from Rohm and Haas, and aromatic amines such as pyridines, benzylamine, N-methylbenzylamine, 2- phenethylamine, aniline, and substituted anilines.

[0059] As used herein, the term "lipophilic" is given its conventional meaning, that is, interacting favorably with or being soluble in non-polar or fatty solvents. A synonym for "lipophilic" is "hydrophobic," which may be contrasted with "hydro- philic." Hydrophobic materials exhibit little or no favorable interaction with water and are generally not appreciably soluble in water or similarly polar solvents. The hydrophobic or hydrophilic character of a material can also be understood to approximately correlate with results derived from the octanol/water partition test. The original form of this test, involving measurement of the equilibrium concentration of a dissolved substance in a two-phase system of n-octanol and water, as well as a chromatographic method, are described in ASTM E-l 147-92. P = C₀ctanoi/C_water- The hydrophilic or hydrophobic nature of an amine in question can be evaluated by comparing its P value with the P values of other amines, as those listed above, which are known to be appropriately lipophilic materials. [0060] These alkylamines and the salts made of the same are described in greater detail in US patent application 2008/0221253.

[0061] In some embodiments the monomers of (B) include 2-acrylamido-2- methypropane-1 -sulfonic acid, a mono or multivalent metal of one or more thereof, an ammonium salt or one or more thereof, an alkylamine salt of one or more thereof or a combination thereof.

[0062] In some embodiments the monomers of (B) include: (ii) one or more carboxylic acid monomers or partial esters, or salts thereof. In such embodiments the monomers of (B) may comprise one or more ethylenically unsaturated polymerizable carboxylic acid monomers, or salts and/or esters thereof. Suitable examples include what are often referred to as carboxylic monomers or acrylate monomers.

[0063] Additional examples of suitable carboxylic acid monomers, or partial esters, full esters, or salts thereof, include: Sipomer COPS®-I, commercially available from Rhodia, which is a 40% aqueous solution of sodium allyl ether sulfonate and sodium 1 -allyloxy-2-hydroxypropyl sulfonate, having a molecular weight of about 218; vinyl benzene sulfonic acids, vinyl benzene sulfonates, alkyl vinyl benzene sulfonic acids, alkyl vinyl benzene sulfonates for example SPINOMAR® NaSS, commercially available from Tosoh, which is a sodium p-styrene sulfonate having a molecular weight of about 206; 2-sulfoethylmetahcrylate; alkylvinyl sulfonic acids, alkyl vinyl sulfonates for example sodium vinyl sulfonate (SVS); sodium al- lylsulfonate (SAS); sodium methally sulfonate (SMAS); acrylic acid-(3- sulfonpropyl)ester and potassium salts thereof (SPA); methacrylic acid-(3- sulfonpropyl)ester and potassium salts thereof (SPM), or any combination thereof.

[0064] In some embodiments the monomers of (B) are essentially free of any acrylate monomers. In some embodiments the monomers of (B) are free of any acrylate monomers. In some embodiments the polymers described herein are essentially free of any acrylate monomers. In some embodiments the polymers described herein are free of any acrylate monomers.

[0065] In other embodiments the monomers of (B) include acrylic acid, methacryl- ic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid or salts and/or esters thereof. The esters thereof include full and partial esters thereof.

[0066] In some embodiments the monomers of (B) include one or more compounds having the structural formula: (R¹²)(R¹³)C=C(R¹⁴)(R¹⁵)

[0067] wherein: R¹² is H or CH₃; R¹³ is H or COOH; R¹⁴ is H or COOH; and R¹⁵ is H, COOH or CH₂COOH; provided that when R¹² is H and R¹³ is COOH, R¹⁴ and R¹⁵ are different and are either H or COOH; when R¹² and R¹³ are both H, R¹⁴ is COOH and R¹⁵ is CH₂COOH; and when R¹² is CH₃, R¹³ is COOH and R¹⁴ and R¹⁵ are different and are either H or COOH. Suitable examples include maleic acid, itaconic acid, fumaric acid, citraconic acid and mesaconic acid.

[0068] In some embodiments the monomers of (B) include: (iii) one or more amide monomers. In such embodiments the monomers of (B) may include one or more acrylamide monomers, which may also be described as ethylenically unsaturated ami do functional monomers.

[0069] Suitable examples include acrylamide, methyl acrylamide, methyl methac- rylamide, N-alkylmethacrylamide, Ν,Ν-dialkylmethacrylamide, N-alkylacrylamide, Ν,Ν-dialkylacrylamide, and any combination thereof.

[0070] In some embodiments the monomers of (B) include Ν,Ν'- dimethylacrylamide, t-butylacrylamide, t-octylacrylamide, or a combination thereof.

[0071] While in certain embodiments polymers prepared from the monomers can be free of PEG type thickeners, in some embodiments the monomers of (B) can include: (iv) one or more alkoxylated hydrophobically modified associative mono- mers.

[0072] The optional (iv) one or more alkoxylated hydrophobically modified associative thickener can be a hydrophobically modified α,β ethylenically unsaturated carboxylic acid monomer according to formula:

where R₃ can be a linear or branched Ci to C₈₀, or C₂ to C70, or C₃ to C₆o alkyl group, or a C₅ to C₃5 alkaryl group, where the alkaryl group can have from 1 to 25 carbon atoms in a linear or branched alkenyl moiety and from 4 to 10 carbon atoms in the aryl moiety; x is an integer in the range of 3 to 200, or 4 to 150, or 5 to 100; y is an integer in the range of 0, 1, 10, or 25 to about 75, 90, 99, or 100; and A is the residue of an unsaturated carbox- ylic acid according to formula:

where R₄ is hydrogen, a linear or branched Ci to C₁₂, Ci to C₁₀, or Ci to C₈ or even a Ci to C₆ alkyl group, or -C(0)OH; and R₅ is hydrogen. In another embodiment, R₃ can be a linear or branched Ci to C₇₅, or C₂ to C₆5, or even a C₄ to C₆o, C₆ to C₅₅ alkyl group, or a C₃ to C₅o, C₄ to C₄o, C₅ to C₃₅, or C₇ to C₃₀ alkaryl group, where the alkaryl group has from 2 to 22 carbon atoms in a linear or branched alkenyl moiety and from 5 to 8 carbon atoms in the aryl moiety; x is an integer in the range of about 6 to about 100; y is an integer in the range of 0 to about 75; R₄ is hydrogen, a linear or branched C₂ to C₆ alkyl group, or a linear or branched C₂ to C₆ alkyl group, -C(0)OH, or -CH₂C(0)OH. In still another embodiment, R₃ is a linear or branched C₈ to C50 alkyl group, or a C₈ to C₂₂ alkaryl group, where the alkaryl group has from 2 to 14 carbon atoms in a linear or branched alkenyl moiety and from 6 to 8 carbon atoms in the aryl moiety; x is an integer in the range of about 7 to about 75; y is an integer in the range of 0 to about 50; R₄ is hydrogen, a linear or branched C₃ to C₅ alkyl group, or -C(0)OH; and R₅ is hydrogen, a linear or branched C₃ to C₅ alkyl group, -C(0)OH, or -CH₂C(0)OH. Here, as well as elsewhere in the specification and claims, individual numerical values (including carbon atom numerical values), or limits, can be combined to form additional non-disclosed and/or non- stated ranges.

[0073] In still yet another embodiment, R₃ is a linear or branched C₁₀ to C₄₀ alkyl group, or a C₈ to C₂₂ alkaryl group, where the alkaryl group has from 2 to 14 carbon atoms in a linear or branched alkenyl moiety and from 6 to 8 carbon atoms in the aryl moiety; x is an integer in the range of about 10 to about 60; y is an integer in the range of 0 to about 30; and A is an acrylic, methacrylic or itaconic acid group. In still yet another embodiment, R₃ is a linear or branched C₁₀ to C₄₀ alkyl group, or a C₈ to C₂₂ alkaryl group, where the alkaryl group has from 2 to 14 carbon atoms in a linear or branched alkenyl moiety and from 6 to 8 carbon atoms in the aryl moiety; x is an integer in the range of about 16 to about 25; y is 0 to about 30; and A is an acrylic, methacrylic or itaconic acid group. Here, as well as elsewhere in the specification and claims, individual numerical values (including carbon atom numerical values), or limits, can be combined to form additional non-disclosed and/or non- stated ranges. [0074] In some embodiments the monomers of (B) include: (v) one or more phosphonic acid monomers or partial esters, such as vinylphosphonic acid (VPA) and vinylphosphonic acid dimethyl ester (VPADME), or salts thereof.

[0075] In some embodiments the monomers of (B) include: (vi) one or more vinyl monomers.

[0076] In some embodiments the polymer further comprises units derived from: (C) a third monomer composition comprising one or more monomer that includes an alkyl group containing 1 to 18 carbon atoms comprising a simple ester, a vinyl ester, an mono-allyl ether, or salts thereof, or any combination thereof.

[0077] In some embodiments the monomers of (C) can include acrylamides, methacrylamides, diacetone acrylamides, acrylic or methacrylic acids or their esters, vinyllactams such as vinyl pyrrolidone or vinyl caprolactam, and vinyl esters. In some embodiments the monomers of (C) include acrylamide, dimethyl amino ethyl methacrylate quaternized with dimethyl sulfate or with an alkyl halide, methacryloyl oxyethyl trimethyl ammonium chloride; methacryloyl oxyethyl trimethyl ammonium methosulfate; or any combination thereof.

[0078] In some embodiments the monomers of (C) may include: vinyl pyrroli- done/dialkylaminoalkyl acrylate or methacrylate, optionally quaternized; dimethyl amino ethyl methacrylate, vinyl caprolactam, and vinyl pyrrolidone; vinyl pyrroli- done and methacrylamidopropyl dimethylamine; vinyl pyrrolidone and quaternized dimethyl amino propyl methacrylamide; and quaternary ammonium salts formed by the reaction of diethyl sulfate and a copolymer of vinyl pyrrolidone and dimethyl aminoethylmethacrylate.

[0079] In some embodiments the monomers of (C) may include vinyl pyrrolidone and/or vinyl imidazole, optionally quaternized; vinyl pyrrolidone, acrylamide and vinyl imidazole, optionally quaternized; vinyl caprolactam, vinyl pyrrolidone and vinyl imidazole, optionally quaternized; vinyl pyrrolidone, vinyl imidazole, and diallyldimethyl ammonium chloride, optionally quaternized; or any combination thereof.

[0080] In still other embodiments the monomers of (C) may include compounds selected form the group consisting of alkyvinyl sulfonic acids, alkyl vinyl sulfonates, vinyl benzene sulfonic acids, vinyl benzene sulfonates, alkyl vinyl benzene sulfonic acids, alkyl vinyl benzene sulfonates, and combinations of two or more thereof. [0081] Suitable examples include but are not limited to compounds selected from the group consisting of N-vinyl acetamide, N-vinyl-N-methyl acetamide, N-vinyl-2- pyrrolidone, N-ethenyl-N-alkyl acetamide, and combinations of two or more thereof.

[0082] Suitable examples include but are not limited to compounds selected from the group consisting of ethylenically unsaturated N-substituted carboxylic acids selected from the group consisting of acrylamide, methyl acrylamide methylmethac- ryamide, N-alkylmethacrylamide, Ν,Ν-dialkylmethacrylamide, N-alkylacrylamide, Ν,Ν-dialkylacrylamide, and combinations of any two or more thereof.

[0083] Suitable examples include but are not limited to compounds selected from the group consisting of acrylic acid, salts of acrylic acid, methacrylic acid, salts of methacrylic acid, itaconic acid, salts of itaconic acid, acrylonitrile, alkoxy esters of acrylic acid, alkoxy esters of methacrylic acid, vinyl sulfonate, vinyl sulfonic acid and combinations of any two or more thereof.

[0084] In some embodiments the monomers of (C) include one or more vinyl esters selected from vinyl acetate, vinyl propionate, vinyl butanoate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl neodecano- ate, vinyl undecanoate, vinyl laurate, or any combination thereof.

[0085] In some embodiments the monomers of (C) include one or more mono- allyl ethers selected from mono-allyl ethers of sucrose, mono-allyl ethers of pentae- rythritol, or any combination thereof.

[0086] In other embodiments the monomers of (C) are essentially free of, or even completely free of, vinyl esters. In other embodiments the monomers of (C) are essentially free of, or even completely free of, mono-allyl ethers. In other embodiments the monomers of (C) are essentially free of, or even completely free of, acrylamides, methacrylamides, diacetone acrylamides, acrylic or methacrylic acids or their esters. In other embodiments the monomers of (C) are essentially free of, or even completely free of, vinyllactams such as vinyl pyrrolidone or vinyl caprolactam, and vinyl esters. In other embodiments the monomers of (C) are essentially free of, or even completely free of, alkyvinyl sulfonic acids, alkyl vinyl sulfonates, vinyl benzene sulfonic acids, vinyl benzene sulfonates, alkyl vinyl benzene sulfonic acids, and alkyl vinyl benzene sulfonates.

[0087] In some embodiments the polymer described herein is essentially free of, or even completely free of, units derived from an alkylene glycol monomer. [0088] In some embodiments the polymer described herein is made up of: 0.1 to 50 percent by weight of monomer units derived from (A); and 1 to 99.9 percent of monomer units derived from (B). Here we are talking about the percent of the total units that make up the polymer which are derived from the monomers of (A) and the percent of the total units that make up the polymer which are derived from the monomers of (B).

[0089] In some embodiments the polymer described herein is made up of: 0.1 to 50 or even 0.1 to 30, or even 0.1 to 10 percent of monomer units derived from (A); and 1 to 98.9 percent by weight of monomer units derived from (B); and 1 to 49 percent of monomer units derived from (C). Here we are talking about the percent of the total units that make up the polymer which are derived from the monomers of (A) and the percent of the total units that make up the polymer which are derived from the monomers of (B) and the percent of the total units that make up the polymer which are derived from the monomers of (C).

[0090] In some embodiments the polymer described herein includes units derived from the compounds of (A) that have the following structure:

R⁷

H,

R¹ -R²

R³

SO3H

wherein: R 1 is an alkyl group containing from 5 to 24 carbon atoms; R 2 is hydrogen or an alkyl group containing from 1 to 10 carbon atoms; R is an alkyl group containing 1 to 4 carbon atoms; R⁷ is hydrogen or a hydrocarbyl group of from 1 to 50 carbon atoms; and the sulfonic group can be an acid, as shown in the structure, or an alkali metal or ammonium salt thereof. In some embodiments R¹ is an alkyl group containing from 5 to 24 carbon atoms or from 6 to 24, or from 8 to 22, or from 6 to 18, or from 10 to 16, or even 10, 14 or 16 carbon atoms. In some embodiments R is hydrogen or an alkyl group containing from 1 to 10 carbon atoms, or from 1 to 8, or even just 8 carbon atoms. In some embodiments R is an alkyl group containing 1 to 4 carbon atoms, or even just 1 carbon atom. In some embodiments R⁷ is hydrogen or a hydrocarbyl group of from 1 to 50 carbon atoms, or even just hydrogen or a methyl group.

[0091] The disclosed technology includes process of making the described poly- mers. Such processes include the step of reacting: (A) a first monomer composition comprising an ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomer, where the monomer includes at least one alkyl group containing 5 to 30 carbon atoms, or salts thereof; and (B) a second monomer composition comprising one or more ethylenically unsaturated polymerizable monomers, or salts thereof; wherein the second monomer composition (B) is different from the first monomer composition (A).

[0092] Any of the monomers of (A) described above may be used in the process. Likewise, any of the monomers of (B) described above may be used in the process.

[0093] The process may be carried out as a solution polymerization, a precipita- tion polymerization, a gel polymerization, or an inverse emulsion polymerization.

[0094] In some embodiments the process is carried out as a solution polymerization. In some embodiments the process is carried out as a precipitation polymerization. In some embodiments the process is carried out as a gel polymerization. In some embodiments the process is carried out as an inverse emulsion polymerization.

[0095] In some embodiments the reaction step of the process further comprises reacting: (C) a third monomer composition comprising one or more monomers that include an alkyl group containing 1 to 18 carbon atoms comprising a simple ester, a vinyl ester, an mono-allyl ether, or any combination thereof; with (A) and (B).

[0096] Any of the monomers of (C) described above may be used in the process.

[0097] The disclosed technology includes the use of the polymer described herein as, for example, a rheology modifier, a fixative, an emulsifier, or a builder. The disclosed technology also includes methods of using the polymer described herein as, for example, a rheology modifier, a fixative, an emulsifier, or a builder. In some embodiments the sulfonic polymers disclosed herein can have a number average molecule weight below 1MM depending on the final application. The sulfonic polymers could also have a weight average molecular weight of less than 10MM.

[0098] In one embodiment, the sulfonic polymers described herein can be employed for chelating ions of hardness (e.g., chelating or sequestering metal ions and the like) from a solution. Many applications in the personal and home care industry are subjected to liquids that contain ions of hardness, for example, hard water. The sulfonic polymers or solutions thereof can be employed as builders to improve detergent performance in, for example, household care products, water treatment products, automotive care, surface care, I&I and personal care products. Exemplary automotive care applications include, for example car washes, car protectants, car cleaners, car shampoos, and the like.

[0099] The sulfonic polymers can be used in home care, and institutional and industrial ("I&I") applications. Typical household and I&I products that may contain sulfonic polymers, include, without being limited thereto, fabric care products, such as laundry detergents (powder, liquid, gel, and unit doses) and fabric softeners (liquids or sheets), ironing sprays, dry cleaning aids, antiwrinkle sprays, stain and spot removers and the like; hard surface cleaners for the kitchen and bathroom and utilities and appliances employed or located therein, such as toilet bowl gels, tub and shower cleaners, hard water deposit removers, floor and tile cleaners, wall cleaners, floor and chrome fixture polishes, alkali-strippable vinyl floor cleaners, marble and ceramic cleaners, air freshener gels, liquid or powder cleaners for dishes (automatic and manual), and the like; disinfectant cleaners, such as toilet bowl and bidet cleaners, disinfectant hand soaps, room deodorizers, heavy duty hand soaps, cleaners and sanitizers, automotive cleaners and the like.

[0100] In an embodiment, the sulfonic polymers or solutions thereof are employed in automatic dish detergents. Such dish detergents can be in different forms, such as, for example, liquid, powder, gels, tablets and unit dose pouches. In another embodiment, the sulfonic polymers can be used in laundry detergents both in powder and liquid form.

[0101 ] Exemplary water treatment applications include, for example, water purification processes for potable & industrial uses, cooling water treatment, boiler water treatment, desalination (e.g., reverse osmosis, distillation), wastewater (e.g., municipal & industrial) treatment, and the like. In one preferred embodiment, the sulfonic polymers are used in water treatment applications as scale inhibitors and/or dispersants.

[0102] Exemplary personal care cleansers include but are not limited to shampoos (e.g., 2-in-l shampoos, conditioning shampoos, bodifying shampoos; moisturizing shampoos, temporary hair color shampoos, 3-in-l shampoos, anti-dandruff shampoos, hair color maintenance shampoos, acid (neutralizing) shampoos, salicylic acid shampoos, medicated shampoos, baby shampoos, and the like), and skin and body cleansers (e.g., moisturizing body washes, antibacterial body washes; bath gels, shower gels, liquid hand soaps, bar soaps, body scrubs, bubble baths, facial scrubs, foot scrubs, and the like). Similarly, the sulfonic polymer can be employed in pet and animal care applications. Exemplary pet and animal care cleansers include but are not limited to shampoos, medicated shampoos, conditioning shampoos (e.g., detangling, antistatic, grooming), and foaming shampoos.

[0103] Health care embodiments in which the instant polymers can be included are medical products, such as topical and non-topical pharmaceuticals, and devices. In the formulation of pharmaceuticals, a sulfonic polymer can be employed as a thickener and/or lubricant in such products as syrups, creams, pomades, gels, pastes, ointments, tablets, gel capsules, purgative fluids (enemas, emetics, colonics, and the like), suppositories, anti-fungal foams, eye products (ophthalmic products, such as eye drops, artificial tears, glaucoma drug delivery drops, contact lens cleaner, and the like), ear products (wax softeners, wax removers, otitis drug delivery drops, and the like), nasal products (drops, ointments, sprays, and the like), and wound care (liquid bandages, wound dressings, antibiotic creams, ointments, and the like), without limitation thereto.

[0104] Other health care embodiments relate to foot care products, such as kerato- lytic corn and callous removers, foot soaks, medicated foot products such as antifungal athlete's foot ointments, gels, sprays, and the like, as well as antifungal, anti- yeast, and antibacterial creams, gels, sprays, and ointments.

[0105] In addition, the instant polymers can be included in topical, ransdermal, and non-topical pharmaceutical applications, and devices as thickeners, spreading aids, suspending agents, and film formers in skin protective sprays, creams, lotions, gels, and sticks for in the formulation of insect repellants, itch relief agents, antiseptic agents, disinfectants, sun blocks, sun screens, skin tightening and toning agents, and in wart removal compositions, and the like.

[0106] In another pharmaceutical aspect, the sulfonic polymers can be employed in the manufacture of pharmaceutical dosage forms (e.g. tablets, caplets, capsules, and the like) for the controlled release and targeted delivery of active pharmacologi- cally active ingredients and medicaments to the stomach and gut. They can be employed as pharmaceutical excipients such as binders, enteric coatings, film formers and controlled release agents. They can be used alone or in combination with other controlled release and/or enteric polymers known in the pharmaceutical arts.

[0107] The sulfonic polymers described herein can also be employed as a rheolo- gy modifier and/or a fixative, or for purposes of emulsification in personal care, home care, health care, and I&I care compositions. While embodiments of the technology as a rheology modifier/fixative may be described in terms of a specific formulation, it is to be noted that the copolymers described herein as well as the ingredients and optional components disclosed herein can be formulated into personal care, home care, health care, and I&I care products for rheology/fixative modification as one of ordinary skill in the respective formulation art can readily determine.

[0108] There is no limitation as to the form of product in which the sulfonic polymers can be incorporated, so long as the purpose for which the product is used is achieved. For example, personal care and health care products containing the sulfonic polymer can be applied to the skin, hair, scalp and nails in the form of, without being limited thereto, gels, sprays (liquid or foam), emulsions (creams, lotions, pastes), liquids (rinses, shampoos), bars, ointments, suppositories, impregnated wipes, patches, and the like. Likewise, while the sulfonic polymers can be employed on their own, the sulfonic polymers can be employed in compositions with optional additional ingredients.

[0109] It is known that formulated compositions for personal care and topical, dermatological, health care, which are applied to the skin and mucous membranes for cleansing or soothing, are compounded with many of the same or similar physiologi- cally tolerable ingredients and formulated in the same or similar product forms, differing primarily in the purity grade of ingredient selected, by the presence of medicaments or pharmaceutically accepted compounds, and by the controlled conditions under which products may be manufactured. Likewise, many of the ingredients employed in products for households, and I&I are the same or similar to the forego- ing, differing primarily in the amounts and material grade employed. It is also known that the selection and permitted amount of ingredients also may be subject to governmental regulations, on a national, regional, local, and international level. Thus, discussion herein of various useful ingredients listed below may apply to personal care, health care products, household and I&I products and industrial applications.

[01 10] The choice and amount of ingredients in formulated compositions containing a sulfonic polymer as described herein will vary depending on the product and its function, as is well known to those skilled in the formulation arts. Formulation ingredients typically can include, but are not limited to, natural and synthetic soaps, solvents, surfactants (as cleaning agents, emulsifying agents, foam boosters, hy- drotropes, solubilizing agents, and suspending agents), non-surfactant suspending agents, anti-redeposition aids, brighteners, fillers (e.g., sodium carbonate, sodium sulfate, sodium silicate and the like), deflocculating agents, enzymes and enzyme stabilizing agents, radical scavengers, corrosion inhibitors, salts, emulsifiers, conditioning agents (emollients, humectants, moisturizers, and the like), fixatives, film- formers, protectants, binders, builders, chelating agents, chelators, co-chelators, antimicrobial agents, antifungal agents, antidandruff agents, abrasives, adhesives, absorbents, dyes, deodorant agents, antiperspirant agents, opacifying and pearlescing agents, antioxidants, preservatives, propellants, spreading aids, sunscreen agents, sunless skin tanning accelerators, ultraviolet light absorbers, pH adjusting agents, botanicals, hair colorants, oxidizing agents, reducing agents, bleaching agents, pigments, physiologically active agents, anti-inflammatory agents, topical anesthet- ics, bacteriacides, fragrance and fragrance solubilizers, and the like, in addition to ingredients previously discussed that may not appear herein. An extensive listing of substances and their conventional functions and product categories appears in the INCI Dictionary, generally, and in Vol. 2, Sections 4 and 5 of the Seventh Edition, in particular, incorporated herein by reference.

[01 11 ] With respect to detergent composition, any cleaning ingredient in addition to builders can be used as part of the detergent product. The levels given are weight per cent and refer to the total composition (excluding the enveloping water-soluble material, in the case of unit dose forms having a wrapper or enveloping material). Detergent compositions can contain a phosphate builder or be free of phosphate builder and comprise one or more detergent active components which may be selected from bleach, bleach activator, bleach catalyst, surfactants, alkalinity sources, polymer, dying aids, anti-corrosion agents (e.g. sodium silicate) and care agents. Particularly suitable cleaning components for use herein include a builder compound, a bleach, an alkalinity source, a surfactant, an a ti-scalmg polymer for example, a polymer, an enzyme and an additional bleaching agent.

Enzymes

[01 12] The compositions can include enzymes. As used herein, enzymes mean any enzyme having a cleaning, stain removing or otherwise beneficial effect in a detergent composition. Preferred enzymes are hydrolases such as proteases, amylases and lipases. Highly preferred for dishwashing are amylases and/or proteases, including both current commercially available types and improved types. Enzymes are normally incorporated in the instant detergent compositions at levels sufficient to provide a "cleaning-effective amount". The term "cleaning-effective amount" refers to any amount capable of producing a cleaning, stain removal or soil removal effect on substrates such tableware.

[01 13] The compositions herein can comprise: from about 0.00] % to about 20%, preferably from about 0.005%» to about 10%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.

Proteases

[01 14] In some compositions a mixture of two or more proteases may be used. A mixture of proteases can contribute to an enhanced cleaning across a broader temperature and/or substrate range and provide superior shine benefits, especially when used in conjunction with the sulfonic polymer.

[01 15] Suitable proteases for use in combination with the sulfonic polymers include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62). Suitable proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred . Chemically or genetically modified mutants are included. The protease may be a serine protease, in one aspect, an alkaline microbial protease or a chymotrypsin or trypsin-iike protease. Examples of neutral or alkaline proteases include:

(a) subtilisins (EC 3.4.21.62), especially those derived from Bacillus, such as Bacillus lentus, B. alkalophilus, B. subtiiis, B. amyloiiquefaciens, Bacillus pumilus and Bacillus gibsonii described in U.S. Patent No. 6,312,936 B l , U.S. Patent No.

5,679,630, U.S. Patent No. 4,760,025, and U.S. Patent Application No. 2009/0170745 Al . (b) trypsin-like or chymotrypsin- like proteases, such as trypsin (e.g. , of porcine or bovine origin), the Fusarium protease described in U.S. Patent No. 5,288,627 and the chymotrypsin proteases derived from Cellumonas described in U.S. Patent Application No. 2008/0063774A1 .

(c) metal!oproteases, especially those derived from Bacil lus amyloliquefaciens described in U.S. Patent Application No. 2009/0263882 Al and U.S. Patent Application No. 2008/029361 OA 1. Suitable commercially available protease enzymes include those sold under the trade names Alcalase®, Savinase®, Pri- mase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Ovozyme®, Neu- trase®, Everlase® and Esperase® by Novozymes A/S (Denmark), those sold under the tradename Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excel lase® and Purafect OXP® by Genencor International (now Danisco US Inc.), and those sold under the tradename Opticlean® and Optimase® by Solvay Enzymes, those available from Henkel/ emira, namely BLAP (sequence shown in Figure 29 of US Patent No. 5,352,604 with the following mutations S99D + S 101 R + S 103A + V1 G4I + G159S, hereinafter referred to as BLAP), BLAP R (BLAP with S3T + V4I + VI 99M + V205I + L217D), BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V1 99M + V205I + L21 7D) - all from Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin with mutations A230V + S256G + S259N) from Kao. In one aspect, commercial proteases selected from the group consisting of Properase®, Purafect®, Ovozyme®, Everlase®, Savinase®, Excellase® and FN3® are employed.

Amylases

[01 16] Amylase enzymes are additional enzymes that are useful in detergent compositions. Suitable amylases include those described in U.S. Patent Application No. 2009/0233831 Al and U.S. Patent Application No. 2009/0314286A1. Suitable commercially available amylases for use herein include STAINZYME®, STAI ZYME PLUS®, STAINZYME ULTRA® and NATALASE® (Novozymes A/S) and Spezyme Xtra™ and Powerase™. STAINZYME PLUS® and Powerase™ may be particularly useful.

Cellulases [01 17] In one aspect, the compositions can comprise a cellulase enzyme. This composition provides excellent results in terms of not only cleaning of the fabric, dishware/tableware but also in terms of cleaning of the machines such as, dishwasher.

[01 18] Cellulase enzymes include microbial-derived endoglucanases exhibiting endo-beta-l,4-glucanase activity (E.C. 3.2.1.4), including a bacterial polypeptide endogenous to a member of the genus Bacillus which has a sequence of at least 90%, 94%, 97% and even 99% identity to the amino acid sequence SEQ ID NO:2 in US Patent No. 7, 141 ,4()3B2) and mixtures thereof. Suitable commercial ly avai lable cellulases for use herein include Celluzyme®, Celiuclean®, Whitezyme® (Novo- zymes A/S) and Puradax HA® (Genencor international - now Danisco US Inc.). Other Additional enzymes

[01 19] Other additional enzymes suitable for use in the compositions can comprise one or more enzymes selected from the group comprising hemicellulases, cellobiose dehydrogenases, peroxidases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and mixtures thereof.

[0120] In one aspect, such additional enzyme may be selected from the group consisting of lipases, including "first cycle lipases" comprising a substitution of an electrically neutral or negatively charged amino acid with R or K at any of positions 3, 224, 229, 231 and 233 on the wild-type of Humicola Lanuginosa, whose sequence is shown as SEQ ID No 1 in pages 5 and 6 of U.S. Patent 6,939,702 Bl, in one aspect. a variant comprising T231 and N233R mutations. One such variant is sold under the tradename Lipex® (Novozymes A/S, Bagsvaerd, Denmark).

Enzyme stabi lizer components

[0121 ] Suitable enzyme stabilizers include oligosaccharides, polysaccharides and inorganic divalent metal salts, such as alkaline earth metal salts, especially calcium salts. Chlorides and sulphates are may be particularly suitable with calcium chloride, in one aspect, being an especially suitable calcium salt. Examples of suitable oligosaccharides and polysaccharides, such as dextrins, can be found in U.S. PATENT APPLICATION NO. 2008/0004201 Al. In case of aqueous compositions comprising protease, a reversible protease inhibitor, such as a boron compound, including borate and 4-formyl phenyl boronic acid or a tripeptide aldehyde, can be added to further improve stability.

[0122] The purpose of an enzyme stabilizing system is to protect the enzymes in the composition between the time the composition is manufactured and the time the composition is used. It is preferred that the enzyme activity remains between about 60% and 100%, more preferably between about 70% and 100%), more preferably about 80% and 100%. In one embodiment, the stabilized enzyme is a protease and the enzyme activity is of such protease.

[0123] The enzyme stabilizing system can be any stabilizing system which can be compatible with the detersive enzyme and with the xanthan gum thickener - thereby excluding boric acid, borax (sodium tetraborate decahydrate) and alkali metal borates. Such stabilizing systems can comprise calcium ion, glycerin, propylene glycol, short chain carboxylic acid and mixtures thereof.

Bleach

[0124] Inorganic and organic bleaches are suitable cleaning actives for use herein. Inorganic bleaches include perhydrate salts such as perborate, percarbonate, perphos- phate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. Alternatively, the salt can be coated. Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for use herein. The percarbonate is most preferably incorporated into the products in a coated form which provides in-product stability. A suitable coating material providing in product stability comprises mixed salt of a water-soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in US Patent No. 4, 105,827. The weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 :200 to 1 :4, from 1 :99 to 1 :9, or from 1 :49 to 1 : 19. In one aspect, the mixed salt is a sodium sulphate and sodium carbonate which has the general formula Na₂S0₄. .Na₂CQ₃ wherein n is from 0.1 to 3, from 0.2 to 1.0 or from 0.2 to 0.5. Another suitable coating material providing in product stability, comprises sodium silicate of Si0₂:Na₂0 ratio from 1.8: 1 to 3.0: 1 , or 1 .8: 1 to 2.4: 1 , and/or sodium metasiiicate, in one aspect, applied at a level of from 2%» to 10%, (normally from 3% to 5%) of Si0₂ by weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating. Coatings that contain silicate and borate salts or boric acids or other inorganics are also suitable.

[0125] Other coatings which contain waxes, oils, fatty soaps can also be used advantageously within the sulfonic polymers.

[0126] Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility herein.

[0127] Typical organic bleaches are organic peroxy acids including diacyl and tetraacyiperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid. Dibenzoyl peroxide is a preferred organic peroxyacid herein. Mono- and diperazelaic acid, mono- and diperbrassylic acid, and naphthaloylaminoperoxicaproic acid are also suitable herein.

[0128] The diacyl peroxide, especially dibenzoyl peroxide, should typically be present in the form of particles having a weight average diameter of from about 0.1 to about 100 microns, from about 0.5 to about 30 microns, or from about 1 to about 10 microns. In one aspect, at least about 25%, at least about 50%, at least about 75%, or at least about 90%, of the particles are smaller than 10 microns, or smaller than 6 microns. Diacyl peroxides within the above particle size range have also been found to provide better stain removal especial ly from plastic dishware, while minimizing undesirable deposition and filming during use in automatic dishwashing machines, than larger diacyl peroxide particles. The optimum diacyl peroxide particle size thus allows the formulator to obtain good stain removal with a low level of diacyl peroxide, which reduces deposition and filming.

[0129] Further typical organic bleaches include the peroxy acids, particular examples being the alkylperoxy acids and the arylperoxy acids. Preferred representa- lives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as al- kylperoxybenzoic acids, but also peroxy-anaphthoic acid and magnesium monoper- phthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzami doperoxycaproic acid, N- nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1 , 12-diperoxycarboxylic acid, ! ,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane- 1 ,4-dioic acid, N,N- terephthaloyldi(6-aminopercaproic acid).

[0130] Formulations may comprise bleaches and if appropriate bleach activators. Bleaches are subdivided into oxygen bleaches and chlorine bleaches. Use as oxygen bleaches is found by alkali metal perborates and hydrates thereof, and also alkali metal percarbonates. Preferred bleaches in this context are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate. Likewise useable as oxygen bleaches are persulfates and hydrogen peroxide. Typical oxygen bleaches are also organic peracids such as perbenzoic acid, peroxyalpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoper- oxycaproic acid, 1 , 12-diperoxydodecanedioic acid, 1 ,9-diperoxyazelaic acid, di- peroxoisophthalic acid or 2-decyldiperoxybutane- 1 ,4-dioic acid. In addition, for example, the following oxygen bleaches may also find use in the detergent formulation: cationic peroxy acids which are described in the patent applications U.S. Patent No. 5,422,028, U.S. Patent No. 5,294,362 and U.S. Patent No. 5,292,447; sul- fonylperoxy acids which are described in the patent application U.S. Patent No. 5,039,447. Oxygen bleaches are used in amounts of generally from 0.5 to 30% by weight, preferably of from 1 to 20% by weight, more preferably of from 3 to 15% by weight, based on the overall detergent formulation. Chlorine bleaches and the combi- nation of chlorine bleaches with peroxidic bleaches may likewise be used. Known chlorine bleaches are, for example, l ,3-dichloro-5,5-dimethylhydantoin, N- chlorosulfamide, chloramine T, dichloramine T, chloramine B, Ν,Ν'- dichlorobenzoylurea, dichloro-p-toluenesulfonamide or trichloroethylamine. Preferred chlorine bleaches are sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate or sodium dichloroisocyanurate. Chlorine bleaches are used in amounts of generally from 0.1 to 20% by weight, preferably of from 0.2 to 10% by weight, more preferably of from 0.3 to 8% by weight, based on the overall detergent formulation. In addition, small amounts of bleach stabilizers, for example phosphonates, borates, metaborates, metasilicates or magnesium salts, may be added. They are described in the patent applications U.S. Patent No.8,262,804.

[0131 ] Although any chlorine bleach compound may be employed in the compositions with the sulfonic polymers, such as dichloro-isocyanurate, dichloro-dimethyl hydantoin, or chlorinated TSP, alkali metal or alkaline earth metal, e.g. potassium, lithium, magnesium and especially sodium, hypochlorite is preferred. The composition should contain sufficient amount of chlorine bleach compound to provide 0.2 to 4.0% by weight of avai lable chlorine, as determined, for example by acidification of 100 parts of the composition with excess hydrochloric acid. A solution containing 0.2 to 4.0% by w^reight of sodium hypochlorite contains or provides roughly the same percentage of available chlorine. 0.8 to 1.6% by weight of available chlorine is especially preferred. For example, sodium hypochlorite (NaOCL) solution of from 1 1 to 13% available chlorine in amounts of 3 to 20%, preferably 7 to 12%., can be advantageously used.

Bleach activators

[0132] Bleach activators are typically organic peracid precursors that enhance the bleaching action in the course of cleaning at temperatures of 60° C and below. Bleach activators suitable for use herein include compounds which, under perhydroi- ysis conditions, give aliphatic peroxoyearboxylie acids having from 1 to 10 carbon atoms, in particular from 2 to 4 carbon atoms, and/or optionally substituted perbenzo- ic acid. Suitable substances bear O-acyl and/or N~ acyl groups of the number of carbon atoms specified and/or optionally substituted benzoyl groups. Preference is given to polyacylated aikylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular l,5-diacetyl-2,4- dioxohexahydro- 1,3,5-triazine (DADHT), acylated glycoluriis, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran and also triethylacetyi citrate (TEAC). Bleach activators if included in the automatic dishwashing detergent compositions containing the sulfonic polymers are in a level of from about 0.1% to about 10%, or from about 0.5% to about 2% by weight of the total composition.

Bleach catalyst

[0133] Bleach catalysts preferred for use herein include the manganese triazacv- clononane and related complexes (US-A-4246612, US-A-5227084); Co, Cu, Mn and Fe bispyridylamine and related complexes (US-A-51 1461 1); and pentamine acetate cobalt(III) and related complexes(US-A-4810410). A complete description of bleach catalysts suitable for use herein can be found in USP 6,599,871 , pages 34, line 26 to page 40, line 16. Bleach catalyst if included in the detergent compositions with the sulfonic polymer are in a level of from about 0.1 % to about 10%, or from about 0.5% to about 2% by weight of the total composition.

Builders

[0134] In addition to the copolymers described herein as a primary builder, other cobuilders suitable to be included in the compositions herein to assist in controlling mineral hardness and dispersancy, with the exception of phosphate builders. Inorgan- ic as well as organic builders can be used. One embodiment employing the sulfonic polymers relates to a gel detergent composition, wherein the builder can be selected from the group consisting of carbonate builders, polycarboxylate compounds, citrate, methyl glycine diacetic acid and/or salts thereof, glutamatic diacetic acid and/or salts thereof and mixtures thereof.

[0135] Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973. Various grades and types of sodium carbonate and sodium sesquicarbonate can be used, certain of which are particularly useful as carriers for other ingredients, especially: detersive surfactants.

[0136] Organic detergent builders suitable for suitable for use with the sulfonic polymers include, but are not restricted to, a wide variety of polycarboxylate compounds.

[0137] Preferred phosphate builders include mono-phosphates, di-phosphates, tri- poiyphosphates or oligomeric-poylphosphates are used. The alkali metal salts of these compounds are preferred, in particular the sodium salts. An especially preferred builder is sodium tripolyphosphate (STPP).

[0138] Other useful detergency bui lders include the ether hydroxypolycarbox- ylates, copolymers of maleic anhydride w^rith ethylene or vinyl methyl ether, 1 , 3, 5- trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various I alkali metal, ammonium and substituted ammonium salts of poiyacetic acids such as ethylenediaminetetraacetic acid and nitriiotriacetic acid, as well as polycarboxylates such as me Mi tic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1 ,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

[0139] Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), builders suitable herein due to their availability from renewable re- sources and their biodegradability.

[0140] Methyl glycine diacetic acid and/or salts thereof (MGDA) may also be utilized as builders in the present composition. A preferred MGDA compound is a salt of methyl glycine diacetic acid. Suitable salts include the di ammonium salt, the dipotassium salt and, preferably, the disodium salt.

[0141 ] Glutamatic diacetic acid and/or salts thereof (GLDA) may also be utilized as builders in the present composition. A preferred GLDA compound is a salt of glutamic diacetic acid. Suitable salts include the diammonium salt, the dipotassium salt and, preferably, the disodium salt.

[0142] Chelating Agents - The compositions herein can also optionally contain one or more transition-metal selective sequestrants, "chelants" or "co-chelating agents", e.g., iron and/or copper and/or manganese chelating agents. Chelating agents suitable for use herein can be selected from the group consisting of aminocarbox- ylates, polyfunctionally-substituted aromatic chelating agents, and mixtures thereof. Commercial chelating agents for use herein include the DEQUEST™ series, and chelants from Monsanto, DuPont, and Nalco, Inc.

[0143] Formulations may comprise other co-builders. It is possible to use water- soluble and water-insoluble builders, whose main task consists in binding calcium and magnesium. The other builders used may be, for example: low molecular weight carboxylic acids and salts thereof, such as alkali metal citrates, in particular anhy- drous trisodium citrate or trisodium citrate dihydrate, alkali metal succinates, alkali metal malonates, fatty acid sulfonates, oxydisuccinate, alkyl or alkenyl disuccinates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate diacetate, a-hydroxypropionic acid; oxidized starches, oxidized polysaccharides; homo- and copolymeric polycarboxylic acids and salts thereof, such as polyacrylic acid, polymethacrylic acid, copolymers of maleic acid and acrylic acid; graft polymers of monoethylenically unsaturated mono- and/or dicarboxylic acids on monosaccharides, oligosaccharides, polysaccharides or polyaspartic acid; ammopolycarboxylates and polyaspartic acid; phosphonates such as 2-phosphono-l ,2,4-butanetricarboxylic acid, aminotri-(methylenephosphonic acid), l -hydroxyethylene(l , l -diphosphonic acid), ethylenediaminetetrameth- ylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid or diethylenetriaminepentamethylenephosphonic acid; silicates such as sodium disili- cate and sodium metasilicate; water-insoluble builders such as zeolites and crystalline sheet silicates.

[0144] In addition, formulations may comprise one or more complexing agents. Preferred complexing agents are selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxy- ethylethylenediaminetriacetic acid, and methylglycinediacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenedia- minedisuccinic acid, aspartic acid diacetic acid, and salts thereof.

[0145] One class of optional compounds for use herein includes chelating agents or mixtures thereof in combination with the sulfonic polymers. Chelating agents can be incorporated in the compositions herein in amounts ranging from 0.0% to 10.0% by weight of the total composition, preferably from 0.01 % to 5.0%.

[0146] Suitable phosphonate chelating agents for use herein may include alkali metal ethane 1 -hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino ami- notri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP). The phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities. Preferred phosphonate chelating agents to be used herein are diethy- lene triamine penta methylene phosphonate (DTPMP) and ethane 1 -hydroxy diphos- phonate (HEDP). Such phosphonate chelating agents are commercially available from Italmatch Chemicals under the trade name DEQUEST™.

[0147] Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. Patent No. 3,812,044, issued May 21 , 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisul- fobenzenes such as l ,2-dihydroxy-3,5-disulfobenzene.

[0148] Co-builders for use herein include phosphate builders and phosphate free builders. If present, builders are used in a level of from 5% to 60%, from 10% to 50%, or even from 10% to 50% by weight of the detergent composition. In some embodiments the detergent product comprises a mixture of phosphate and non- phosphate builders.

Drying aids

[0149] In another embodiment, detergent compositions containing the sulfonic polymers comprises a drying aid. By "drying aid" herein is meant an agent capable of decreasing the amount of water left on washed items, in particular in plastic items that are more prone to be wet after the washing process due to their hydrophobic nature. Suitable drying aids include polyesters, especially anionic polyesters derived from terephthalic acid, 5-sulphoisophthalic acid or a salt of 5-sulphoisophthalic, ethyleneglycol or polyethyleneglycol, propyleneglvcoi or polypropyleneglycol, and, polyalkyleneglycol monoalkylethers, optionally together with further monomers with 3 to 6 functionalities which are conducive to polycondensation, specifical ly acid, alcohol or ester functionalities. Suitable polyesters to use as drying aids are disclosed in WO 2008/1 10816 and preferably have one or more of the following properties:

(a) a number average molecular weight of from about 800 Da to about 25,000 Da, or from about 1 ,200 Da to about 12,000 Da.

(b) a softening point greater than about 40°C from about 41 °C to about 200°C, or even 80°C to about 150°C;

(c) a solubility greater than about 6% by weight in water of 3 ° German hardness at 200°C.

[0150] At 30°C the solubility will typically be greater than about 8%> by weight, at 40°C and 50°C , the solubility will typically be greater than about 40% by as measured in water of 3 ° German hardness.

[0151 ] Other suitable drying aids include specific polycarbonate-, polyurethane- and/or polyurea- polyorganosiloxane compounds or precursor compounds thereof of the reactive cyclic carbonate and urea type, as described in U.S. PATENT APPLICATION NO. 2010/0041574 Al and U.S. PATENT APPLICATION NO. 2010/0022427 Al. Improved drying can also be achieved by use of non-ionic surfac- ta ts, such as:

(a) R¹0-[CH₂Cil(CH₃)01_x[CH₂CH₂0]_y[CH₂CH(CH₃)0]_zCH₂CH(OH)-R², in which R ' represents a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof and R~ represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, x and z represent integers from 0 to 40, and y represents a integer of at least 15, or from 15 to 50. See for example as in WO 2009/033972; or

(b) O-i CJ ίί 1 [ί Κ ^! )() ] Ι < Ί (} i_i::K ί H I !( R ^j }() J^ ^'i 0 )- ' where R is a branched or unbranched alkyl radical having 8 to 16 carbon atoms, R^a and R^l independently of one another, are hydrogen or a branched or unbranched alkyl radical having 1 to 5 carbon atoms, R^z is an unbranched alkyl radical having 5 to 17 carbon atoms; 1 and n are independently of one another, an integer from 1 to 5 and m is an integer from 13 to 35, as described in U.S. PATENT APPLICATION NO. 2008/016721.

[0152] Examples of suitable materials include Plurafac LF731 or Plurafac LF- 7319 (BASF) and the Dehy quart® CSP and Poly quart* range (BASF).

[0153] In one aspect, detergent compositions containing the sulfonic polymers can comprise from about 0.1% to about 10%, from about 0.5% to about 5% and especially from about 1 % to about 4% by weight of the composition of a drying aid. Metal care agents

[0154] Metal care agents may prevent or reduce the tarnishing, corrosion or oxidation of metals, including aluminium, stainless steel and non-ferrous metals, such as silver and copper. Suitable examples include one or more of the following:

(a) benzatriazoles, including benzotriazole or bis-benzotriazole and substituted derivatives thereof. Benzotriazole derivatives are those compounds in which the available substitution sites on the aromatic ring are partially or completely substituted. Suitable substituents include linear or branch-chain Ci-C₂o- alkyl groups and hydroxy l, thio, phenyl or halogen such as fluorine, chlorine, bromine and iodine.

(b) metal salts and complexes chosen from the group consisting of zinc, manganese, titanium, zirconium, hafnium, vanadium, cobalt, gallium and cerium salts and/or complexes, the metals being in one of the oxidation states II, III, IV, V or VI. In one aspect, suitable metal salts and/or metal complexes may be chosen from the group consisting of Mn(II) sulphate, Mn(II) citrate, Mn(II) stearate, Mn(II) acetylacetonate, K₂TiF6, K₂ZrF6, C0SO4, Co(N03)₂ and Ce(N0₃)₃, zinc salts, for example zinc sul- phate, hydrozincite or zinc acetate.;

(c) silicates, including sodium or potassium silicate, sodium disilicate, sodium metasilicate, crystalline phyllosilicate and mixtures thereof. Further suitable organic and inorganic redox-active substances that act as silver/copper corrosion inhibitors are disclosed in USP 5,888,954.

[0155] In one aspect, detergent compositions containing the sulfonic polymers can comprise from 0.1% to 5%, from 0.2% to 4% or from 0.3% to 3% by weight of the total composition of a metal care agent.

[0156] The corrosion inhibitors used may, for example, be silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotria- zoles, the alky lamino triazoles and the transition metal salts or complexes. Particular preference is given to using benzotriazole and/or alkylaminotriazole. In addition, active chlorine-containing agents which can distinctly reduce the corrosion of the silver surface frequently find use in detergent formulations. In chlorine-free detergents, preference is given to using oxygen- and nitrogen-containing organic redox- active compounds such as di- and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol and derivatives of these compound classes. Salt- and complex-type inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce frequently also find use. Preference is given in this context to the transition metal salts which are selected from the group of the manganese and/or cobalt salts and/or complexes, more preferably from the group of the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, and of manganese sulfate. It is likewise possible to use zinc compounds or bismuth compounds or sodium silicate to prevent corrosion on the ware.

[0157] The formulations can also contain one or more material care agents which are effective as corrosion inhibitors and/or anti-tarnish aids.

Fillers

[0158] Fillers enable the adjustment of the active matter in the detergent to the doses used. Filler products include sodium sulphate in powders, water and solvents in liquids.

Silicates

[0159] Suitable silicates are sodium silicates such as sodium disilicate, sodium metasilicate and crystallme phyllosilicates. Silicates if present are at a level of from about 1% to about 20%, or from about 5% to about 15% by weight of the automatic dishwashing detergent composition. Unit Dose

[0160] In one aspect, detergent compositions containing the sulfonic polymers can be in unit dose form. Detergent products in unit dose form include tablets, capsules, sachets, pouches, pods, etc. The detergent compositions may he in a form of liquid, gel or powder. In one aspect, for use herein are tablets wrapped with a water-soluble film and water-soluble pouches. The weight of the composition can be from about 10 to about 25 grams, from about 12 to about 24 grams or even from 14 to 22 grams. These weights are extremely convenient for detergent product dispenser fit. In the cases of unit dose products having a water-soluble material enveloping the detergent composition, the water-soluble material is not considered as part of the composition. In one aspect, the unit dose form is a water-soluble pouch (i.e., w^rater- soluble film enveloping detergent composition), in one aspect, a multicompartment pouch having a plurality of films forming a plurality of compartments. This configuration contributes to the flexibility and optimization of the composition. It allows for the separation and controlled release of different ingredients. In one aspect, one compartment contains detergent composition in solid form and another compartment contains detergent composition in liquid form.

[0161 ] In one aspect, the films of these two compartments have different dissolution profiles, allowing the release of the same or different agents at different times. For example, the agent from one compartment (first compartment) can be delivered early in the washing process to help with soil removal and a second agent from another compartment (second compartment) can be delivered at least two minutes, or even at least five minutes later than the agent from the first compartment.

[0162] A multi-compartments pack is formed by a plurality of water-soluble enveloping materials which form a plurality of compartments, one of the compartments would contain the automatic detergent composition, another compartment can contain a liquid composition, the liquid composition can be aqueous (i.e. comprises more than 10% of water by weight of the liquid composition) and the compartment can be made of warm water soluble material. In some embodiments the compartment comprising the dishwashing detergent composition is made of cold water soluble material. It allows for the separation and controlled release of different ingredients. In other embodiments all the compartments are made of warm water soluble material. [0163] While the sulfonic polymers disclosed herein can be employed for rheology control themselves, compositions containing the sulfonic polymers can be formulated in combination with one or more auxiliary rheology modifiers and thickeners. Suitable rheology modifiers and thickeners include synthetic and semi-synthetic rheology modifiers. Exemplary synthetic rheology modifiers include acrylic based polymers and copolymers. One class of acrylic based rheology modifiers are the carboxyl functional alkali-swellable and alkali-soluble thickeners (ASTs) produced by the free-radical polymerization of acrylic acid alone or in combination with other ethylenically unsaturated monomers. The polymers can be synthesized by sol- vent/precipitation as well as emulsion polymerization techniques. Exemplary synthetic rheology modifiers of this class include homopolymers of acrylic acid or methacrylic acid and copolymers polymerized from one or more monomers of acrylic acid, substituted acrylic acid, and salts and C₁ -C30 alkyl esters of acrylic acid and substituted acrylic acid. As defined herein, the substituted acrylic acid contains a substituent positioned on the alpha and/or beta carbon atom of the molecule, wherein in one aspect the substituent is independently selected from Ci_₄ alkyl, -CN, and - COOH. Optionally, other ethylenically unsaturated monomers such as, for example, styrene, vinyl acetate, ethylene, butadiene, acrylonitrile, as well as mixtures thereof can be copolymerized into the backbone. The foregoing polymers are optionally crosslinked by a monomer that contains two or more moieties that contain ethylenic unsaturation. In one aspect, the crosslinker is selected from a polyalkenyl polyether of a polyhydric alcohol containing at least two alkenyl ether groups per molecule. Other exemplary crosslinkers are selected from allyl ethers of sucrose and allyl ethers of pentaerythritol, and mixtures thereof. These polymers are more fully described in U.S. Patent No. 5,087,445; U.S. Patent No. 4,509,949; and U.S. Patent No. 2,798,053 herein incorporated by reference.

[0164] In one aspect, the AST rheology modifier or thickener is a crosslinked homopolymer polymerized from acrylic acid or methacrylic acid and is generally referred to under the INCI name of Carbomer. Commercially available Carbomers include Carbopol^® polymers 934, 940, 941 , 956, 980 and 996 available from Lubrizol Advanced Materials, Inc. In a further aspect, the rheology modifier is selected from a crosslinked copolymer polymerized from a first monomer selected from one or more monomers of acrylic acid, substituted acrylic acid, salts of acrylic acid and salts of substituted acrylic acid and a second monomer selected from one or more C 10-C30 alkyl acrylate esters of acrylic acid or methacrylic acid. In one aspect, the monomers can be polymerized in the presence of a steric stabilizer such as disclosed in U.S. Patent No. 5,288,814, which is herein incorporated by reference. Some of the forgo- ing polymers are designated under INCI nomenclature as Acrylates/C 10-30 Alkyl Acrylate Crosspolymer and are commercially available under the trade names Carbo- pol^® 1342 and 1382, Carbopol^® Ultrez 20 and 21 , Carbopol^® ETD 2020 and Pemu- len^® TR-1 and TR-2 from Lubrizol Advanced Materials, Inc.

[0165] In another aspect, the auxiliary rheology modifier can be a crosslinked, linear poly(vinyl amide/acrylic acid) copolymer as disclosed in U.S. Patent No. 7,205,271 , the disclosure of which is herein incorporated by reference.

[0166] Another class of optional synthetic rheology modifiers and thickeners suitable for use with the sulfonic polymers includes the hydrophobically modified ASTs, commonly referred to as hydrophobically modified alkali-swellable and alkali- soluble emulsion (HASE) polymers. Typical HASE polymers are free radical addition polymers polymerized from pH sensitive or hydrophilic monomers (e.g., acrylic acid and/or methacrylic acid), hydrophobic monomers (e.g., C 1-C30 alkyl esters of acrylic acid and/or methacrylic acid, acrylonitrile, styrene), an "associative monomer", and an optional crosslinking monomer. The associative monomer comprises an ethylenically unsaturated polymerizable end group, a non-ionic hydrophilic midsection that is terminated by a hydrophobic end group. The non-ionic hydrophilic midsection comprises a polyoxyalkylene group, e.g., polyethylene oxide, polypropylene oxide, or mixtures of polyethylene oxide/polypropylene oxide segments. The terminal hydrophobic end group is typically a C8-C40 aliphatic moiety. Exemplary aliphatic moieties are selected from linear and branched alkyl substituents, linear and branched alkenyl substituents, carbocyclic substituents, aryl substituents, aralkyl substituents, arylalkyl substituents, and alkylaryl substituents. In one aspect, associative monomers can be prepared by the condensation (e.g., esterification or etheri- fication) of a polyethoxylated and/or polypropoxylated aliphatic alcohol (typically containing a branched or unbranched C8-C40 aliphatic moiety) with an ethylenically unsaturated monomer containing a carboxylic acid group (e.g., acrylic acid, methacrylic acid), an unsaturated cyclic anhydride monomer (e.g., maleic anhydride, itaconic anhydride, citraconic anhydride), a monoethylenically unsaturated monoiso- cyanate (e.g., α,α-dimethyl-m-isopropenyl benzyl isocyanate) or an ethylenically unsaturated monomer containing a hydroxyl group (e.g., vinyl alcohol, allyl alcohol). Polyethoxylated and/or polypropoxylated aliphatic alcohols are ethylene oxide and/or propylene oxide adducts of a monoalcohol containing the C8-C40 aliphatic moiety. Non-limiting examples of alcohols containing a C8-C40 aliphatic moiety are capryl alcohol, iso-octyl alcohol (2-ethyl hexanol), pelargonic alcohol (1-nonanol), decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetyl alcohol, cetearyl alcohol (mixture of C₁₆-C₁₈ monoalcohols), stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, montanyl alcohol, melissyl, lacceryl alcohol, geddyl alcohol, and C2-C20 alkyl substituted phenols (e.g., nonyl phenol), and the like.

[0167] Exemplary HASE polymers are disclosed in U.S. Patent Nos. 3,657, 175; 4,384,096; 4,464,524; 4,801 ,671 ; and 5,292,843, which are herein incorporated by reference. In addition, an extensive review of HASE polymers is found in Gregory D. Shay, Chapter 25, "Alkali-Swellable and Alkali-Soluble Thickener Technology A Review", Polymers in Aqueous Media - Performance Through Association, Advances in Chemistry Series 223, J. Edward Glass (ed.), ACS, pp. 457-494, Division Polymeric Materials, Washington, DC (1989), the relevant disclosures of which are incorporated herein by reference. Commercially available HASE polymers are sold under the trade names, Aculyn^® 22 (INCI Name: Acrylates/Steareth-20 Methacrylate Copolymer), Aculyn^® 44 (INCI Name: PEG-150/Decyl Alcohol/SMDI Copolymer), Aculyn 46^® (INCI Name: PEG-150/Stearyl Alcohol/SMDI Copolymer), and Aculyn^® 88 (INCI Name: Acrylates/Steareth-20 Methacrylate Crosspolymer) from Rohm & Haas, and Novethix™ L-10 (INCI Name: Acrylates/Beheneth-25 Methacrylate Copolymer) from Lubrizol Advanced Materials, Inc.

[0168] In another embodiment, acid swellable associative polymers can be used with the sulfonic polymer. Such polymers generally have cationic and associative characteristics. These polymers are free radical addition polymers polymerized from a monomer mixture comprising an acid sensitive amino substituted hydrophilic monomer (e.g., dialkylamino alkyl (meth)acrylates or (meth)acrylamides), an associative monomer (defined hereinabove), a lower alkyl (meth)acrylate or other free radically polymerizable comonomers selected from hydroxyalkyl esters of (meth)acrylic acid, vinyl and/or allyl ethers of polyethylene glycol, vinyl and/or allyl ethers of polypropylene glycol, vinyl and/or allyl ethers of polyethylene gly- col/polypropylene glycol, polyethylene glycol esters of (meth)acrylic acid, polypropylene glycol esters of (meth)acrylic acid, polyethylene glycol/polypropylene glycol esters of (meth)acrylic acid), and combinations thereof. These polymers can option- ally be crosslinked. By acid sensitive is meant that the amino substituent becomes cationic at low pH values, typically ranging from about 0.5 to about 6.5. Exemplary acid swellable associative polymers are commercially available under the trade name Structure^® Plus (INCI Name: Acrylates/Aminoacrylates/C10-C30 Alkyl PEG-20 Itaconate) from Akzo Nobel, and Carbopol^® Aqua CC (INCI Name: Poly aery lates-1 Crosspolymer) from Lubrizol Advanced Materials, Inc. In one aspect, the acid swellable polymer is a copolymer of one or more C 1-C5 alkyl esters of (meth)acrylic acid, C₁ -C4 dialkylamino Ci-C₆ alkyl methacrylate, PEG/PPG-30/5 allyl ether, PEG 20-25 C 10-C30 alkyl ether methacrylate, hydroxy C₂-C6 alkyl methacrylate cross- linked with ethylene glycol dimethacrylate. Other useful acid swellable associative polymers are disclosed in U.S. Patent No. 7,378,479, the disclosure of which is herein incorporated by reference.

[0169] Hydrophobically modified alkoxylated methyl glucoside, such as, for example, PEG- 120 Methyl Glucose Dioleate, PEG- 120 Methyl Glucose Trioleate, and PEG-20 Methyl Glucose Sesquistearate, available from Lubrizol Advanced Materials, Inc., under the trade names, Glucamate^® DOE- 120, Glucamate™ LT, and Glucamate™ SSE 20, respectively, are also suitable as auxiliary rheology modifiers.

[0170] Polysaccharides obtained from tree and shrub exudates, such as gum Arabic, gum gahatti, and gum tragacanth, as well as pectin; seaweed extracts, such as alginates and carrageenans (e.g., lambda, kappa, iota, and salts thereof); algae ex- tracts, such as agar; microbial polysaccharides, such as xanthan, gellan, and wellan; cellulose ethers, such as ethylhexylethylcellulose, hydroxybutylmethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and micro- fibrous cellulose such as disclosed in U.S. Patent No. 7,776,807; polygalactoman- nans, such as fenugreek gum, cassia gum, locust bean gum, tara gum, and guar gum; starches, such as corn starch, tapioca starch, rice starch, wheat starch, potato starch and sorghum starch can also be employed in the compositions herein as suitable auxiliary thickeners, suspending agents, and rheology modifiers. [0171 ] The auxiliary rheology modifiers, when employed, can be used alone or in combination and typically are used in an amount ranging from about 0.1 wt. % to about 8 wt. % in one aspect, from about 0.3 wt. % to about 3 wt. % in another aspect, and from about 0.5 wt. % to about 2 wt. % in further aspect, based on the total weight of a composition containing the sulfonic polymer.

[0172] The auxiliary anionic thickeners are simultaneously neutralized with alkaline pH adjusting agents that are utilized to neutralize the polymers described hereins of the technology.

[0173] Combinations of powdered polymers conforming to the INCI designation of Carbomer or powdered copolymers conforming to INCI designation Acry- lates/C 10-30 Alkyl Acrylate Crosspolymer with the polymers described herein could give superior gel and styling properties such as, for example, clarity, yield value, short flow, and viscosity profiles. Increasing the fixative polymer level in a hair styling composition does not adversely affect gel consistency (e.g., clarity, shear thinning, and yield value is maintained) and viscosity profiles. Consequently, the styling performance of a hair styling composition can be enhanced without deleteri- ously affecting gel properties and viscosity.

[0174] By the term "powder" is meant that the polymer is in solid form (not an emulsion) and passes through a 20 mesh screen (U.S. Standard Mesh). The term powder is defined in Hawley's Condensed Chemical Dictionary, 14^th Edition, 2001 , John Wiley & Sons, Inc., New York, on page 921 , which is herein incorporated by reference for the disclosure thereof.

[0175] Polymers conforming to the INCI designation Carbomer are homopoly- mers of (meth)acrylic acid crosslinked with allyl ether of pentaerythritol, an allyl ether of sucrose, or an allyl ether of propylene.

[0176] Polymers conforming to the INCI designation Acrylates/C 10-30 Alkyl Acrylate Crosspolymer are copolymers of C 10-C30 alkyl acrylates with one or more monomers selected from (meth)acrylic acid, C₁-C₄ alkyl esters of (meth)acrylic acid, and combinations thereof, crosslinked with an allyl ether of sucrose or an allyl ether of pentaerythritol.

[0177] If desired, the viscosity of the hair styling gel and personal care compositions of the technology can be adjusted. The viscosity of the hair styling gels should be effective to provide hair fixative properties to the gels. Where the viscosity of the polymer is too high, the gels and films formed therefrom exhibit unacceptable haziness. Where the viscosity is too low, properties such as stiffness and humidity resistance, gel, and gel aesthetics are adversely affected. Higher molecular weight fixative polymers give gels of higher viscosities, while lower molecular weight fixative polymers give gels with lower viscosities. The viscosity profiles of the polymers in the gels can also be adjusted by controlling the degree of neutralization (DN) of the fixative polymer. Higher DN values result in higher gel viscosities, while lesser degrees of neutralization result in lower gel viscosities. In one aspect of the technology, the DN of the fixative/thickener polymer ranges from about 50% to about 70%. In another aspect of the technology, the DN of the polymer is >70%. In still another aspect, for high clarity gels a DN of >70% can be utilized. In addition, a salt such as sodium chloride or sodium sulfate can be added to the composition to lower the viscosity to a desired level.

[0178] The alkaline neutralizing agents that can be used to neutralize the poly- mers described herein fixative/thickeners of the present technology and the optional anionic auxiliary thickeners include inorganic bases, organic bases, and combinations thereof. Examples of inorganic bases include but are not limited to the alkali metal hydroxides (especially lithium, sodium, potassium, magnesium, and ammonium), and alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phos- phate, sodium pyrophosphate, and the like; and mixtures thereof. Examples of organic bases include but are not limited to triethanolamine (TEA), diisopropanola- mine, triisopropanolamine, aminomethyl propanol (2-Amino-2-methyl-l -propanol), dodecylamine, cocamine, oleamine, morpholine, triamylamine, triethylamine, tetrakis(hydroxypropyl)ethylenediamine, L-arginine, methyl glucamine, isopropyla- mine, aminomethyl propanol, tromethamine (2-amino 2-hydroxymethyl-l,3- propanediol), and PEG- 15 cocamine. Alternatively, other alkaline materials can be used alone or in combination with the above mentioned inorganic and organic bases.

[0179] The polymers of the technology can be formulated solely in water as the solvent, or the diluent system can be a blend of polar organic solvent and water. Typically, the organic solvent will be selected from an alcohol, a ketone, an ether, and mixtures thereof. In one aspect, suitable solvents are low boiling alcohols selected from C₁-C₄ linear or branched alcohols and denatured alcohols. Exemplary polar solvents include, but are not limited to, ethanol, propanol, isopropanol, butanol, acetone, methyl ethyl ketone, dimethylether, and dimethoxymethane. Another exemplary polar solvent includes methyl acetate. Mixtures of the individual solvents disclosed above are also contemplated. In one aspect, the amount of solvent ranges from about 1 wt.% to about 40 wt.%, from about 5 wt.% to about 25 wt.% in another aspect, and from about 6 wt.% to about 10 wt.% in a further aspect of the technology, based on the total wt. of the composition.

[0180] With respect to personal care formulations, the polymers of the technology can include an optional auxiliary fixative agent. Suitable optional auxiliary hair fixative polymers include natural and synthetic polymers such as, for example, polyacrylates, polyvinyls, polyesters, polyurethanes, polyamides, modified cellulose, starches, and mixtures thereof. These polymers can be nonionic, anionic, cationic and amphoteric in nature and include without limitation one or more of polyoxyeth- ylenated vinyl acetate/crotonic acid copolymers, vinyl acetate crotonic acid copolymers, vinyl methacrylate copolymers, monoalkyl esters of poly(methyl vinyl ether (PVM)/maleic anhydride (MA)), such as, for example, ethyl, butyl and isopropyl esters of PVM/MA copolymer acrylic acid/ethyl acrylate/N-tert-butyl-acrylamide terpolymers, and poly (methacrylic acid/acrylamidomethyl propane sulfonic acid), acrylates copolymer, octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, acrylates/octylacrylamide copolymer, vinyl acetate (VA)/crotonates/vinyl neodeanoate copolymer, poly(N-vinyl acetamide), poly(N-vinyl formamide), corn starch modified, sodium polystyrene sulfonate, polyquaterniums such as, for example, Polyquaternium-4, Polyquaternium-10, Polyquaternium-1 1 , Polyquaternium-24, Polyquaternium-28, Polyquaternium-29, Polyquaternium-32, Polyquaternium-34, Polyquaternium-37, Polyquaternium-39, Polyquaternium-44, Polyquaternium-46, Polyquaternium-47, Polyquarternium-55, Polyquaternium-68, Polyquaternium-69, Polyquaternium-87, polyether-1 , VA/acrylates/lauryl methacrylate copolymer, adipic acid/dimethylaminohydroxypropyl diethylene AMP/acrylates copolymer, methacrylol ethyl betaine/acrylates copolymer, acrylamide/sodium acryloyldimethyltau- rate/acrylic acid, polyvinylpyrrolidone (PVP), vinyl pyrrolidone (VP)/dimethylaminoethylmethacrylate copolymer, acrylic acid/VP crosspolymer, VP/methacrylamide/vinyl imidazole copolymer, VP/dimethylaminopropylamine (DMAPA) acrylates copolymer, VP/vinylcaprolactam/DMAPA acrylates copolymer, vinyl caprolactam/VP/dimethylaminoethyl methacrylate copolymer, VA/butyl male- ate/isobornyl acrylate copolymer, VA/crotonates copolymer, acrylate/acrylamide copolymer, VA/crotonates/vinyl propionate copolymer, VP/vinyl acetate/vinyl propionate terpolymers, VP/vinyl acetate copolymer, VP/acrylates copolymer, VA/crotonic acid/vinyl proprionate, acrylates/acrylamide, acrylates/octylacrylamide, acrylates/hydroxyacrylates copolymer, acrylates/hydroxyesteracrylates copolymer, acrylates/stereth-20 methacrylate copolymer, tert-butyl aery late/acry lie acid copolymer, diglycol/cyclohexanedimethanol/isophthalates/sulfoisophthalates copolymer, VA/alkylmaleate half ester/N- substituted acrylamide terpolymers, vinyl caprolac- tam/VP/ methacryloamidopropyl trimethylammonium chloride terpolymer, methacry- lates/acrylates copolymer/amine salt, polyvinylcaprolactam, hydro xypropyl guar, poly (methacrylic acid/acrylamidomethyl propane sulfonic acid (AMPSA), ethylene- carboxamide (EC)/AMPSA/methacrylic acid (MAA), poylurethane/acrylate copolymers and hydroxypropyl trimmonium chloride guar, acrylates crosspolymer, AMP- acrylates/allyl methacrylate copolymer, polyacrylate-14, poly aery late -2 crosspoly- mer, acrylates/lauryl acrylate/stearyl acrylate/ethylamine oxide methacrylate copolymer, methacryloyl ethyl betaines/methacrylates copolymer, polyurethane/acrylates copolymer, pyrrolidone carboxylic acid salt of chitosan, chitosan glycolate, cationic polygalactomannans, such as, for example, quaternized derivatives of guar, such as, for example, guar hydroxypropyl trimmonium chloride, cassia hydroxypropyl trim- monium chloride and hydroxypropyl guar hydroxypropyl trimmonium chloride. Many of the foregoing polymers are referred to by their INCI nomenclature set forth in the International Cosmetic Ingredient Dictionary published by the Cosmetic, Toiletry, and Fragrance Association, Washington D.C. Other suitable auxiliary fixative polymers are disclosed in U.S. Patent No. 7,205,271 , the disclosure of which is herein incorporated by reference.

[0181 ] The auxiliary fixative polymer typically comprises about 0.01 wt. % to about 8 wt. % in one aspect, from about 0.1 wt. % to about 5 wt. % in another aspect, and about 0.2 wt. % to about 3 wt. % in a further aspect of the total weight of the composition.

[0182] In one aspect of the technology, the viscosity of a hair styling gel composition or personal care composition comprising a fixative/thickener polymer of the technology with and without the optional Carbomers or powdered Acrylates/C 10-30 Alkyl Acrylate copolymers in water is from about 8,000 to about 80,000 mPa-s in one aspect, from about 10,000 to about 60,000 mPa-s in another aspect, from about 12,000 to about 40,000 mPa-s in a further aspect, and from about 15,000 to about 30,000 mPa-s in a still further aspect, as measured on a Brookfield viscometer with a No. 5 or 6 spindle at 20 rpm, and at ambient room temperature.

[0183] In addition to other rheology modifiers, compositions prepared with the sulfonic polymers can contain other chelating agents to help stabilize the compositions against the deleterious effects of metal ions and UV radiation (e.g., sunlight). When utilized, suitable chelating agents include EDTA (ethylene diamine tetraacetic acid) and salts thereof such as disodium EDTA, citric acid and salts thereof, cy- clodextrins, and the like, and mixtures thereof. The chelating agents typically comprise about 0.001 wt. % to about 3 wt. % in one aspect, from about 0.01 wt. % to about 2 wt. % in another aspect, and from about 0.01 wt. % to about 1 wt. % in a further aspect of the total weight of the compositions of the present technology.

[0184] The polymers of the present technology can be formulated with or without at least one surfactant.

Surfactants

[0185] In one aspect, an embodiment of the present technology relates to stable, aqueous compositions comprising the polymer rheology modifier/fixative and a surfactant(s). Suitable surfactants include anionic, cationic, amphoteric, and non- ionic surfactants, as well as mixtures thereof. Such compositions are useful in personal care cleansing compositions that contain various components such as substantially insoluble materials requiring suspension or stabilization (e.g., a silicone, an oily material, a pearlescent material, aesthetic and cosmeceutical beads and particles, gaseous bubbles, exfoliants, and the like). The technology further relates to the incorporation of acidic materials before or after the addition of an alkaline material to reduce the pH of the composition without negatively impacting the viscosity, rheological, and clarity properties of the composition.

[0186] The anionic surfactant can be any of the anionic surfactants known or previously used in the art of aqueous surfactant compositions. Suitable anionic surfactants include but are not limited to alkyl sulfates, alkyl ether sulfates, alkyl sulphonates, alkaryl sulfonates, a-olefin-sulphonates, alkylamide sulphonates, alkarylpolyether sulphates, alkylamidoether sulphates, alkyl monoglyceryl ether sulfates, alkyl monoglyceride sulfates, alkyl monoglyceride sulfonates, alkyl succinates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl ether sulphosuccinates, alkyl amidosul- fosuccinates; alkyl sulphoacetates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alkyl amidoethercarboxylates, N-alkylamino acids, N-acyl amino acids, alkyl peptides, N-acyl taurates, alkyl isethionates, carboxylate salts wherein the acyl group is derived from fatty acids; and the alkali metal, alkaline earth metal, ammonium, amine, and triethanolamine salts thereof.

[0187] In one aspect, the cation moiety of the forgoing salts is selected from sodium, potassium, magnesium, ammonium, mono-, di- and triethanolamine salts, and mono-, di-, and tri-isopropylamine salts. The alkyl and acyl groups of the foregoing surfactants contain from about 6 to about 24 carbon atoms in one aspect, from 8 to 22 carbon atoms in another aspect and from about 12 to 18 carbon atoms in a further aspect and may be unsaturated. The aryl groups in the surfactants are selected from phenyl or benzyl. The ether containing surfactants set forth above can contain from 1 to 10 ethylene oxide and/or propylene oxide units per surfactant molecule in one aspect, and from 1 to 3 ethylene oxide units per surfactant molecule in another aspect.

[0188] Examples of suitable anionic surfactants include sodium, potassium, lithium, magnesium, and ammonium salts of laureth sulfate, trideceth sulfate, myreth sulfate, C 12-C 13 pareth sulfate, C₁₂-C₁₄ pareth sulfate, and C₁₂-C₁₅ pareth sulfate, ethoxylated with 1 , 2, and 3 moles of ethylene oxide; sodium, potassium, lithium, magnesium, ammonium, and triethanolamine lauryl sulfate, coco sulfate, tridecyl sulfate, myrstyl sulfate, cetyl sulfate, cetearyl sulfate, stearyl sulfate, oleyl sulfate, and tallow sulfate, disodium lauryl sulfosuccinate, disodium laureth sulfosuccinate, sodium cocoyl isethionate, sodium C₁₂-C₁₄ olefin sulfonate, sodium laureth-6 car- boxylate, sodium methyl cocoyl taurate, sodium cocoyl glycinate, sodium myristyl sarcocinate, sodium dodecylbenzene sulfonate, sodium cocoyl sarcosinate, sodium cocoyl glutamate, potassium myristoyl glutamate, triethanolamine monolauryl phosphate, and fatty acid soaps, including the sodium, potassium, ammonium, and triethanolamine salts of a saturated and unsaturated fatty acids containing from about 8 to about 22 carbon atoms.

[0189] The cationic surfactants can be any of the cationic surfactants known or previously used in the art of aqueous surfactant compositions. Suitable classes of cationic surfactants include but are not limited to alkyl amines, alkyl imidazolines, ethoxylated amines, quaternary compounds, and quaternized esters. In addition, alkyl amine oxides can function as a cationic surfactant at a low pH.

[0190] Alkylamine surfactants can be salts of primary, secondary and tertiary fatty C 12-C22 alkylamines, substituted or unsubstituted, and substances sometimes referred to as "amidoamines". Non-limiting examples of alkylamines and salts thereof include dimethyl cocamine, dimethyl palmitamine, dioctylamine, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated stearylamine, dihydroxy ethyl stearylamine, arachidylbehenylamine, dimethyl lauramine, stearylamine hydrochlo- ride, soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloride, and amodimethicone (INCI name for a silicone polymer and blocked with amino functional groups, such as aminoethylamino propylsiloxane).

[0191 ] Non-limiting examples of amidoamines and salts thereof include stear- amido propyl dimethyl amine, stearamidopropyl dimethylamine citrate, palmitami- dopropyl diethylamine, and cocamidopropyl dimethylamine lactate.

[0192] Non-limiting examples of alkyl imidazoline surfactants include alkyl hydroxyethyl imidazoline, such as stearyl hydroxyethyl imidazoline, coco hydroxy- ethyl imidazoline, ethyl hydroxymethyl oleyl oxazoline, and the like.

[0193] Non-limiting examples of ethyoxylated amines include PEG- cocopolyamine, PEG- 15 tallow amine, quaternium-52, and the like.

[0194] Among the quaternary ammonium compounds useful as cationic surfactants, some correspond to the general formula: (R⁵R⁶R⁷R⁸N ) E^", wherein R⁵, R⁶, R⁷,

Q

and R are independently selected from an aliphatic group having from 1 to about 22 carbon atoms, or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having 1 to about 22 carbon atoms in the alkyl chain; and E^" is a salt-forming anion such as those selected from halogen, (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfate, and alkylsulfate. The aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, ester linkages, and other groups such as amino groups. The longer chain aliphatic groups, e.g., those of about 12 carbons, or higher, can be saturated or unsaturated. In one aspect, the aryl groups are selected from phenyl and benzyl.

[0195] Exemplary quaternary ammonium surfactants include, but are not limited to cetyl trimethylammonium chloride, cetylpyridinium chloride, dicetyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, dieicosyl dimethyl ammonium chloride, didocosyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium acetate, behenyl trimethyl ammonium chloride, benzalkonium chloride, benzethonium chloride, and di(coconutalkyl) dimethyl ammonium chloride, ditallowdimethyl ammonium chloride, di (hydro genated tallow) dimethyl ammonium chloride, di(hydrogenated tallow) dimethyl ammonium acetate, ditallowdimethyl ammonium methyl sulfate, ditallow dipropyl ammonium phosphate, and ditallow dimethyl ammonium nitrate.

[0196] At low pH, amine oxides can protonate and behave similarly to N-alkyl amines. Examples include, but are not limited to, dimethyl- dodecylamine oxide, oleyldi(2-hydroxyethyl) amine oxide, dimethyltetradecylamine oxide, di(2- hydroxy- ethyl)-tetradecylamine oxide, dimethylhexadecylamine oxide, behenamine oxide, cocamine oxide, decyltetradecylamine oxide, dihydroxyethyl C I 2- 15 alkoxypropyl- amine oxide, dihydroxyethyl cocamine oxide, dihydroxyethyl lauramine oxide, dihydroxyethyl stearamine oxide, dihydroxyethyl tallowamine oxide, hydrogenated palm kernel amine oxide, hydrogenated tallowamine oxide, hydroxyethyl hydroxy- propyl C 12-C15 alkoxypropylamine oxide, lauramine oxide, myristamine oxide, cetylamine oxide, oleamidopropylamine oxide, oleamine oxide, palmitamine oxide, PEG-3 lauramine oxide, dimethyl lauramine oxide, potassium trisphosphonomethyl- amine oxide, soyamidopropylamine oxide, cocamidopropylamine oxide, stearamine oxide, tallowamine oxide, and mixtures thereof.

[0197] Amphoteric or zwitterionic surfactants are molecules that contain acidic and basic moieties and have the capacity of behaving either as an acid or a base. Suitable surfactants can be any of the amphoteric surfactants known or previously used in the art of aqueous surfactant compositions. Exemplary amphoteric surfactant classes include but are not limited to amino acids (e.g., N-alkyl amino acids and N- acyl amino acids), betaines, sultaines, and alkyl amphocarboxylates.

[0198] Amino acid based surfactants suitable in the practice of the present tech- nology include surfactants represented by the formula:

wherein R represents a saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms or an acyl group containing a saturated or unsaturated hydrocarbon group having 9 to 22 carbon atoms, Y is hydrogen or methyl, Z is selected from hydrogen, -CH₃, -CH(CH₃)₂, -CH₂CH(CH₃)₂, -CH(CH₃)CH₂CH₃, -CH₂C₆H₅, -

CH₂C₆H₄OH, -CH₂OH, -CH(OH)CH₃, -(CH₂)₄NH₂,

-(CH₂)₃NHC(NH)NH₂, -CH₂C(0)0^~M⁺, -(CH₂)₂C(0)0^~M⁺. M is a salt forming cation. In one aspect, R¹⁰ represents a radical selected from a linear or branched C₁₀ to C₂₂ alkyl group, a linear or branched C₁₀ to C₂₂ alkenyl group, an acyl group represented by RⁿC(0)-, wherein R¹¹ is selected from a linear or branched C to C₂₂ alkyl group, a linear or branched C₉ to C₂₂ alkenyl group. In one aspect, M⁺ is selected from sodium, potassium, ammonium, and triethanolamine (TEA).

[0199] The amino acid surfactants can be derived from the alkylation and acyla- tion of a-amino acids such as, for example, alanine, arginine, aspartic acid, glutamic acid, glycine, isoleucine, leucine, lysine, phenylalanine, serine, tyrosine, and valine. Representative N-acyl amino acid surfactants are, but not limited to the mono- and di- carboxylate salts (e.g., sodium, potassium, ammonium and TEA) of N-acylated glutamic acid, for example, sodium cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium palmitoyl glutamate, sodium stearoyl glutamate, disodium cocoyl glutamate, disodium stearoyl glutamate, potassium cocoyl glutamate, potassium lauroyl glutamate, and potassium myristoyl glutamate; the carboxylate salts (e.g., sodium, potassium, ammonium and TEA) of N-acylated alanine, for example, sodium cocoyl alaninate, and TEA lauroyl alaninate; the carboxylate salts (e.g., sodium, potassium, ammonium and TEA) of N-acylated glycine, for example, sodium cocoyl glycinate, and potassium cocoyl glycinate; the carboxylate salts (e.g., sodium, potassium, ammonium and TEA) of N-acylated sarcosine, for example, sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate, sodium oleoyl sarcosinate, and ammonium lauroyl sarcosinate; and mixtures of the foregoing surfactants. [0200] The betaines and sultaines useful in the present technology are selected from alkyl betaines, alkylamino betaines, and alkylamido betaines, as well as the corresponding sulfobetaines (sultaines) represented by the formulas:

12 13

wherein R is a C7-C₂₂ alkyl or alkenyl group, each R independently is a C₁-C₄ alkyl group, R¹⁴ is a C₁-C5 alkylene group or a hydroxy substituted C₁-C5 alkylene group, n is an integer from 2 to 6, A is a carboxylate or sulfonate group, and M is a

12

salt forming cation. In one aspect, R is a Cn-C₁₈ alkyl group or a Cn-C₁₈ alkenyl group. In one aspect, R¹³ is methyl. In one aspect, R¹⁴ is methylene, ethylene or hydroxy propylene. In one aspect, n is 3. In a further aspect, M is selected from sodium, potassium, magnesium, ammonium, and mono-, di- and triethanolamine cations.

[0201] Examples of suitable betaines include, but are not limited to, lauryl betaine, coco betaine, oleyl betaine, cocohexadecyl dimethylbetaine, lauryl amidopropyl betaine, cocoamidopropyl betaine, and cocamidopropyl hydroxysultaine.

[0202] The alkylamphocarboxylates such as the alkylamphoacetates and alkylamphopropionates (mono- and disubstituted carboxylates) can be represented by the formula:

wherein R¹² is a C7-C22 alkyl or alkenyl group, R¹⁵ is -CH₂C(0)0^" M⁺, -CH₂CH₂C(0)0^~ M⁺, or -CH₂CH(OH)CH₂S0₃ ^" M⁺, R¹⁶ is a hydrogen or -CH₂C(0)0^" M⁺, and M is a cation selected from sodium, potassium, magnesium, ammonium, and mono-, di- and triethanolamine.

[0203] Exemplary alkylamphocarboxylates include, but are not limited to, sodium cocoamphoacetate, sodium lauroamphoacetate, sodium capryloamphoacetate, disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, and disodium capryloamphodipropionate.

[0204] The non-ionic surfactant can be any of the non-ionic surfactants known or previously used in the art of aqueous surfactant compositions. Suitable non-ionic surfactants include, but are not limited to, aliphatic (C₆-C₁₈) primary or secondary linear or branched chain acids, alcohols or phenols; alkyl ethoxylates; alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy moieties); block alkylene oxide condensates of alkyl phenols; alkylene oxide condensates of alkanols; and ethylene oxide/propylene oxide block copolymers. Other suitable non-ionic surfactants include mono- or dialkyl alkanolamides; alkyl polyglucosides (APGs); sorbitan fatty acid esters; polyoxyethylene sorbitan fatty acid esters; polyoxy ethylene sorbitol esters; polyoxyethylene acids, and polyoxyethylene alcohols. Other examples of suitable non-ionic surfactants include coco mono- or diethanolamide, coco glucoside, decyl diglucoside, lauryl diglucoside, coco diglucoside, polysorbate 20, 40, 60, and 80, ethoxylated linear alcohols, cetearyl alcohol, lanolin alcohol, stearic acid, glyceryl stearate, PEG- 100 stearate, laureth 7, and oleth 20.

[0205] In another embodiment, non-ionic surfactants include, but are not limited to, alkoxylated methyl glucosides such as, for example, methyl gluceth-10, methyl gluceth-20, PPG- 10 methyl glucose ether, and PPG-20 methyl glucose ether, available from Lubrizol Advanced Materials, Inc., under the trade names, Glucam^®

E10, Glucam^® E20, Glucam^® P10, and Glucam^® P20, respectively; and hydrophobically modified alkoxylated methyl glucosides, such as PEG 120 methyl glucose dioleate, PEG- 120 methyl glucose trioleate, and PEG-20 methyl glucose sesquistearate, available from Lubrizol Advanced Materials, Inc., under the trade names, Glucamate^® DOE-120, Glucamate™ LT, and Glucamate™ SSE-20, respectively, are also suitable. Other exemplary hydrophobically modified alkoxylated methyl glucosides are disclosed in United States Patent Nos. 6,573,375 and 6,727,357, the disclosures of which are hereby incorporated by reference in their entirety.

[0206] Other surfactants which can be utilized in the present technology are set forth in more detail in WO 99/21530, U.S. Patent No. 3,929,678, U.S. Patent No. 4,565,647, U.S. Patent No. 5,720,964, and U.S. Patent No. 5,858,948. In addition, suitable surfactants are also described in McCutcheon's Emulsifiers and Detergents (North American and International Editions, by Schwartz, Perry and Berch) which is hereby fully incorporated by reference.

[0207] While the amounts of the surfactant utilized in a composition comprising the polymer of the technology can vary widely depending on a desired application, the amounts which are often utilized generally range from about 1 % to about 80% by weight in one aspect, from about 3% to about 65%> weight in another aspect, from about 5% to about 30% by weight in a still another aspect, from about 6% to about 20%) by weight in a further aspect, and from about 8% to about 16%> by weight, based upon the total weight of the personal care, home care, heath care, and institutional and industrial care composition in which it is included.

[0208] In one aspect of the technology, the personal care, home care, health care and I&I care compositions of the technology comprise a polymer in combination with at least one anionic surfactant. In another aspect of the technology, the compositions comprise a polymer with at least one anionic surfactant and at least one amphoteric surfactant. In one aspect, the anionic surfactant is selected from alkyl sulfates, alkyl ether sulfates, alkyl sulphonates, alkaryl sulfonates, alkarylpolyether sulphates, and mixtures thereof wherein the alkyl group contains 10 to 18 carbon atoms, the aryl group is a phenyl, and the ether group contains 1 to 10 moles of ethylene oxide. Representative anionic surfactants include, but are not limited to, sodium and ammonium lauryl ether sulfate (ethoxylated with 1 , 2, and 3 moles of ethylene oxide), sodium, ammonium, and triethanolamine lauryl sulfate. [0209] In one aspect, the amphoteric surfactant is selected from an alkyl betaine, an alkylamino betaine, an alkylamido betaines, and mixtures thereof. Representative betaines include but are not limited to lauryl betaine, coco betaine, cocohexadecyl dimethylbetaine, cocoamidopropyl betaine, cocoamidopropylhyrdoxy sultaine, and mixtures thereof.

[0210] In one embodiment of the technology, the copolymers of the technology can be formulated in combination with derivatized and non-derivatized hydrocolloids obtained from natural sources such as, for example, polysaccharides obtained from tree, shrub, and fruit exudates, such as gum arabic, gum gahatti, and gum tragacanth, and pectin; seaweed extracts, such as alginates and carrageenans; algae extracts, such as agar; microorganism produced polysaccharides, such as xanthan, gellan, and wellan gums; cellulose ethers, such as ethylhexylethylcellulose (EHEC), hydroxybutylmethylcellulose (HBMC), hydroxyethylmethylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC), methyl cellulose (MC), carboxymethylcellulose (CMC), hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC) and cetyl hydroxyethylcellulose; polygalactomannan gums selected from fenugreek, cassia, locust bean, tara and guar; and mixtures thereof.

[021 1 ] By derivatized hydrocolloid is meant that the above mentioned hydrocolloids can be derivatized with a functionalization agent reactive with a functional group, e.g., a hydroxyl group, contained on the hydrocolloid backbone. For example, derivatives of the cellulose ethers containing quaternary ammonium groups can be made by reacting a cellulose ether, e.g., hydroxyethylcellulose, with an epoxide containing a trialkyl ammonium salt group, e.g., glycidyltrimethylammonium chloride, to give the corresponding quaternary substituted cellulose.

[0212] Derivatized hydrocolloids can also be made by quaternizing a polygalactomannan such as locust bean gum, cassia or guar with a quaternizing agent. Quaternized polygalactomannans can be made by reacting guar gum with a haloalkyl substituted quaternary ammonium compound, e.g., 4-chloro-2-butenyl trimethylammonium chloride. A process for producing derivatized polygalactomannan gums is described in U.S. Patent No. 4,031 ,307. [0213] When the above mentioned hydrocolloids are formulated into the compositions of the present technology the weight ratio of copolymer rheology modifier/fixative described herein to hydrocolloid(s) range from about 1 : 10 to about 10: 1 in one aspect, from about 2:8 to about 8:2 in another aspect, from about 2.5 :7.5 to about 7.5 :2.5 in a further aspect, from about 1 :5 to about 5 : 1 in another aspect, and from about 1 :2 to about 2: 1 in a still further aspect.

[0214] In one embodiment of the technology, compositions can be prepared by mixing the polymers described herein in water and neutralizing the polymer with an alkaline material to a desired degree of neutralization. The amount of polymer utilized in the composition ranges from about 0.1 wt.% to about 15 wt.% in one aspect, from about 0.5 wt.% to about 10 wt.% in another aspect, and from about 1 wt.% to about 5 wt. % in a further aspect, based on the weight of the total components in the composition. All polymer weight percents are based upon 100 percent total active polymer solids (T.S.). The polymer can be neutralized to a pH ranging from about 0.5 to about 12. The desired pH for the compositions of the present technology is obviously dependent upon the specific end product applications. Generally, personal care applications have a desired pH range of about 3 to about 1 1 , or from about 3.5 to about 10, or about 4 to about 9, or from about 5 to about 8. In some embodiments the pH can be about 6 to about 7 or from about 6.4 to about 7.5. Generally, home care applications have a desired pH range of about 1 to about 12 in one aspect, and from about 3 to about 10 in another aspect, depending on the desired end-use application. Compositions with the copolymer described herein can form clear formulations while maintaining desirable rheology properties (e.g., viscosity and yield values).

[0215] The pH of the compositions containing the polymers described herein can be adjusted with any combination of acidic and/or basic pH adjusting agents known to the art. The polymeric rheology modifiers of the disclosed technology are generally supplied in their acidic form. These polymers modify the rheology of a formulation through the neutralization of ionic groups (e.g., sulfonic acid groups) on the polymer with an alkaline material. Without wishing to be bound by theory, this causes ionic repulsion between like charged moieties along the backbone of the polymer and a three dimensional expansion of the polymer network, resulting in an increase in viscosity and other rheological properties. This is phenomenon is referred to in the literature as a "space filling" mechanism as compared to an associative thickening mechanism of the HASE polymers.

[0216] In one embodiment, compositions comprising the polymers of the technology can be acidified (pH reduction) without neutralizing the polymer. In another embodiment, compositions comprising the polymers can be neutralized with an alkaline material. In a further embodiment, compositions comprising the polymers of the technology can be neutralized subsequent to being acidified. In a still further embodiment, compositions comprising the polymers of the technology can be acidified subsequent to neutralization.

[0217] An alkaline material is incorporated to neutralize the polymer and can be referred to as a neutralizing agent or pH adjusting agent. Many types of neutralizing agents can be used in the present technology, including inorganic and organic bases, and combinations thereof. Examples of inorganic bases include but are not limited to the alkali metal hydroxides (especially sodium, potassium, and ammonium), and alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, and the like; and mixtures thereof. Examples of organic bases include, but are not limited to, triethanolamine (TEA), diisopropanolamine, triisopropanolamine, aminomethyl propanol, dodecylamine, cocamine, oleamine, morpholine, triamylamine, triethylamine, tetrakis(hydroxypropyl)ethylenediamine, L-arginine, aminomethyl propanol, tromethamine (2-amino 2-hydroxymethyl- 1 ,3 -propanediol), and PEG-15 cocamine. Alternatively, other alkaline materials can be used alone or in combination with the above-mentioned inorganic and organic bases. Such materials include surfactants, surfactant mixtures, pre-neutralized surfactants or materials that when combined in a composition containing a polymer of the technology is capable of neutralizing or partially neutralizing the carboxyl groups on the polymer backbone. Any material capable of increasing the pH of the composition is suitable.

[0218] Various acidic materials can be utilized as a pH adjusting agent in the present technology. Such acidic materials include organic acids and inorganic acids, for example, acetic acid, citric acid, tartaric acid, alpha-hydroxy acids, beta-hydroxy acids, salicylic acid, lactic acid, glycolic acid, and natural fruit acids, or inorganic acids, for example, hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid, phosphoric acid, and combinations thereof. As discussed above, the addition of the acidic pH adjusting agent can be incorporated before or after the addition of the basic pH adjusting agent in a desired composition. The addition of the acidic material after the addition of the alkaline neutralizing agents yields significantly improved rheological properties. This is discussed in greater detail under the "back acid" formulation technique below.

[0219] As with the alkaline pH adjusting agents, other acidic materials can be used alone or in combination with the above mentioned inorganic and organic acids. Such materials include materials which when combined in a composition containing the 1 polymer of the technology is capable of reducing the pH of the composition. It will be recognized by the skilled artisan that various of the acidic pH adjusting agents can serve more than one function. For example, acidic preservative compounds and acid based cosmeceutical compounds (e.g., alpha- and beta-hydroxy acids) not only serve their primary preservative and cosmeceutical functions, respectively, they can also be utilized to reduce or maintain the pH of a desired formulation.

[0220] Buffering agents can be used in the compositions of the technology. Suitable buffering agents include, but are not limited to, alkali or alkali earth metal carbonates, phosphates, bicarbonates, citrates, borates, acetates, acid anhydrides, succinates, and the like, such as sodium phosphate, sodium citrate, sodium acetate, sodium bicarbonate, and sodium carbonate.

[0221 ] The pH adjusting agent and/or buffering agent is utilized in any amount necessary to obtain and/or maintain a desired pH value in the composition.

Back Acid Formulation

[0222] The polymeric rheology modifiers of the present technology do not start to build substantial viscosity until a pH of about 5 or 6 is achieved. There are some Home and Personal Care applications, however, that require a pH of less than 6 for optimal and desired performance. This has limited the use of such polymers in such compositions. Additionally, it is difficult to even formulate stable applications at this lower pH range.

[0223] It has been found that if these compositions are raised to a near neutral or even alkaline pH and then subsequently reduced in pH, the viscosity and yield value generally remain unchanged or often actually increase. This formulating technique is referred to herein as "Back Acid" thickening or "Back Acid Addition". This formulating technique broadens the scope of application of the present polymers and now allows for formulation in the acidic pH regime. Additionally, the process of "Back Acid" thickening can also be used to further increase the viscosity and stability of compositions formulated in the slightly acidic and in the alkaline pH regime.

[0224] The one or more polymers of the technology can be formulated into a desired composition in any order during the formulation procedure. An alkaline material is added and mixed to increase the pH of the composition to at least about 5 in one aspect, to at least about 6 in another aspect, and most to at least about 6.5 in a further aspect. The alkaline material can be any compound that can neutralize the polymer to a specified pH. In one aspect, the alkaline material is selected from any of the alkaline pH adjusting agents described above, such as, for example, sodium hydroxide, potassium hydroxide, triethanolamine, or another fatty acid amine neutralizing agent commonly used in said applications. Alternatively, other alkaline materials can be used, such as surfactants. In one aspect, the pH can be adjusted to at least about 0.5, 1 , 1.5 or 2 pH units above the final target pH of the composition. In another aspect, the pH can be adjusted to at least 3, 4, or even 5 pH units above the final target pH of the composition. Subsequent to the pH adjustment with the alkaline material, an acidic material is added to reduce the pH of the composition to the desired target pH for the composition. In one aspect of the technology, the target pH ranges from about 3.5 to about 6, from about 4 to about 5.5 in another aspect, and from about 4.5 to 5 in a further aspect.

[0225] The material used to decrease the pH of the composition can be any acidic material. In one aspect, the acidic material is selected from any of the acidic pH adjusting agents described above, such as, for example, an organic acid, such as citric acid, acetic acid, alpha-hydroxy acid, beta-hydroxy acid, salicylic acid, lactic acid, glycolic acid, natural fruit acids, or combinations thereof. In addition, inorganic acids, for example, hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid, phosphoric acid, and combinations thereof can be utilized. Mixtures of organic acids and inorganic acids are also contemplated.

Auxiliary Solvents and Diluents

[0226] The personal care, home care, health care, and institutional care compositions containing the sulfonic polymers in combination with one or more of the foregoing active ingredients and/or with the one or more additives and/or adjuvants, conventionally or popularly included in personal care, health care, home care, and institutional care products discussed above can be prepared as water-free or water-based formulations, and formulations containing water-miscible auxiliary solvents and/or diluents, but are not limited thereto. Useful solvents commonly employed are typically liquids, such as water (deionized, distilled or purified), alcohols, fatty alcohols, polyols, and the like, and mixtures thereof. Non-aqueous or hydrophobic auxiliary solvents are commonly employed in substantially water-free products, such as nail lacquers, aerosol propellant sprays, or for specific functions, such as removal of oily soils, sebum, make-up, or for dissolving dyes, fragrances, and the like, or are incorporated in the oily phase of an emulsion. Non-limiting examples of auxiliary solvents, other than water, include linear and branched alcohols, such as ethanol, propanol, isopropanol, hexanol, and the like; aromatic alcohols, such as benzyl alcohol, cyclohexanol, and the like; saturated C₁₂ to C30 fatty alcohol, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and the like. Non-limiting examples of polyols include polyhydroxy alcohols, such as glycerin, propylene glycol, butylene glycol, hexylene glycol, C₂ to C₄ alkoxylated alcohols and C₂ to C₄ alkoxylated polyols, such as ethoxylated, propoxylated, and butoxylated ethers of alcohols, diols, and polyols having about 2 to about 30 carbon atoms and 1 to about 40 alkoxy units, polypropylene glycol, polybutylene glycol, and the like. Non-limiting examples of non-aqueous auxiliary solvents or diluents include silicones, and silicone derivatives, such as cyclomethicone, and the like, ketones such as acetone and methylethyl ketone; natural and synthetic oils and waxes, such as vegetable oils, plant oils, animal oils, essential oils, mineral oils, C₇ to C₄o isoparaffins, alkyl carboxylic esters, such as ethyl acetate, amyl acetate, ethyl lactate, and the like, jojoba oil, shark liver oil, and the like. Some of the foregoing non-aqueous auxiliary solvents or diluents may also be conditioners and emulsifiers.

Botanicals

[0227] Optionally, the compositions of the technology can contain botanical material extracts. Extracted botanical materials can include any water soluble or oil soluble material extracted from a particular plant, fruit, nut, or seed. Suitable botanical agents can include, for example, extracts from Echinacea (e.g., sp. angustifolia, purpurea, pallida), yucca glauca, willow herb, basil leaves, Turkish oregano, carrot root, grapefruit, fennel seed, rosemary, tumeric, thyme, blueberry, bell pepper, blackberry, spirulina, black currant fruit, tea leaves, such as for, example, Chinese tea, black tea (e.g., var. Flowery Orange Pekoe, Golden Flowery Orange Pekoe, Fine Tippy Golden Flowery Orange Pekoe), green tea (e.g., var. Japanese, Green Darjeeling), oolong tea, coffee seed, dandelion root, date palm fruit, gingko leaf, green tea, hawthorn berry, licorice, sage, strawberry, sweet pea, tomato, vanilla fruit, comfrey, arnica, centella asiatica, cornflower, horse chestnut, ivy, magnolia, oat, pansy, skullcap, seabuckthorn, white nettle, and witch hazel, and combinations thereof. Other botanical extracts include, for example, chlorogenic acid, glutathione, glycyrrhizin, neohesperidin, quercetin, rutin, morin, myricetin, absinthe, and chamomile. The botanical actives can be present in an amount ranging from about 0.1 wt.% to about 10 wt.% in one aspect, from about 0.5 wt.% to about 8 wt.% in another aspect, and from about 1 wt.% to about 5 wt.% in a further aspect, based of the total weight of the composition.

Cationic Polymers and Compounds

[0228] Cationic polymers and compounds are useful in compositions with the sulfonic polymers. Those of ordinary skill in the art will recognize that many of these cationic agents serve multiple functions. Typically, these agents are useful as conditioners (e.g., hair and skin), antistatic agents, fabric softening, and as antimicrobial agents. Cationic polymers can be synthetically derived or obtained by modifying natural polymers such as the cationically modified polysaccharides and polygalactomannans .

[0229] Representative cationic polymers include but are not limited to homopolymers and copolymers derived from free radically polymerizable acrylic or methacrylic ester or amide monomers. The copolymers can contain one or more units derived from acrylamides, methacrylamides, diacetone acrylamides, acrylic or methacrylic acids or their esters, vinyllactams such as vinyl pyrrolidone or vinyl caprolactam, and vinyl esters. Exemplary polymers include copolymers of acrylamide and dimethyl amino ethyl methacrylate quaternized with dimethyl sulfate or with an alkyl halide; copolymers of acrylamide and methacryloyl oxyethyl trimethyl ammonium chloride; the copolymer of acrylamide and methacryloyl oxyethyl trimethyl ammonium methosulfate; copolymers of vinyl pyrrolidone/dialkylaminoalkyl acrylate or methacrylate, optionally quaternized, such as the products sold under the name GAFQUAT™ by International Specialty Products Inc., Wayne, NJ; the dimethyl amino ethyl methacrylate/vinyl caprolactam/vinyl pyrrolidone terpolymers, such as the product sold under the trade name GAFFIX™ VC 713 by International Specialty Products Inc.; the vinyl pyrrolidone/methacrylamidopropyl dimethylamine copolymer, marketed under the trade name STYLEZE™ CC 10 available from International Specialty Products Inc.; and the vinyl pyrrolidone/quaternized dimethyl amino propyl methacrylamide copolymers such as the product sold under the trade name GAFQUAT™ HS 100 by International Specialty Products, Inc.

[0230] Cationic agents can also be selected from the quaternary polymers of vinyl pyrrolidone and vinyl imidazole such as the products sold under the trade name Luviquat^® (product designations FC 370, FC 550, Excellence, Style, and Ultracare); the quaternary polymers of vinyl pyrrolidone, acrylamide and vinyl imidazole such as the products sold under the trade name Luviquat^® (product designation Supreme), the quaternary polymers of vinyl capralactum, vinyl pyrrolidone and vinyl imidazole such as the products sold under the trade name Luviquat^® (product designation Hold), the quaternary polymers of vinyl pyrrolidone, vinyl imidazole, and diallyldimethyl ammonium chloride such as the products sold under the trade name Luviquat^® Sensation by BASF. Other cationic polymer agents that can be used in compositions with the sulfonic polymers include polyalkyleneimines such as polyethyleneimines, polymers containing vinyl pyridine or vinyl pyridinium units, condensates of polyamines and epichlorhydrins, quaternary polysaccharides, quaternary polyurethanes, quaternary silicones, and quaternary derivatives of chitin.

[0231 ] Non-limiting examples of quaternary ammonium compounds (monomeric and polymeric) useful as cationic agents with the sulfonic polymers include acetamidopropyl trimonium chloride, behenamidopropyl dimethylamine, behenamidopropyl ethyldimonium ethosulfate, behentrimonium chloride, behentrimonium methosulfate, cetethyl morpholinium ethosulfate, cetrimonium chloride, cocoamidopropyl ethyldimonium ethosulfate, dicetyldimonium chloride, dimethicone hydroxypropyl trimonium chloride, hydroxyethyl behenamidopropyl dimonium chloride, Silicone Quaternium-8, Quaternium-22, Quaternium-26, Quaternium-27, Quaternium-52, Quaternium-53, Quaternium-63, Quaternium-70, Quaternium-72, Quaternium-76, hydrolyzed collagen, PEG-2-cocomonium chloride, PPG-9 diethylmonium chloride, PPG-25 diethylmonium chloride, PPG-40 diethylmonium chloride, stearalkonium chloride, stearamidopropyl ethyl dimonium ethosulfate, steardimonium hydroxypropyl hydrolyzed wheat protein, steardimonium hydroxypropyl hydrolyzed collagen, wheat germamidopropalkonium chloride, wheat germamidopropyl ethyldimonium ethosulfate, Polyquaternium-1 , Polyquaternium-4, Polyquaternium-6, Polyquaternium-7, Polyquaternium-10, Polyquaternium-11 , Polyquaternium-15, Polyquarternium-16, Polyquaternium-22, Polyquaternium-24, Polyquaternium-28, Polyquaternium-29, Polyquaternium-32, Polyquaternium-33, Polyquaternium-35, Polyquaternium-37, Polyquaternium-39, Polyquaternium-44, Polyquaternium-46, Polyquaternium-47, Polyquaternium-52, Polyquaternium-53, Polyquarternium-55, Polyquaternium-59, Polyquaternium-61 , Polyquaternium-64, Polyquaternium-65, Polyquaternium-67, Polyquaternium-69, Polyquaternium-70, Polyquaternium-71 , Polyquaternium-72, Polyquaternium-73, Polyquaternium-74, Polyquaternium-76, Polyquaternium-77, Polyquaternium-78, Polyquaternium-79, Polyquaternium-80, Polyquaternium-81 , Polyquaternium-82, Polyquaternium-84, Polyquaternium-85, Polyquaternium-87, Polyquaternium-89, Polyquaternium-90, Polyquaternium-91 , Polyquaternium-92, Polyquaternium-94, Polyquaternium-95, Polyquaternium-96, PEG-2-cocomonium chloride; and mixtures thereof.

[0232] Other useful cationic polymers include the cationic polygalactomannans (e.g., quaternized derivatives of guar and cassia, such as, guar hydroxypropyl trimmonium chloride, hydroxypropyl guar hydroxypropyl trimmonium chloride, and cassia hydroxypropyl trimmonium chloride).

[0233] Cationic agents useful with the sulfonic polymers also include, but are not limited to, proteins and protein derivatives, amines, protonated amine oxides, betaines, and the like. Protein derivatives include cocodimonium hydroxypropyl hydrolyzed casein, cocodimonium hydroxypropyl hydrolyzed collagen, cocodimonium hydroxypropyl hydrolyzed hair keratin, cocodimonium hydroxypropyl hydrolyzed rice protein, cocodimonium hydroxypropyl hydrolyzed silk, cocodimonium hydroxypropyl hydrolyzed soy protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed silk amino acids, hydroxypropyl trimonium hydrolyzed collagen, hydroxypropyl trimonium hydrolyzed keratin, hydroxypropyl trimonium hydrolyzed silk, hydroxypropyl trimonium hydrolyzed rice bran, hydroxypropyl trimonium hydrolyzed soy protein, hydroxypropyl trimonium hydrolyzed vegetable protein, hydroxypropyl trimonium hydrolyzed wheat protein, hydrolyzed wheat protein, hydrolyzed sweet almond protein, hydrolyzed rice protein, hydrolyzed soy protein, hydrolyzed milk protein, hydrolyzed vegetable protein, hydrolyzed keratin, hydrolyzed collagen, hydrolyzed wheat gluten, potassium cocoyl hydrolyzed collagen, hydroxypropyl trimonium hydrolyzed collagen, cocodimonium hydroxypropyl hydrolyzed milk protein, lauryldimonium hydroxypropyl hydrolyzed wheat protein, lauryldimonium hydroxypropyl hydrolyzed collagen, keratin amino acids, collagen amino acids, soyethyldimonium ethosulfate, soyethyl morpholinium ethosulfate, and the like.

[0234] The monomeric quaternary ammonium compounds include, for example, alkylbenzyldimethyl ammonium salts, betaines, heterocyclic ammonium salts, and tetraalkylammonium salts. Long-chain (fatty) alkylbenzyldimethyl ammonium salts are utilized as conditioners, as antistatic agents, and as fabric softeners, discussed in more detail below.

[0235] Non-limiting examples of alkylbenzyldimethylammonium salts include, but are not limited to, stearalkonium chloride, benzalkonium chloride, Quaternium- 63, olealkonium chloride, didecyldimonium chloride, and the like. The betaine compounds include the alkylamidopropyl betaines and the alkylamidopropyl hydroxysultaines, as described in the formulas set forth previously above. Non- limiting examples of alkyl betaine compounds include oleyl betaine, coco-betaine, cocoamidopropyl betaine, coco-hydroxy sultaine, coco/oleamidopropyl betaine, coco-sultaine, cocoamidopropylhydroxy sultaine, and sodium lauramidopropyl hydro xyp ho staine .

[0236] The heterocyclic ammonium salts include the alkylethyl morpholinium ethosulfates, isostearyl ethylimidonium ethosulfate, and the alkylpyridinium chlorides. Non-limiting examples of heterocyclic ammonium salts include, but are not limited to, cetylpyridinium chloride, isostearylethylimidonium ethosulfate, and the like.

[0237] Non-limiting examples of tetraalkylammonium salts include cocamidopropyl ethyldimonium ethosulfate, hydroxyethyl cetyldimonium chloride, Quaternium-18, and cocodimonium hyroxypropyl hydrolyzed protein, such as hair keratin, and the like. [0238] A number of quaternary ammonium compounds are used as antistatic agents for fabric conditioning and fabric care. They include long-chain alkylated quaternary ammonium compounds such as dialkyldimethyl quaternary ammonium compounds, imidazoline quaternary compounds, amidoamine quaternary compounds, dialkyl ester quat derivatives of dihydroxypropyl ammonium compounds; dialkyl ester quat derivatives of methyltriethanol ammonium compounds, ester amide amine compounds, and diester quat derivatives of dimethyldiethanol ammonium chloride, as described in the review article by Whalley, "Fabric Conditioning Agents", HAPPI, pp. 55-58 (February 1995), incorporated herein by reference.

[0239] Non-limiting examples of dialkyldimethyl quaternary ammonium compounds, include N,N-dioleyl-N,N-dimethylammonium chloride, N,N-ditallowyl- Ν,Ν-dimethylammonium ethosulfate, N,N-di(hydrogenated-tallowyl)-N,N- dimethylammonium chloride, and the like. Non-limiting examples of imidazoline quaternary compounds include l -N-methyl-3-N-tallowamidoethylimidazolium chloride, 3 -methyl- l -tallowylamidoethyl-2-tallowylimidazolinium methylsulfate, and the like. Non-limiting examples of amidoamine quaternary compounds include N- alkyl-N-methyl-N,N-bis(2-tallowamidoethyl)ammonium salts where the alkyl group can be methyl, ethyl, hydroxyethyl, and the like. Non-limiting examples of dialkyl ester quat derivatives of dihydroxypropyl ammonium compounds include l ,2-ditallowoyloxy-3-N,N,N-trimethylammoniopropane chloride, 1 ,2-dicanoloyloxy- 3-N,N,N-trimethylammoniopropane chloride, and the like.

[0240] In addition, other types of long chain (e.g., natural oil and fatty acid- derived) alkylated quaternary ammonium compounds are suitable fabric softening agents. In one aspect, the long-chain alkyl groups are derived from tallow, canola oil, or from palm oil, however, other alkyl groups derived from soybean oil and coconut oil, for example, are also suitable, as are lauryl, oleyl, ricinoleyl, stearyl, and palmityl groups. Representative compounds include, but not limited, to N,N- di(alkyloxyethyl)-N,N-dimethylammonium salts such as N,N-di(tallowyloxyethyl)- Ν,Ν-dimethylammonium chloride, N,N-di(canolyloxyethyl)-N,N- dimethylammonium chloride, and the like; N,N-di(alkyloxyethyl)-N-methyl-N-(2- hydroxyethyl)ammonium salts such as N,N-di(tallowyloxyethyl)-N-methyl-N-(2- hydroxyethyl)ammonium chloride, N,N-di(canolyloxyethyl)-N-methyl-N-(2- hydroxyethyl)ammonium chloride, and the like; N,N-di(2-alkyloxy-2-oxoethyl)-N,N- dimethylammonium salts, such as N,N-di(2-tallowyloxy-2-oxoethyl)-N,N- dimethylammonium chloride, N,N-di(2-canolyloxy-2-oxoethyl)-N,N- dimethylammonium chloride, and the like; N,N-di(2- alkyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium salts, such as N,N-di(2- tallowyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium chloride, N,N-di(2- canolyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium chloride, and the like; N-(2-alkanoyloxy-2-ethyl)-N-(2-alkyloxy-2-oxoethyl)-N,N-dimethyl ammonium salts, such as N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxoethyl)-N,N- dimethyl ammonium chloride, N-(2-canoloyloxy-2-ethyl)-N-(2-canolyloxy-2- oxoethyl)-N,N-dimethyl ammonium chloride, and the like; N,N,N-tri(alkyloxyethyl)- N-methyl ammonium salts, such as N,N,N-tri(tallowyloxyethyl)-N-methylammonium chloride, N,N,N-tri(canolyloxyethyl)-N-methylammonium chloride, and the like; N- (2-alkyloxy-2-oxoethyl)-N-alkyl-N,N-dimethyl ammonium salts, such as N-(2- tallowyloxy-2-oxoethyl)-N-tallowyl-N,N-dimethyl ammonium chloride, N-(2- canolyloxy-2-oxoethyl)-N-canolyl-N,N-dimethyl ammonium chloride, and the like.

[0241 ] In another aspect, quaternary ammonium fabric softening compounds include N-methyl-N,N-bis(tallowamidoethyl)-N-(2-hydroxyethyl)ammonium methylsulfate and N-methyl-N,N-bis(hydrogenated-tallowamidoethyl)-N-(2- hydroxyethyl) ammonium methylsulfate, dialkyl esterquat derivatives of methyltriethanol ammonium salts such as the bis(acyloxyethyl)hydroxyethylmethylammonium methosulfate esterquats, and the like; and N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride, where the tallow chains are at least partially unsaturated.

[0242] In a further aspect, fabric softening agents include the well-known dialkyldimethyl ammonium salts such as N,N-ditallowyl-N,N-dimethyl ammonium methylsulfate, N,N-di(hydrogenated-tallowyl)-N,N-dimethyl ammonium chloride, N,N-distearyl-N,N-dimethyl ammonium chloride, N,N-dibehenyl-N,N- dimethylammonium chloride, N,N-di(hydrogenated tallow)-N,N-dimethyl ammonium chloride, N,N-ditallowyl-N,N-dimethyl ammonium chloride, N,N-distearyl-N,N- dimethyl ammonium chloride, N,N-dibehenyl-N,N-dimethyl ammonium chloride, and N,N-dimethyl-N-stearyl-N-benzylammonium chloride.

[0243] The foregoing monomeric and polymeric quaternary ammonium salt compounds can have any anionic group as a counter-ion, for example, chloride, bromide, methosulfate (i.e., methylsulfate), acetate, formate, sulfate, nitrate, and the like.

[0244] For fabric softening applications, any suitable quaternary ammonium agent can be utilized in combination with the sulfonic polymers. For ester-containing fabric softening agents, the pH of the compositions can influence the stability of the fabric softening agents, especially in prolonged storage conditions. The pH, as defined in the present context, is measured in the neat compositions at about 20°C. In one aspect, the pH of the composition is less than about 6. In another aspect, the pH is in the range of from about 2 to about 5, and from about 2.5 to about 3.5 in a further aspect.

[0245] In one aspect, the cationic agent(s) can be employed in amounts ranging from about 0.05% to 15% by weight, from about 0.1% to about 10% by weight in another aspect, and from about 0.5% to about 3% by weight in a further aspect, based on the weight of the final composition, but is not limited thereto.

Conditioners

[0246] Any conditioning agent suitable for use in hair styling and skin care compositions can be used in the compositions of the present technology. Conditioning agents can be selected from mineral oils, vegetable oils, fluorinated oils, vegetable oils, natural and synthetic waxes, fatty acids and fatty acid derivatives, proteins, hydrolyzed proteins, silicones (e.g. polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, cyclomethicones, dimethicones, dimethicone copolyols, amodimethicones, and the like), and cationic polymers and compounds. The silicones can be in the form of fluids, oils, emulsions (micro- or macro-emulsions), gums, or resins, and can be volatile or non-volatile, and water soluble or water insoluble.

[0247] In one aspect, cationic conditioning agents can be employed in the compositions disclosed herein. Those of ordinary skill in the art will recognize that many of these cationic conditioning agents serve multiple functions. Typically, these agents are useful as conditioners (e.g., hair and skin), fixatives, antistatic agents, and as antimicrobial agents. Cationic polymers can be synthetically derived or obtained by modifying natural polymers such as the cationically modified polysaccharides and polygalactomannans . [0248] Exemplary conditioning agents include, but are not limited to, homopolymers and copolymers derived from free radically polymerizable acrylic or methacrylic ester or amide monomers. The copolymers can contain one or more units derived from acrylamides, methacrylamides, diacetone acrylamides, acrylic or methacrylic acids or their esters, vinyllactams such as vinyl pyrrolidone or vinyl caprolactam, and vinyl esters. Exemplary polymers include copolymers of acrylamide and dimethyl amino ethyl methacrylate quaternized with dimethyl sulfate or with an alkyl halide; copolymers of acrylamide and methacryloyl oxyethyl trimethyl ammonium chloride; the copolymer of acrylamide and methacryloyl oxyethyl trimethyl ammonium methosulfate; copolymers of vinyl pyrrolidone/dialkylaminoalkyl acrylate or methacrylate, optionally quaternized, such as the products sold under the name GAFQUAT™ by International Specialty Products Inc., Wayne, NJ; the dimethyl amino ethyl methacrylate/vinyl caprolactam/vinyl pyrrolidone terpolymers, such as the product sold under the trade name GAFFIX™ VC 713 by International Specialty Products Inc.; the vinyl pyrrolidone/methacrylamidopropyl dimethylamine copolymer, available from International Specialty Products Inc.; and the vinyl pyrrolidone/quaternized dimethyl amino propyl methacrylamide copolymers such as the product sold under the trade name GAFQUAT™ HS 100 by International Specialty Products, Inc; and the polymeric quaternary ammonium salt formed by the reaction of diethyl sulfate and a copolymer of vinyl pyrrolidone and dimethyl aminoethylmethacrylate such as the product sold under the trade name GAFQUAT™ 755 by International Specialty Products, Inc.

[0249] As described above, many of the disclosed ingredients described herein are multifunctional and, hence, can serve more than one purpose in the formulations of the technology. Thus, as is apparent to those of ordinary skill in the art, many of the ingredients described herein and below (e.g., moisturizers, emollients, emulsifiers, plasticizers, vitamins, and the like) can serve as a conditioning agent herein so long as they function to improve the cosmetic and cosmeceutical properties of the hair.

[0250] In one aspect, the cationic conditioning agent(s) can be employed in amounts ranging from about 0.005 wt.% to 5 wt.%, from about 0.01 wt.% to about 3 wt.% in another aspect, and from about 0.05 wt. % to about 1 wt.% in a further aspect, based on the total weight of the composition, but is not limited thereto.

Cosmeceuticals

[0251 ] In one cosmeceutical aspect, the sulfonic polymers can be employed as a thickener for active skin treatment lotions and creams containing, as active ingredients, acidic anti-aging, anti-cellulite, and anti-acne agents, hydroxy carboxylic acids, such as alpha-hydroxy acid (AHA), beta-hydroxy acid (BHA), alpha-amino acid, alpha-keto acids (AKAs), and mixtures thereof. In one aspect, AHAs can include, but are not limited to, lactic acid, glycolic acid, fruit acids, such as malic acid, citric acid, tartaric acid, extracts of natural compounds containing AHA, such as apple extract, apricot extract, and the like, honey extract, 2-hydroxyoctanoic acid, glyceric acid (dihydroxypropionic acid), tartronic acid (hydroxypropanedioic acid), gluconic acid, mandelic acid, benzilic acid, azelaic acid, alpha-lipoic acid, salicylic acid, AHA salts and derivatives, such as arginine glycolate, ammonium glycolate, sodium glycolate, arginine lactate, ammonium lactate, sodium lactate, alpha- hydroxybutyric acid, alpha-hydroxyisobutyric acid, alpha-hydroxyisocaproic acid, alpha-hydroxyisovaleric acid, atrolactic acid, and the like. BHAs can include, but are not limited to, 3 -hydroxy propanoic acid, beta-hydroxybutyric acid, beta-phenyl lactic acid, beta-phenylpyruvic acid, and the like. Alpha-amino acids include, without being limited thereto, alpha-amino dicarboxylic acids, such as aspartic acid, glutamic acid, and mixtures thereof, sometimes employed in combination with fruit acid. AKAs include pyruvic acid. In some antiaging compositions, the acidic active agent may be retinoic acid, a halocarboxylic acid, such as trichloroacetic acid, an acidic antioxidant, such as ascorbic acid (vitamin C), a mineral acid, phytic acid, lysophosphatidic acid, and the like. Some acidic anti-acne actives, for example, can include salicylic acid, derivatives of salicylic acid, such as 5-octanoylsalicylic acid, retinoic acid, and its derivatives, and benzoic acid.

[0252] A discussion of the use and formulation of active skin treatment compositions is in COSMETICS & TOILETRIES, C&T Ingredient Resource Series, "AHAs & Cellulite Products How They Work", published 1995, and "Cosmeceuticals", published 1998, both available from Allured Publishing Corporation, incorporated herein by reference. Compositions containing alpha- amino acids acidified with ascorbic acid are described in U.S. No. 6,197,317 B l , and a commercial cosmeceutical preparation utilizing these acids in an anti-aging, skin care regimen is sold under the tradename, AFAs, by exCel Cosmeceuticals (Bloomfield Hills, MI). The term "AFA", as described in the supplier's trade literature, was coined by the developer to describe the amino acid/vitamin C combination as Amino Fruit Acids and as the acronym for "Amino acid Filaggrin based Antioxidants."

Electrolytes

[0253] Electrolytes or electrolyte salts are generally known to reduce the viscosity obtained with conventional carbomer polymer thickeners. The compositions of this technology also can contain electrolytes as a viscosity modifier to adjust the viscosity of the hair styling or personal care composition. The electrolyte salts include, but are not limited to aluminum chlorohydrate and the alkali metal salts, e.g., sodium, potassium or lithium salts, these salts preferably being halides, such as the chloride. Exemplary alkali metal halide salts include, but are not limited to sodium chloride, potassium chloride, lithium chloride, and mixtures thereof. The amount of electrolyte that can be included in the composition ranges from about 0.1 wt.% to about 3 wt.% in one aspect, from about 0.5 wt.% to about 2 wt.% in another aspect, and from about 0.6 wt.% to about 1 wt.% in further aspect of the technology, based on the total weight of the composition.

Emollients

[0254] Suitable emollients and lubricants include but are not limited to compositions selected from silicone fluids (e.g., volatile silicone oils and nonvolatile silicone oils); mineral oils; petrolatums, hydrocarbon oils, liquid polyolefin oils, fluorinated and perfluorinated oils, natural oils (e.g., vegetable oils; fish oils), glycerin and glyceride derivatives, fatty alcohols, alkoxylated fatty alcohols, fatty acids; fatty acid and fatty alcohol esters, alkoxylated fatty acid esters, benzoate esters, Guerbet esters, alkyl ether derivatives of polyethylene glycols, such as, for example, methoxypolyethylene glycol (MPEG); and polyalkylene glycols, lanolin and lanolin derivatives, natural and synthetic waxes; and the like.

[0255] The volatile silicones include cyclic and linear polydimethylsiloxanes, and the like. "Volatile" means that the silicone has a measurable vapor pressure, or a vapor pressure of at least 2 mm of Hg at 20°C. The linear volatile silicones are silicone fluids, as described above, having viscosities of not more than about 25 mPa A Byers, "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, Vol.

91 (1), pp. 27-32 (1976), and in Kasprzak, "Volatile Silicones", Soap/Cosmetics/Chemical Specialties, pp. 40-43 (December 1986), each incorporated herein by reference.

[0256] The volatile cyclic polysiloxanes (cyclomethicones) contain about 3 to about 7 silicon atoms, alternating with oxygen atoms, in a cyclic ring structure represented as follows:

wherein R is an aliphatic group, independently selected from alkyl, alkenyl, and aryl, and k ranges from about 3 to about 7. In one aspect, R 20 is independently selected from a methyl and phenyl. However, each R 20 substituent and the number of repeating units, k, in the formula are selected so that the compound is volatile.

Typically, the R 20 substituent is substituted with two alkyl groups (e.g., methyl).

[0257] The volatile linear polydimethylsiloxanes can be represented by the formula:

wherein R is defined as above, and w ranges from 1 to about 8,000 in one aspect, from about 1 to 1000 in another aspect, from 1 to about 500 in a further aspect, and from about 1 to about 250 in a still further aspect. In one aspect, R 20 is independent- ly selected from a methyl and phenyl. However, each R 20 substituent and the number of repeating units, w, in the formula are selected so that the compound is volatile.

[0258] Exemplary volatile cyclomethicones are D4 cyclomethicone (octamethylcyclotetrasiloxane), D5 cyclomethicone (decamethylcyclopentasiloxane), D6 cyclomethicone (dodecamethylcyclohexasiloxane), and blends thereof (e.g., D4/D5 and D5/D6). Volatile cyclomethicones and cyclomethicone blends are commercially available from Momentive Performance Materials Inc. as SF1202, SF 1214, SF1256, and SF1258, Dow Corning, Midland, MI under the Xiameter^® cyclomethicone fluid product designations PMX-0244, PMX-245, PMX-246, PMX- 345, and Dow Corning^® 1401 fluid. Blends of volatile cyclomethicones and volatile linear dimethicones are also contemplated within the scope of the technology.

[0259] Exemplary volatile linear dimethicones include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and blends thereof. Volatile linear dimethicones and dimethicone blends are commercially available from Dow Corning as Xiameter^® PMX-200 silicone fluids (e.g., product designations 0.65 CS, 1 CS, 1.5 CS, and 2 CS) and Xiameter^® PMX 2- 1 184 silicone fluid.

[0260] Silicone oils include polyalkyl, polyaryl siloxanes, or polyalkylaryl siloxanes which conform to the following formula:

wherein R is an aliphatic group, independently selected from alkyl, alkenyl, and

20

aryl, R can be substituted or unsubstituted, and w is an integer from 1 to about

20

8,000. Suitable unsubstituted R groups for use in the present technology include, but are not limited to alkoxy, aryloxy, alkaryl, arylalkyl, arylalkenyl, alkamino, and ether-substituted, hydroxyl-substituted, and halogen-substituted aliphatic and aryl

20

groups. Suitable R groups also include amines, cationic amines and quaternary ammonium groups (e.g., amodimethicone).

[0261 ] In one aspect of the technology, exemplary R²⁰ alkyl and alkenyl

20 substituents include C 1 -C5 alkyl and C 1-C5 alkenyl groups. In another aspect, R is methyl. The aliphatic portions of other alkyl- and alkenyl-containing groups (such as alkoxy, alkaryl, and alkamino) can be straight or branched chains, and contain from C 1-C5 in one aspect, from C 1 -C4 in another aspect, and from C 1-C2 in a further aspect.

20

As discussed above, the R substituents can also contain amino functionalities (e.g., alkamino groups), which can be primary, secondary or tertiary amines or quaternary ammonium. These include mono-, di- and tri-alkylamino and alkoxyamino groups, wherein the aliphatic portion chain length is as described above. Exemplary aryl groups in the foregoing embodiments include phenyl and benzyl.

[0262] Exemplary siloxanes are polydimethyl siloxane, polydiethylsiloxane, and polymethylphenylsiloxane. These siloxanes are available, for example, from Momentive Performance Materials in their Viscasil R and SF 96 series, and from Dow Corning marketed under the Dow Corning 200 series. Exemplary polyalkylaryl siloxane fluids that may be used, include, for example, polymethylphenylsiloxanes. These siloxanes are available, for example, from Momentive Performance Materials as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid, or from Wacker Chemical Corporation, Adrian, MI, under the trade name Wacker- Belsil^® PDM series of phenyl modified silicones (e.g., PDM 20, PDM 350 and PDM 1000).

[0263] Mineral oils and petrolatums include cosmetic, USP and NF grades and are commercially available from Penreco under the Drakeol^® and Penreco^® trade names. Mineral oil includes hexadecane and paraffin oil.

[0264] Hydrocarbon oils having at least about 10 carbon atoms, such as cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated), and branched chain aliphatic hydrocarbons (saturated or unsaturated), including polymers and mixtures thereof. Straight chain hydrocarbon oils typically contain about 12 to 19 carbon atoms. Branched chain hydrocarbon oils, including hydrocarbon polymers, typically will contain more than 19 carbon atoms. Specific non-limiting examples of these hydrocarbon oils include paraffin oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, polybutene, polydecene, and mixtures thereof. Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used, examples of which include highly branched, saturated or unsaturated, alkanes such as the permethyl- substituted isomers, e.g., the permethyl-substituted isomers of hexadecane and eicosane, such as 2,2,4,4,6,6,8,8-dimethyl-lO-methylundecane and 2,2,4,4,6,6-dimethyl-8-methylnonane, available from Permethyl Corporation. Hydrocarbon polymers such as polybutene and polydecene. [0265] Liquid polyolefin oils can be used in the compositions of the present technology. The liquid polyolefin agents are typically poly-a-olefins that have been hydrogenated. Polyolefins for use herein can be prepared by the polymerization of C₄ to about C₁₄ olefinic monomers. Non-limiting examples of olefinic monomers for use in preparing the polyolefin liquids herein include ethylene, propylene, 1 -butene, 1 -pentene, 1 -hexene, 1 -octene, 1 -decene, 1 -dodecene, 1 -tetradecene, and 1 -hexadecene, branched isomers such as isobutylene, 4-methyl- 1-pentene, and mixtures thereof. In one aspect, a suitable hydrogenated polyolefin is the copolymer of isobutylene and butene. A commercially available material of this type is Panalane^® L-14E (INCI Name: Hydrogenated Polyisobutene) marketed by Lipo Chemicals Inc, Patterson, N.J.

[0266] Fluorinated and perfluorinated oils contemplated within the scope of the present technology include perfluoropolyethers described in European Patent No. EP 0 486 135 and the fluorohydrocarbon compounds described in International Patent Application Publication No. WO 93/1 1 103. The fluorinated oils may also be fluorocarbons such as fluoramines, e.g., perfluorotributylamine, fluoridated hydrocarbons, such as perfluorodecahydronaphthalene, fluoroesters, and fluoroethers.

[0267] Natural oils that are useful in the practice of this technology include, but are not limited to, peanut, sesame, avocado, coconut, cocoa butter, canola, babassu, almond, corn, grape seed, cottonseed, sesame seed, walnut, castor, olive, jojoba, palm, palm kernel, soybean, wheat germ, linseed, safflower, shea nut, sunflower seed, eucalyptus, lavender, vetiver, litsea, cubeba, lemon, sandalwood, rosemary, chamomile, savory, nutmeg, cinnamon, hyssop, caraway, orange, geranium, cade, and bergamot oils, fish oils, as well as glycerides (mono- di- and triglycerides) derived from plant oils, vegetable oils, and animal fats (e.g., tallow and lard); and mixtures thereof. The hydrogenated derivatives of natural oils also are contemplated.

[0268] Suitable glycerides (mono-, di-, and triglycerides) can be derived through the esterification of glycerol, a monoglyceride, or a diglyceride with a fatty acid(s) by techniques well known in the art, or by glycerolysis of animal fats and vegetable oils in the presence of a base at elevated temperature and under an inert atmoshere (See RSC Green Chemistry Book Series, The Royal Society of Chemistry, The Future of Glycerol: New Uses Of A Versatile Material, Chapter 7, Mario Pagliaro and Michele Rossi, © 2008). Fatty acids suitable for use in the esterification reaction include saturated and unsaturated C8-C30 fatty acids.

[0269] The fatty alcohols suitable for use in the compositions of the technology include, but are not limited to, the saturated and unsaturated C8-C30 fatty alcohols. Exemplary fatty alcohols include capryl alcohol, pelargonic alcohol, capric alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, isocetyl alcohol, stearyl alcohol, isostearyl alcohol, cetearyl alcohol, palmitoleyl alcohol, elaidyl alcohol, sterol, oleyl alcohol, linoleyl alcohol, elaidolinoleyl alcohol, linolenyl alcohol, ricinoleyl alcohol, arachidyl alcohol, icocenyl alcohol, behenyl alcohol, erucyl alcohol, lignoceryl alcohol, ceryl alcohol, montanyl alcohol, myricyl alcohol, and mixtures thereof. Fatty alcohols are widely available and can be obtained through the hydrogenation of esterified vegetable and animal oils and fats.

[0270] Alkoxylated fatty alcohol compounds are ethers formed from the reaction of a fatty alcohol with an alkylene oxide, generally ethylene oxide or propylene oxide. Suitable ethoxylated fatty alcohols are adducts of fatty alcohols and polyethylene oxide. In one aspect of the technology, the ethoxylated fatty alcohols can be represented by the formula

wherein R"' represents the aliphatic residue of the parent fatty alcohol and n" represents the number of ethylene oxide units. In another aspect of the technology, R'" is derived from a fatty alcohol containing 8 to 30 carbon atoms. In one aspect, n" is an integer ranging from 2 to 50, 3 to 25 in another aspect, and 3 to 10 in a further aspect. In a still further aspect, R'" is derived from a fatty alcohol set forth immediately in the paragraph above. Exemplary ethoxylated fatty alcohols are but are not limited to capryl alcohol ethoxylate, lauryl alcohol ethoxylate, myristyl alcohol ethoxylate, cetyl alcohol ethoxylate, stearyl alcohol ethoxylate, cetearyl alcohol ethoxylate, sterol ethoxylate, oleyl alcohol ethoxylate, and, behenyl alcohol ethoxylate, wherein the number of ethylene oxide units in each of the foregoing ethoxylates can range from 2 and above in one aspect, and from 2 to about 150 in another aspect. It is to be recognized that the propoxylated adducts of the foregoing fatty alcohols and mixed ethoxylated/propoxylated adducts of the foregoing fatty alcohols are also contemplated within the scope of the technology. The ethylene oxide and propylene oxide units of the ethoxylated/propoxylated fatty alcohols can be arranged in random or in blocky order. [0271 ] Exemplary ethoxylated sterols include ethoxylated vegetable oil sterols such as, for example, soya sterols. The degree of ethoxylation is greater than about 5 in one aspect, and at least about 10 in another aspect. Suitable ethoxylated sterols are PEG- 10 Soy Sterol, PEG- 16 Soy Sterol and PEG-25 Soy Sterol.

[0272] Additional examples of ethoxylated alcohols are but are not limited to Beheneth 5-30 (the 5-30 meaning the range of repeating ethylene oxide units), Ceteareth 2-100, Ceteth 1-45, Cetoleth 24-25, Choleth 10-24, Coceth 3-10, C9-1 1 Pareth 3-8, C I 1 -15 Pareth 5-40, C I 1 -21 Pareth 3-10, C 12-13 Pareth 3-15, Deceth 4- 6, Dodoxynol 5-12, Glycereth 7-26, Isoceteth 10-30, Isodeceth 4-6, Isolaureth 3-6, isosteareth 3-50, Laneth 5-75, Laureth 1-40, Nonoxynol 1 -120, Nonylnonoxynol 5- 150, Octoxynol 3-70, Oleth 2-50, PEG 4-350, Steareth 2- 100, and Trideceth 2-10.

[0273] Specific examples of propoxylated alcohols are but are not limited to PPG- 10 Cetyl Ether, PPG-20 Cetyl Ether, PPG-28 Cetyl Ether, PPG-30 Cetyl Ether, PPG- 50 Cetyl Ether, PPG-2 Lanolin Alcohol Ether, PPG-5 Lanolin Alcohol Ether, PPG- 10 Lanolin Alcohol Ether, PPG-20 Lanolin Alcohol Ether, PPG-30 Lanolin Alcohol Ether, PPG-4 Lauryl Ether, PPG-7 Lauryl Ether, PPG- 10 Oleyl Ether, PPG-20 Oleyl Ether, PPG-23 Oleyl Ether, PPG-30 Oleyl Ether, PPG-37 Oleyl Ether, PPG-50 Oleyl Ether, PPG- 1 1 Stearyl Ether, PPG- 15 Stearyl Ether, PPG-2 Lanolin Ether, PPG-5 Lanolin Ether, PPG- 10 Lanolin Ether, PPG-20 Lanolin Ether, PPG-30 Lanolin Ether, and PPG-1 Myristyl Ether.

[0274] Specific examples of ethoxylated/propoxylated alcohols are but are not limited to PPG-1 Beheneth-15, PPG-12 Capryleth-18, PPG-2-Ceteareth-9, PPG-4- Ceteareth-12, PPG-lO-Ceteareth-20, PPG-1 -Ceteth- 1 , PPG-l -Ceteth-5, PPG-1- Ceteth-10, PPG-l -Ceteth-20, PPG-2-Ceteth-l , PPG-2-Ceteth-5, PPG-2-Ceteth-10, PPG-2-Ceteth-20, PPG-4-Ceteth-l , PPG-4-Ceteth-5, PPG-4-Ceteth-10, PPG-4- Ceteth-20, PPG-5-Ceteth-20, PPG-8-Ceteth-l , PPG-8-Ceteth-2, PPG-8-Ceteth-5, PPG-8-Ceteth-10, PPG-8-Ceteth-20, PPG-2 C 12-13 Pareth-8, PPG-2 C 12-15 Pareth- 6, PPG-4 C 13-15 Pareth-15, PPG-5 C9-15 Pareth-6, PPG-6 C9-1 1 Pareth-5, PPG-6 C 12-15 Pareth-12, PPG-6 C 12-18 Pareth-11 , PPG-3 C 12-14 Sec-Pareth-7, PPG-4 C 12-14 Sec-Pareth-5, PPG-5 C 12-14 Sec-Pareth-7, PPG-5 C12-14 Sec-Pareth-9, PPG-l-Deceth-6, PPG-2-Deceth-3, PPG-2-Deceth-5, PPG-2-Deceth-7, PPG-2- Deceth-10, PPG-2-Deceth-12, PPG-2-Deceth-15, PPG-2-Deceth-20, PPG-2-Deceth- 30, PPG-2-Deceth-40, PPG-2-Deceth-50, PPG-2-Deceth-60, PPG-4-Deceth-4, PPG- 4-Deceth-6, PPG-6-Deceth-4, PPG-6-Deceth-9, PPG-8-Deceth-6, PPG-14-Deceth-6, PPG-6-Decyltetradeceth-12, PPG-6-Decyltetradeceth-20, PPG-6-Decyltetradeceth- 30, PPG-13-Decyltetradeceth-24, PPG-20-Decyltetradeceth-10, PPG-2-Isodeceth-4, PPG-2-Isodeceth-6, PPG-2-Isodeceth-8, PPG-2-Isodeceth-9, PPG-2-Isodeceth-10, PPG-2-lsodeceth-12, PPG-2-Isodeceth-18, PPG-2-Isodeceth-25, PPG-4-Isodeceth-10, PPG-12-Laneth-50, PPG-2-Laureth-5, PPG-2-Laureth-8, PPG-2-Laureth-12, PPG-3- Laureth-8, PPG-3-Laureth-9, PPG-3-Laureth-10, PPG-3-Laureth-12, PPG-4 Laureth- 2, PPG-4 Laureth-5, PPG-4 Laureth-7, PPG-4-Laureth-15, PPG-5-Laureth-5, PPG-6- Laureth-3, PPG-25-Laureth-25, PPG-7 Lauryl Ether, PPG-3-Myreth-3, PPG-3- Myreth-1 1 , PPG-20-PEG-20 Hydrogenated Lanolin, PPG-2-PEG-1 1 Hydrogenated Lauryl Alcohol Ether, PPG-12-PEG-50 Lanolin, PPG-12-PEG-65 Lanolin Oil, PPG- 40-PEG-60 Lanolin Oil, PPG-l -PEG-9 Lauryl Glycol Ether, PPG-3-PEG-6 Oleyl Ether, PPG-23-Steareth-34, PPG-30 Steareth-4, PPG-34-Steareth-3, PPG-38 Steareth-6, PPG-1 Trideceth-6, PPG-4 Trideceth-6, and PPG-6 Trideceth-8.

[0275] Suitable fatty acids include saturated and unsaturated C₈ to C30 fatty acids. Exemplary fatty acids include, but are not limited to, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, ricinoleic acid, vaccenic acid, linoleic acid, a-linolenic acid, γ-linolenic acid, arachidic acid, gadoleic acid, arachidonic acid, EPA (5,8, 1 1 ,14, 17-eicosapentaenoic acid), behenic acid, erucic acid, DHA (4,7, 10, 13, 16,19-docosahexaenoic acid), lignoceric acid, and mixtures thereof.

[0276] Fatty acids can be esterified by alcohols in the presence of a suitable acid catalyst to give a desired fatty acid ester. In one aspect, any of the saturated and unsaturated C₈ to C30 fatty acids disclosed above can be esterified by a saturated or unsaturated Ci to C₂₂ alcohol to give the respective fatty acid ester. In another aspect, longer chain fatty acid esters can be derived from the esterification of the above mentioned fatty acids by a saturated or unsaturated C₈ to C30 fatty alcohol and can be represented by the formula: R C(0)OR wherein R" independently represents a saturated and unsaturated, linear and branched alkyl group containing 1 to 24 carbon atoms. Suitable fatty alcohols include the fatty alcohols that are disclosed above.

[0277] Exemplary fatty acid esters include, but are not limited to, methyl laurate, hexyl laurate, isohexyl laurate, decyl oleate, methyl cocoate, isopropyl stearate, isopropyl isostearate, butyl stearate, decyl stearate, octyl stearate, cetyl stearate, stearyl stearate, oleyl stearate, myristyl myristate, octyldodecyl stearoyl stearate, octylhydroxystearate, isopropyl myristate, oleyl myristate, isopropyl palmitate, ethyl hexyl palmitate, cetyl palmitate, decyl oleate, isodecyl oleate, oleyl oleate, isodecyl neopentanoate, diisopropyl sebacate, isostearyl lactate, lauryl lactate, cetearyl octanoate, and mixtures thereof.

[0278] Still other fatty acid esters suitable for use in the fixative compositions of the present technology are mono-, di- and tri-alkyl and alkenyl esters of carboxylic acids, such as esters of C₂ to Cg monocarboxylic acids, C₄ to C₁₀ dicarboxylic acids, and C₆ to C₁₀ tricarboxylic acids (e.g., Ci to C₂₂ esters of acetic acid, lactic acid, succinic acid, glutaric acid, adipic acid, citric acid, trimelletic acid, trimesic acid, and 1 ,3,5-pentane tricarboxylic acid). Specific non-limiting examples of mono-, di- and tri-alkyl and alkenyl esters of carboxylic acids include lauryl acetate, cetyl propionate, lauryl lactate, myristyl lactate, cetyl lactate, diisopropyl adipate, dihexyldecyl adipate, dioleyl adipate, and tristearyl citrate.

[0279] Other fatty esters suitable for use in the compositions of the present technology are those known as polyhydric alcohol esters. Such polyhydric alcohol esters include alkylene glycol esters, such as ethylene glycol mono- and di-fatty acid esters, diethylene glycol mono- and di-fatty acid esters, polyethylene glycol mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid esters, polypropylene glycol mono- and di-fatty acid esters, and sorbitol mono- and di-fatty esters, wherein the acyl portion of the fatty acid ester is derived from a saturated or unsaturated Cg to C₂₂ fatty acid. These esters can be optionally ethoxylated. Representative polyhydric alcohol fatty acid esters include, but are not limited to, polypropylene glycol monooleate, polypropylene glycol monostearate, glyceryl mono- and di-fatty acid esters, polyglycerol poly-fatty acid esters, ethoxylated glyceryl monostearate, 1 ,3-butylene glycol monostearate, 1 ,3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.

[0280] Other polyhydric alcohol esters include the partial esters of polyglycerols. These esters contain 2 to 10 glycerol units and are esterified with 1 to 4 saturated or unsaturated, linear or branched, optionally hydroxylated Cg to C30 fatty acid residues. Representative partial esters of polyglycerols include, but are not limited to, diglycerol monocaprylate, diglycerol monocaprate, diglycerol monolaurate, triglycerol monocaprylate, triglycerol monocaprate, triglycerol monolaurate, tetraglycerol monocaprylate, tetraglycerol monocaprate, tetraglycerol monolaurate, pentaglycerol monocaprylate, pentaglycerol monocaprate, pentaglycerol monolaurate, hexaglycerol monocaprylate, hexaglycerol monocaprate, hexaglycerol monolaurate, hexaglycerol monomyristate, hexaglycerol monostearate, decaglycerol monocaprylate, decaglycerol monocaprate, decaglycerol monolaurate, decaglycerol monomyristate, decaglycerol monoisostearate, decaglycerol monostearate, decaglycerol monooleate, decaglycerol monohydroxystearate, decaglycerol dicaprylate, decaglycerol dicaprate, decaglycerol dilaurate, decaglycerol dimyristate, decaglycerol diisostearate, decaglycerol distearate, decaglycerol dioleate, decaglycerol dihydroxystearate, decaglycerol tricaprylate, decaglycerol tricaprate, decaglycerol trilaurate, decaglycerol trimyristate, decaglycerol triisostearate, decaglycerol tristearate, decaglycerol trioleate, decaglycerol trihydroxystearate, and mixtures thereof.

[0281 ] Suitable benzoate esters are obtained by the reaction of benzoic acid with a fatty alcohol such as those described above. In one aspect, the fatty alcohol utilized in the esterification reaction is a C₁₂-C₁₅ fatty alcohol. Such esters are described in U.S. Patent No. 4,275,222 which is incorporated herein by reference.

[0282] Guerbet esters are also suitable in the fixative compositions of the technology. Guerbet esters can be formed from the esterification of a mono- or polyfunctional carboxylic acid by a Guerbet alcohol. Alternatively, the ester can be formed by reacting a Guerbet acid with a mono- or polyfunctional alcohol. For a review of Guerbet chemistry, see O'Lenick, A. J., Jr. 2001. Guerbet chemistry. Journal of Surfactants and Detergents 4: 31 1-315. Guerbet esters are commercially available from Lubrizol Advanced Materials, Inc. under product designations G-20, G-36, G-38, and G-66.

[0283] Lanolin and lanolin derivatives are selected from lanolin, lanolin wax, lanolin oil, lanolin alcohols, lanolin fatty acids, esters of lanolin fatty acids such as the isopropyl esters of lanolin fatty acid (e.g., isopropyl lanolates), alkoxylated lanolin (ethoxylated, propoxylated, and combinations thereof), acetylated lanolin alcohols; and combinations thereof. Lanolin and lanolin derivatives are commercially available from Lubrizol Advanced Materials, Inc. under the trade names Lanolin LP 108 USP, Lanolin USP AAA, Acetulan™, Ceralan™, Lanocerin™, Lanogel™ (product designations 21 and 41), Lanogene™, Modulan™, Ohlan™, Solulan™ (product designations 16, 75, L-575, 98, and C-24), and Vilvanolin™ (product designations C, CAB, L- 101 , and P).

[0284] The emollient can be used alone or in combination with one or more emollients of the present technology. The emollient(s) can be utilized in an amount ranging from about 0.5 wt.% to about 30 wt.% in one aspect, from about 0.1 wt.% to about 25 wt.% in another aspect, and from about 5 wt.% to about 20 wt.% in a further aspect, based on the total weight of the composition. Although the ingredients mentioned herein are generally defined as emollients, they may also possess other properties such as moisturizing or other conditioning properties.

Emulsifiers

[0285] In one aspect, the emulsifiers useful in the compositions of the technology are nonionic. Useful nonionic emulsifiers include, but are not limited to, the aliphatic (C6-C30) fatty alcohols, alkoxylated fatty alcohols, and ethoxylated sterols disclosed above, alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy moieties); block alkylene oxide condensates of alkyl phenols; alkylene oxide condensates of alkanols; and ethylene oxide/propylene oxide block copolymers; and mixtures thereof.

[0286] Other suitable nonionic emulsifiers include mono- or dialkyl alkanolamides; alkyl polyglucosides (APGs); sorbitan fatty acid esters (e.g, sorbitan laurate, sorbitan stearate); polyoxyethylene sorbitan fatty acid esters (e.g., Polysorbate-20, Polysorbate-40, Polysorbate-60, Polysorbate-80); polyoxyethylene acids, and polyoxyethylene alcohols. Other examples of suitable nonionic surfactants include coco mono- or diethanolamide, coco glucoside, decyl diglucoside, lauryl diglucoside, coco diglucoside, cetearyl alcohol, lanolin alcohol, stearic acid, glyceryl stearate, PEG- 100 stearate, laureth-7, and oleth-20; Hydrogenated Castor Oil, PEG-40 Hydrogenated Castor Oil, PEG-50 Hydrogenated Castor Oil, PEG-60 Hydrogenated Castor Oil, PEG-60 Almond Glycerides, PEG-70 Mango Glycerides, PEG- 192 Apricot Kernel Glycerides; and mixtures thereof.

[0287] Still other nonionic emulsifiers include, but are not limited to, alkoxylated methyl glucosides such as, for example, methyl gluceth-10, methyl gluceth-20, PPG- 10 methyl glucose ether, and PPG-20 methyl glucose ether, available from Lubrizol Advanced Materials, Inc. under the trade names, Glucam E10, Glucam E20, Glucam^® P10, and Glucam^® P20, respectively; and hydrophobically modified alkoxylated methyl glucosides, such as PEG 120 methyl glucose dioleate, PEG-120 methyl glucose trioleate, and PEG-20 methyl glucose sesquistearate, available from Lubrizol Advanced Materials, Inc., under the trade names, Glucamate^® DOE- 120, Glucamate™ LT, and Glucamate™ SSE-20, respectively; and mixtures thereof, are also suitable. Mixtures of any of the emulsifiers disclosed herein also are contemplated herein. The amount of emulsifier can range from about 1 wt.% to about 25 wt.% in one aspect, from about 3 wt.% to about 20 wt.% in another aspect, and from about 5 wt.% to about 15 wt.% in a further aspect, based on the weight of the total composition.

Fragrances

[0288] A variety of fragrances may be used in the compositions of the present technology. The term "fragrance" is meant to encompass any component reacting with the human olfactory sites and imparting a pleasurable odor, essence or scent. Fragrances that may be used in accordance with the present technology include any synthetic as well as natural fragrance and mixtures thereof. Typically, a multiplicity of fragrances is employed to achieve the desired scent. Fragrance base materials comprise inter alia alcohols, ketones, aldehydes, esters, ethers, nitrites, and cyclic and acyclic alkenes, especially terpenes. A further way of classifying fragrances is in accordance with generally recognized scents they produce. Descriptors used by those skilled in the art of fragrances are inter alia "rose", "floral", "green", "citrus", "spicy", "honey", "musk", "herbal", "jasmin", "lilac", lily of the valley", "orange", "peach", "oriental", "watermelon" "chypre" and "lemon", "woody", "fruity", and the like, all of which may be formulated with the compositions of the present technology. A listing of common fragrance base materials can be found in various reference sources, for example, "Perfume and Flavor Chemicals", Vols. I and II; Steffen Arctander Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology"; Muller, P. M. and Lamparsky, D., Blackie Academic and Professional (1994) both incorporated herein by reference.

[0289] Examples of synthetic fragrances that may be used in accordance with the present technology include without limitation acetanisole, acetophenone, acetyl cedrene, butylphenyl methylpropional, hydroxyisohexyl 3-cyclohexene carboxaldehyde, alpha-isomethyl ionone, methyl nonyl acetaldehyde, musk anbrette, heliotropin, citronellol, limonene, sandella, methoxycitranellal, hydroxycitranellal, phenyl ethyl acetate, phenylethylisobutarate, butylphenyl methylpropional, gamma methyl ionone, geraniol, anethole, benzaldehyde, benzyl acetate, benzyl salicylate, linalool, cinnamic alcohol, phenyl acetaldehyde, alpha-amyl cinnamic aldehyde, caphore; p-tertiary butyl cyclohexyl acetate, citral, hexyl cinnamal, cinnamyl acetate, cinnamyl alcohol, citral diethyl acetal, coumarin, ethylene brasslate, eugenol, 1 - menthol, vanillin, and mixtures thereof.

[0290] Examples of natural fragrances of use herein include without limitation Zingiber Officinale root extract, Melaleuca Alternifolia Leaf Oil, lavandin, heliotropin, sandlewood oil, oak moss, pathouly, ambergris tincture, ambrette seed absolute, angelic root oil, bergamont oil; benzoin Siam resin, buchu leaf oil, cassia oil; cedarwood oil, cassia oil, castoreum, civet absolute, chamomile oil, geranium oil, lemon oil, lavender oil, Ylang Ylang oil, and mixtures thereof. Mixtures of the foregoing synthetic and natural fragrances also are contemplated.

[0291 ] In one aspect, the composition contains less than about 2 wt.% of fragrance(s) based on the total weight of the wetting composition. In another aspect, the composition contains from about 0.01 wt.% to about 3 wt.% percent of fragrance(s). In a further aspect of the technology, the composition contains from about 0.01 wt.%> to about 0.5 wt.%> of fragrance(s), all based on the total weight of the composition.

[0292] Further, a variety of fragrance solubilizers may be used in the compositions of the present technology. Suitable fragrance solubilizers include, but are not limited to, benzyl benzoate, Polysorbate 20, propylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, dipropylene glycol, diethyl phthalate, ethoxydiglycol, and triethyl citrate. In one aspect, the composition contains less than about 5 wt.% of fragrance solubilizers, from about 0.01 wt.% to about 1 wt.% in another aspect, and from about 0.01 wt.% to about 0.5 wt.% in a further aspect, based on the total weight of the composition.

Hair Colorants

[0293] The polymers of the technology can be utilized in the formulation of temporary, semi-permanent, or permanent hair color styling gels. The composition of the technology can contain a hair dye selected from thermochromic dyes, neutral acid or cationic nitrobenzene dyes, neutral acid or cationic azo dyes, quinone dyes, neutral, acid or cationic anthraquinone dyes, azine dyes, triarylmethane dyes, indoamine dyes and natural dyes. In one aspect of the technology, cationic dyes are utilized. Such dyes are generally known to the art and to the literature and are commonly described in two different manners. The dye name (e.g., Basic Brown 16) relates to its INCI name (International Nomenclature Cosmetic Ingredient) and/or its CTFA name (Cosmetic, Toiletry and Fragrance Association) name. These dyes also are referenced through the Color Index No. (e.g., CI 12250) which is used by the European Union. Both sets of numbers are set forth in the "International Cosmetic Ingredient Dictionary and Handbook" for example, the 7^th Edition, 1997, published by The Cosmetic, Toiletry, and Fragrance Association, Washington, D.C., U.S.A. Specific cationic dyes which can be utilized include, but are not limited to, the various azo dyes such as Basic Brown 16 (CI 12250), Basic Brown 17 (CI 12251), Basic Red 76 (CI 12245), Basic Yellow 57 (CI 12719), as well as various anthraquinone dyes such as Basic Blue 99 (CI 56059), and the like. The dye or dyes can be present in a concentration from about 0.001 wt.% to about 20 wt.% in one aspect, from about 0.005 wt.% to about 10 wt % in another aspect, and from about 0.1 wt.% to about 5 wt.%> in a further aspect, based upon the total weight of the composition.

Insoluble Components

[0294] Cosmetic beads, flakes, capsules, powders, particulates (e.g., micronized silica), gas bubbles, and combinations thereof can be included in the composition for aesthetic appearance or can function as micro- and macro-encapsulants for the delivery of benefit agents (e.g., vitamins, conditioners, moisturizers, etc.) to the scalp and hair. Exemplary bead components include, but are not limited to, agar beads, alginate beads, jojoba beads, gelatin beads, Styrofoam™ beads, polyacrylate, polymethylmethacrylate (PMMA), polyethylene beads, Unispheres^™ and Unipearls™ cosmetic beads (Induchem USA, Inc., New York, NY), Lipocapsule™, Liposphere™, and Lipopearl™ microcapsules (Lipo Technologies Inc., Vandalia, OH), and Confetti II™ dermal delivery flakes (United-Guardian, Inc., Hauppauge, NY). Aesthetic bubbles of air or an inert gas can be incorporated into the compositions of the technology by well known techniques. The amount of insoluble component(s) that is incorporated into the compositions of the technology will depend upon the desired aesthetic property the formulator is conveying with the end product. Any amount of insoluble component can be utilized as long as the rheology and fixative properties of the composition are not deleteriously affected. In one aspect, the compositions of the technology can contain from about 0.1 wt.% to about 10 wt.%, from about 0.5 wt.% to about 5 wt.% in another aspect, and from about 3 wt.% to about 5 wt.% in a further aspect based on the total weight of the composition.

Silicones

[0295] In one aspect, silicones are utilized as conditioning agents which are commonly used in rinse off hair conditioner products and in shampoo products, such as the so-called "two-in-one" combination cleansing/conditioning shampoos. In one aspect, the conditioning agent is an insoluble silicone conditioning agent. Typically, the conditioning agent will be mixed in the shampoo composition to form a separate, discontinuous phase of dispersed, insoluble particles (also referred to as droplets). The silicone hair conditioning agent phase can be a silicone fluid and can also comprise other ingredients, such as a silicone resin, to improve silicone fluid deposition efficiency or enhance the glossiness of the hair especially when high refractive index (e.g., above about 1.6) silicone conditioning agents are used. The optional silicone hair conditioning agent phase may comprise volatile silicone, nonvolatile silicone, or combinations thereof. The silicone conditioning agent particles may comprise volatile silicone, non-volatile silicone, or combinations thereof. In one aspect, non-volatile silicone conditioning agents are utilized. If volatile silicones are present, they will typically be incidental to their use as a solvent or carrier for commercially available forms of non-volatile silicone materials ingredients, such as silicone gums and resins. The silicone hair conditioning agents for use with the sulfonic polymers have a viscosity of from about 0.5 to about 50,000,000 centistokes (1 centistokes equals 1 x 10^'"6 m²/s) in one aspect, from about 10 to about 30,000,000 centistokes in another aspect, from about 100 to about 2,000,000 in a further aspect, and from about 1 ,000 to about 1 ,500,000 centistokes in a still further aspect, as measured at 25 °C.

[0296] In one embodiment, the silicone conditioning agent particles can have a volume average particle diameter ranging from about 0.01 μιη to about 500 μιη. For small particle application to hair, the volume average particle diameters range from about 0.01 μηι to about 4 μηι in one aspect, from about 0.01 μιη to about 2 μιη in another aspect, and from about 0.01 μιη to about 0.5 μιη in still another aspect. For larger particle application to hair, the volume average particle diameters typically range from about 5 μιη to about 125 μιη in one aspect, from about 10 μιη to about 90 μιη in another aspect, from about 15 μιη to about 70 μιη in still another aspect, and from about 20 μιη to about 50 μιη in a further aspect.

[0297] Background material on silicones including sections discussing silicone fluids, gums, and resins, as well as manufacture of silicones, are found in Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp 204-308, John Wiley & Sons, Inc. (1989), incorporated herein by reference. Silicone fluids are generally described as alkylsiloxane polymers. Non-limiting examples of suitable silicone conditioning agents, and optional suspending agents for the silicone, are described in U.S. Reissue Patent No. 34,584, U.S. Patent No. 5, 104,646, and U.S. Patent No. 5,106,609, which descriptions are incorporated herein by reference.

[0298] Silicone oils include polyalkyl, polyaryl siloxanes, or polyalkylaryl siloxanes which conform to the following formula:

wherein R is an aliphatic group, independently selected from alkyl, alkenyl, and

20

aryl, R can be substituted or unsubstituted, and w is an integer from 1 to about

20

8,000. Suitable unsubstituted R groups for use with the sulfonic polymers include, but are not limited to alkoxy, aryloxy, alkaryl, arylalkyl, arylalkenyl, alkamino, and ether-substituted, hydroxyl-substituted, and halogen-substituted aliphatic and aryl

20

groups. Suitable R groups also include amines, cationic amines and quaternary ammonium groups.

[0299] In one aspect, exemplary R²⁰ alkyl and alkenyl substituents include C 1-C5 alkyl and ups. In another aspect, R 20

C 1-C5 alkenyl gro is methyl. The aliphatic portions of other alkyl- and alkenyl-containing groups (such as alkoxy, alkaryl, and alkamino) can be straight or branched chains, and contain from C 1-C5 in one aspect, from C 1-C4 in another aspect, and from C 1-C2 in a further aspect. As discussed above, the R substituents can also contain amino functionalities (e.g., alkamino groups), which can be primary, secondary or tertiary amines or quaternary ammonium. These include mono-, di- and tri-alkylamino and alkoxyamino groups, wherein the aliphatic portion chain length is as described above. Exemplary aryl groups in the foregoing embodiments include phenyl and benzyl.

[0300] Exemplary siloxanes are polydimethyl siloxane, polydiethylsiloxane, and polymethylphenylsiloxane. These siloxanes are available, for example, from Momentive Performance Materials in their Viscasil R and SF 96 series, and from Dow Corning marketed under the Dow Corning 200 series. Exemplary polyalkylaryl siloxane fluids that may be used, include, for example, polymethylphenylsiloxanes. These siloxanes are available, for example, from Momentive Performance Materials as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid, or from Wacker Chemical Corporation, Adrian, MI, under the trade name Wacker- Belsil^® PDM series of phenyl modified silicones (e.g., PDM 20, PDM 350 and PDM 1000).

[0301 ] Cationic silicone fluids are also suitable for use with the sulfonic polymers. The cationic silicone fluids can be represented, but are not limited, to the general formula):

wherein G is hydrogen, phenyl, hydroxy, or Ci-C₈ alkyl (e.g., methyl or phenyl); e is 0 or an integer having of from 1 to 3; f is 0 or 1 ; g is a number from 0 to 1 ,999; h is an integer from 1 to 2,000 in one aspect, and from 1 to 10 in another aspect; the sum of g and h is a number from 1 to 2,000 in one aspect, and from 50 to 500 in another aspect; R 21 is a monovalent radical conforming to the general formula C_qH_2qL, wherein q is an integer having a value from 2 to 8 and L is selected from the following groups:

a) -N(R²²)CH₂CH₂N(R²²)₂

b) -N(R²²)₂

c) -N⁺(R²²)₃ CA^"

d) -N(R²²)CH₂CH₂N⁺H₂R²² CA^" wherein R is independently selected from hydrogen, C 1 -C20 alkyl, phenyl, benzyl; and CA is a halide counter ion selected from chloride, bromide, fluoride, and iodide.

[0302] In another aspect, a cationic silicone useful in with the sulfonic polymers can be represented by the formula:

wherein R represents a radical selected from a Ci-Ci₈ alkyl and Ci-Ci₈ alkenyl

24

group; R independently represents a radical selected from a Ci-Cig alkylene radical or a C 1 -C 18 alkyleneoxy radical; CA is a halide ion; r represents an integer ranging from 2 to 20 in one aspect, and from 2 to 8 in another aspect; s represents an integer ranging from 20 to 200 in one aspect, and from 20 to 50 in another aspect. In one aspect, R 23 is methyl. In another aspect, CA is a chloride ion. An example of a quaternary silicone polymer useful with the sulfonic polymers is Abil^® T Quat 60, available from Evonik Goldschmidt Corporatiion, Hopewell, VA.

[0303] Another class of suitable silicone fluids is the insoluble silicone gums. These gums are polysiloxane materials having a viscosity at 25°C of greater than or equal to 1 ,000,000 centistokes. Silicone gums are described in U.S. Patent No. 4, 152,416; Noll and Walter, Chemistry and Technology of Silicones, New York: Academic Press 1968; and in General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54, and SE 76, all of which are incorporated herein by reference. The silicone gums typically have a mass molecule weight in excess of about 200,000 daltons, generally between about 200,000 to about 1 ,000,000 daltons, specific examples of which include polydimethylsiloxane, polydimethylsiloxane/methylvinylsiloxane copolymer, polydimethylsiloxane/diphenyl siloxane/methylvinylsiloxane) copolymer, and mixtures thereof.

[0304] Another category of nonvolatile, insoluble silicone fluid conditioning agents are the high refractive index polysiloxanes, having a refractive index of at least about 1.46 in one aspect, at least about 1.48 in another aspect, at least about 1.52 in a further aspect, and at least about 1.55 in a still further aspect. The refractive index of the polysiloxane fluid will generally be less than about 1.70, typically less than about 1.60. In this context, polysiloxane "fluid" includes oils, resins, and gums.

[0305] The high refractive index polysiloxane fluid includes those represented by the general formula set forth for the polyalkyl, polyaryl, and polyalkylaryl siloxanes described above, as well as cyclic polysiloxanes (cyclomethicones) represented by the formula:

20

wherein the substituent R is as defined above, and the number of repeat units, k, ranges from about 3 to about 7 in one aspect, and from 3 to 5 in another aspect. The high refractive index polysiloxane fluids can contain an amount of aryl containing

20

R substituents sufficient to increase the refractive index to a desired level, which is

20

described above. Additionally, R and k must be selected so that the material is non- volatile. Aryl containing substituents include those which contain alicyclic and heterocyclic five and six member aryl rings and those which contain fused five or six member rings. The aryl rings can be substituted or unsubstituted. Substituents include aliphatic substituents, and can also include alkoxy substituents, acyl substituents, ketones, halogens (e.g., CI and Br), amines, etc. Exemplary aryl containing groups include substituted and unsubstituted arenes, such as phenyl, and phenyl derivatives such as phenyls with C i-C₅ alkyl or alkenyl substituents, e.g., allylphenyl, methyl phenyl and ethyl phenyl, vinyl phenyls such as styrenyl, and phenyl alkynes (e.g., phenyl C2-C4 alkynes). Heterocyclic aryl groups include substituents derived from furan, imidazole, pyrrole, pyridine, etc. Fused aryl ring substituents include, for example, naphthalene, coumarin, and purine.

[0306] The high refractive index polysiloxane fluids can have a degree of aryl containing substituents of at least about 15% by weight in one aspect, at least about 20%) by weight in another aspect, at least about 25% by weight in a further aspect, at least about 35% by weight in still further aspect, and at least about 50%> by weight in an additional aspect, based on the weight of the polysiloxane fluid. Typically, the degree of aryl substitution will be less than about 90% by weight, more typically less than about 85% by weight, and can generally range from about 55% to about 80% by weight of the polysiloxane fluid.

[0307] In another aspect, the high refractive index polysiloxane fluids have a combination of phenyl or substituted phenyl derivatives. The substituents can be selected from C₁-C₄ alkyl (e.g., methyl), hydroxy, and C₁-C₄ alkylamino.

[0308] When high refractive index silicones (silicone resins, silicone waxes, and phenyl modified silicones) are used in compositions with the sulfonic polymers, they optionally can be used in solution with a spreading agent, such as a silicone resin or a suitable surfactant, to reduce the surface tension by a sufficient amount to enhance spreading and thereby augment the glossiness (subsequent to drying) of hair treated with such compositions. Silicone fluids suitable for use in compositions with the sulfonic polymers are disclosed in U.S. Patent Nos. 2,826,551 ; 3,964,500; 4,364,837, and British Patent No. 849,433, all of which are incorporated herein by reference. High refractive index polysiloxanes and polyaryl siloxanes (trimethyl pentaphenyl trisiloxane, available under the trade name DC PH-1555 HRI) are offered from Dow Corning Corporation (Midland, MI), Huls America (Piscataway, N.J.), and Mo- mentive Performance Materials Inc. (Albany, N.Y.). Examples of silicone waxes include SF 1632 (INCI Name: Ceteryl Methicone) and SF1642 (INCI Name: C30-45 Alkyl Dimethicone), also available from Momentive Performance Materials, Inc.

[0309] Silicone resins and resin gels can be included as a silicone conditioning agent suitable for use in compositions with the sulfonic polymers. These resins are crosslinked polysiloxanes. The crosslinking is introduced through the incorporation of trifunctional and tetra-functional silanes with monofunctional and/or difunctional silanes during manufacture of the silicone resin.

[0310] As is well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional and tetra-functional siloxane monomer units (and hence, a sufficient level of crosslinking) such that they form a rigid or hard film are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. Silicone materials which have at least about 1.1 oxygen atoms per silicon atom will generally be silicone resins herein. In one aspect, the ratio of oxygen: silicon atoms is at least about 1.2: 1.0. Silanes used in the manufacture of silicone resins include monome- thyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and terachlorosilane, with the methyl-substituted silanes being most commonly utilized. In one aspect, suitable silicone resins are SS4230 (INCI Name: Cyclopetasiloxane (and) Trimethylsiloxysilicate) and SS4267 (INCI Name: Dimethicone (and) Trimethylsiloxysilicate) available from Momentive Performance Materials, Inc. Suitable silicone resin gels include RG100 (INCI Name: Cyclopetasiloxane (and) Dimethicone/ vinyltrimethylsiloxysilicate crosspolymer) from Wacker Chemical Corporation.

[031 1 ] Silicone materials and silicone resins can be identified according to a shorthand nomenclature system known to those of ordinary skill in the art as "MDTQ" nomenclature. Under this naming system, the silicone is described according to the presence of various siloxane monomer units which make up the silicone. Briefly, the symbol M denotes the monofunctional unit (CH₃)₃SiOo.5 ; D denotes the difunctional unit (CH₃)₂SiO; T denotes the trifunctional unit (CH₃)SiOi.₅; and Q denotes the quadra- or tetra-functional unit Si0₂. Primes of the unit symbols (e.g. M', D', , and Q') denote substituents other than methyl, and must be specifically defined for each occurrence. Typical alternate substituents include groups such as vinyl, phenyls, amines, hydroxyls, etc. The molar ratios of the various units, either in terms of subscripts to the symbol indicating the total number of each type of unit in the silicone (or an average thereof) or as specifically indicated ratios in combina- tion with molecular weight complete the description of the silicone material under the MDTQ system. Higher relative molar amounts of T, Q, T' and/or Q' to D, D', M and/or M' in a silicone resin is indicative of higher levels of crosslinking. As discussed before, however, the overall level of crosslinking can also be indicated by the oxygen to silicon ratio.

[0312] Exemplary silicone resins for use with the sulfonic polymers include, but are not limited to MQ, MT, MTQ, MDT and MDTQ resins. In one aspect, methyl is the silicone resin substituent. In another aspect, the silicone resin is selected from a MQ resins, wherein the M:Q ratio is from about 0.5 : 1.0 to about 1.5 : 1.0 and the average molecular weight of the silicone resin is from about 1000 to about 10,000 daltons.

[0313] When employed with non-volatile silicone fluids having a refractive index below 1.46, the weight ratio of the non-volatile silicone fluid to the silicone resin component, ranges from about 4: 1 to about 400: 1 in one aspect, from about 9: 1 to about 200: 1 in another aspect, from about 19: 1 to about 100: 1 in a further aspect, particularly when the silicone fluid component is a polydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluid and polydimethylsiloxane gum as described above. Insofar as the silicone resin forms a part of the same phase in the composi- tions hereof as the silicone fluid, i.e., the conditioning active, the sum of the fluid and resin should be included in determining the level of silicone conditioning agent in the composition.

[0314] The volatile silicones described above include cyclic and linear polydime- thylsiloxanes, and the like. As described previously in the formula for cyclic pol- ysiloxanes (cyclomethicones), they typically contain about 3 to about 7 silicon atoms, alternating with oxygen atoms, in a cyclic ring structure. However, each R 20 substituent and repeating unit, k, in the formula is selected so that the compound is

20

non-volatile. Typically, the R substituent is substituted with two alkyl groups (e.g., methyl groups). The linear volatile silicones are silicone fluids, as described above, having viscosities of not more than about 25 mPa-s. "Volatile" means that the silicone has a measurable vapor pressure, or a vapor pressure of at least 2 mm of Hg at 20°C. Non-volatile silicones have a vapor pressure of less than 2 mm Hg at 20°C. A description of cyclic and linear volatile silicones is found in Todd and Byers, "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, Vol. 91 (1), pp. 27-32 (1976), and in Kasprzak, "Volatile Silicones", Soap/Cosmetics/Chemical Specialities, pp. 40-43 (December 1986), each incorporated herein by reference.

[0315] Exemplary volatile cyclomethicones are D4 cyclomethicone (octamethyl- cyclotetrasiloxane), D5 cyclomethicone (decamethylcyclopentasiloxane), D6 cyclomethicone (dodecamethylcyclohexasiloxane), and blends thereof (e.g., D4/D5 and D5/D6). Volatile cyclomethicones and cyclomethicone blends are commercially available from Momentive Performance Materials Inc as SF1202, SF 1214, SF1256, and SF1258, Dow Corning, Midland, MI under the Xiameter^® cyclomethicone fluid product designations PMX-0244, PMX-245, PMX-246, PMX-345, and Dow Corn- ing 1401 fluid. Blends of volatile cyclomethicones and volatile linear dimethicones are also contemplated.

[0316] Exemplary volatile linear dimethicones include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and blends thereof. Volatile linear dimethicones and dimethicone blends are commercially available from Dow Corning as Xiameter^® PMX-200 silicone fluids (e.g., product designations 0.65 CS, 1 CS, 1.5 CS, and 2 CS) and Xiameter^® PMX 2-1 184 silicone fluid.

[0317] Emulsified silicones are also suitable for use with the sulfonic polymers. In one aspect, suitable emulsified silicones are emulsions of dimethicone with at least one emulsifier selected from non-ionic, anionic, amphoteric, cationic surfactant, and/ or cationic polymer and mixtures thereof. In one aspect, useful silicone emulsions have an average silicone particle size in the composition of less than 30 μιη, less than 20 μιη in another aspect, and less than 10 μιη in a further aspect. In another aspect, the average silicone particle size of the emulsified silicone in the composition is less than 2 μιη, and in another it ranges from 0.01 to 1 μιη. Silicone emulsions having an average silicone particle size of <0.15 μιη are generally termed micro-emulsions. Particle size may be measured by means of a laser light scattering technique, using a 2600D Particle Sizer from Malvern Instruments. Suitable silicone emulsions for use with the sulfonic polymers are also commercially available in a pre-emulsified form. Examples of suitable pre-formed commercially available emulsions include Dow Corning^® emulsions MEM-1664, 2-1352, MEM-1764, MEM-1784, HMW 2220, 2- 1865, MEM-1310, MEM-1491 , and 5-7137. These are emulsions/microemulsions of dimethiconol. Preformed emulsions of amino functional silicone are also available from suppliers of silicone oils such as Dow Corning (CE-8170, 5-71 13, 2-8194, 949, and CE 8401) and Momentive Performance Materials. Particularly suitable are emulsions of amino functional silicone oils with non ionic and/or cationic surfactant. Examples include Dow Corning^® 939 cationic emulsion, 949 cationic emulsion, 2- 8194 cationic microemulsion, and 2-8299 cationic emulsion, and 2-8177 non-ionic emulsion; as well as SM21 15 and SME253, non-ionic microemulsions supplied by Momentive Performance Materials. Mixtures of any of the above types of silicone may also be used. Other examples of amino functional silicones are the aminosili- cone oils. Suitable commercially available aminosilicone oils include Dow Corning Q2-8166, Q2-8220, and 2-8566; and SF 1708, (Momentive Performance Materials).

[0318] Other suitable silicone oils include the dimethicone copolyols, which are linear or branched copolymers of dimethylsiloxane (dimethicone) modified with alkylene oxide units. The alkylene oxide units can be arranged as random or block copolymers. A generally useful class of dimethicone polyols are block copolymers having terminal and/or pendent blocks of polydimethylsiloxane and blocks of poly- alkylene oxide, such as blocks of polyethylene oxide, polypropylene oxide, or both. Dimethicone copolyols can be water soluble or insoluble depending on the amount of polyalkylene oxide present in the dimethicone polymer and can be anionic, cationic, or non-ionic in character.

[0319] Water soluble or water dispersible silicones can also be used in compositions with the sulfonic polymers. Such water soluble silicones contain suitable anionic functionality, cationic functionality, and/or non-ionic functionality to render the silicone water soluble or water dispersible. In one aspect, the water soluble silicones contain a polysiloxane main chain to which is grafted at least one anionic moiety. The anionic moiety can be grafted to a terminal end of the polysiloxane backbone, or be grafted as a pendant side group, or both. By anionic group is meant any hydrocarbon moiety that contains at least one anionic group or at least one group that can be ionized to an anionic group following neutralization by a base. As discussed previously, the quantity of the hydrocarbon groups of anionic character which are grafted onto the silicone chain are chosen so that the corresponding silicone derivative is water-soluble or water-dispersible after neutralization of the ionizable groups with a base. The anionic silicone derivatives can be selected from existing commercial products or can be synthesized by any means known in the art. The non-ionic silicones contain alkylene oxide terminal and/or pendant side chain units (e.g., the dimethicone copolyols discussed above). Another example of non- ionic silicones is the silicone polyglucosides from Wacker (e.g., Wacker-Belsil^® SPG 128 VP, SPG 130 VP, and VSR 100 VP).

[0320] Silicones with anionic groups can be synthesized by reaction between (i) a polysiloxane containing a silinic hydrogen and (ii) a compound containing olefinic unsaturation that also contains an anionic functional group. Exemplary of such a reaction is the hydrosilylation reaction between poly(dimethylsiloxanes) containing a Si-H group(s) and an olefin, CH₂=CHR , wherein R represents a moiety containing an anionic group. The olefin can be monomeric, oligomeric or polymeric. Pol- ysiloxane compounds that contain a pendant reactive thio (-SH) group(s) are also suitable for grafting an unsaturated anionic group containing compound to the poly(siloxane) backbone.

[0321 ] According to one aspect, the anionic monomers containing ethylenic unsaturation are used alone or in combination and are selected from linear or branched, unsaturated carboxylic acids. Exemplary unsaturated carboxylic acids are acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and crotonic acid. The monomers can optionally be partially or completely neutralized by base to form an alkali, alkaline earth metal, and ammonium salt. Suitable bases include but are not limited to the alkali, alkaline earth (e.g., sodium, potassium, lithium, magnesium, calcium) and ammonium hydroxides. It will be noted that, similarly, the oligomeric and polymeric graft segments formed from the forgoing monomers can be post-neutralized with a base (sodium hydroxide, aqueous ammonia, etc.) to form a salt. Examples of such silicone derivatives which are suitable for use with the sulfonic polymers are described in European Patent Application No. EP 0 582 152 and International Patent Application Publication No. WO 93/23009. An exemplary class of silicone polymers are the polysiloxanes containing repeat units represented by the following structure:

1 2

wherein G represents hydrogen, Ci-Cio alkyl and phenyl radical; G represents Ci- Cio alkylene; G represents an anionic polymeric residue obtained from the polymerization of at least one anionic monomer containing ethylenic unsaturation; j is 0 or 1 ; t is an integer ranging from 1 to 50; and u is an integer from 10 to 350. In one

1 3

embodiment, G is methyl; j is 1 ; and G₂ is propylene radical; G represents a polymeric radical obtained from the polymerization of at least one unsaturated monomer containing a carboxylic acid group (e.g., acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, maleic acid, or aconitic acid, and the like).

[0322] In one aspect, the carboxylate group content in the final polymer ranges from 1 mole of carboxylate per 200 g of polymer to 1 mole of carboxylate per 5000 g of polymer. In one aspect, the number average molecular weight of the silicone polymer ranges from about 10,000 to about 1 ,000,000 daltons, and from 10,000 to 100,000 daltons in another aspect. Exemplary unsaturated monomers containing carboxylic acid groups are acrylic acid and methacrylic acid. In addition, to the carboxylic acid group containing monomers, C 1-C20 alkyl esters of acrylic acid and methacrylic acid can be copolymerized into the polymeric backbone. Exemplary esters include but are not limited to the ethyl and butyl esters of acrylic and methacrylic acid. A commercially available silicone-acrylate polymer is marketed by the 3M Company under the trademark Silicones "Plus" Polymer 9857C (VS80 Dry). These polymers contain a polydimethylsiloxane (PDMS) backbone onto which is grafted (through a thiopropylene group) random repeating units of poly(meth)acrylic acid and the butyl ester of poly(meth)acrylate. These products can be obtained conventionally by radical copolymerization between thiopropyl functionalized polydimethylsiloxane and a mixture of monomers comprising (meth)acrylic acid and of butyl(meth)acrylate.

[0323] In another aspect, the water soluble silicone copolyol useful with the sulfonic polymers are silicone copolyol carboxylates represented by the formula:

wherein R and R are independently selected from C 1-C30 alkyl, C₆-Ci₄ aryl, C7-C15

32 aralkyl, C 1-C15 alkaryl, or an alkenyl group of 1 to 40 carbons, hydroxyl, -R -G' or -(CH₂)₃0(EO)_a(PO)_b(EO)_c-G*, with the proviso that both R²⁸ and R²⁹ are not methyl; 30

R is selected from C 1-C5 alkyl or phenyl; in this formula a, b, and c are integers independently ranging from 0 to 100; EO is ethylene oxide, -(CH₂CH₂0)-; PO is propylene oxide, -(CH₂CH(CH₃)0)-; in this formula o is an integer ranging from 1 to 200, p is an integer ranging from 0 to 200, and q is an integer ranging from to 1000; R 31

0 is hydrogen, C 1-C30 alkyl, aryl, C7-C15 aralkyl, C7-C 15 alkaryl, or alkenyl group of 1 to 40 carbons or -C(0)-X wherein X is C 1-C30 alkyl, C₆-Ci₄ aryl, C7-C15 aralkyl, Ci-Ci₅alkaryl, or an alkenyl group of 1 to 40 carbons, or a mixture thereof; R 32 is a divalent group selected from alkylene radical of 1 to 40 carbon atoms which may be interrupted with arylene group of 6 to 18 carbons or an alkylene group containing unsaturation of 2 to 8 carbons; and G' is independently selected from a moiety represented by the formula:

O O O I I I I ^{■ ■} I I

-C-OH -C-O M — S-OH

II O

O O O I I II I I

s- -S-OH -s-

II I I II O O O

— C-R-C-OH . — C-R-C-O M

wherein R is a divalent group selected from alkylene of 1 to 40 carbons, an unsaturated group containing 2 to 5 carbon atoms, or an arylene group of 6 to 12 carbon atoms; where M is a cation selected from Na, K, Li, NH_4; or an amine containing at least one C 1 -C 10 alkyl, C6-C14 aryl (e.g., phenyl, naphthyl), C2-C10 alkenyl, C 1-C10 hydroxyalkyl, C7-C24 arylalkyl or C7-C24 alkaryl groups. Representative R 33 radicals are: -CH₂CH₂-, -CH=CH-, -CH=CHCH₂-, and phenylene.

[0324] In another embodiment, the water soluble silicones useful with the sulfonic polymers can be represented an anionic silicone copolyol represented by the formula: wherein is R³⁴ is methyl or hydroxyl; R³⁵ is selected from Ci-C₈ alkyl or phenyl; R³⁶ represents the radical -(CH₂)₃0(EO)_x(PO)_y(EO)_z-S0₃ ^~M⁺; where M is a cation selected from Na, K, Li, or NH₄; in this formula x, y and z are integers independently ranging from 0 to 100; R³⁷ represents the radical -(CH₂)₃0(EO)_x(PO)_y(EO)_z-H; in this formula a and c independently represent integers ranging from 0 to 50, and b is an integer ranging from 1 to 50; EO is ethylene oxide, e.g., -(CH₂CH₂0)-; PO is propylene oxide, e.g., -(CH₂CH(CH₃)0)-.

[0325] In still another embodiment, the water soluble silicones useful with the sulfonic polymers can be represented an anionic silicone copolyol represented by the formula:

wherein R 38 and R 39 independently are -CH₃ or a radical represented by:

-(CH₂)₃0(EO)_a(PO) _b(EO)_c-C(0)-R⁴¹-C(0)OH, subject to the proviso that both R³⁸ and R³⁹are not -CH₃ at the same time; R⁴¹ is selected from the divalent radical - CH₂CH₂, -CH=CH-, and phenylene; R⁴⁰ is selected from Ci-C₅ alkyl or phenyl; in this formula a, b and c are integers independently ranging from 0 to 20; EO is an ethylene oxide residue, e.g., -(CH₂CH₂0)-; PO is a propylene oxide residue, e.g., - (CH₂CH(CH₃)0)-; in this formula o is an integer ranging from 1 to 200 and q is an integer ranging from 0 to 500.

[0326] Other water soluble silicones useful with the sulfonic polymers are quaternized silicone copolyol polymers. These polymers have a pendant quaternary nitrogen functional group present and are represented by the formula: R42CH₂C(O)O-(EO)_z(PO)_v(EO)_x-(CH₂2)/3

wherein R represents a quaternary substituent -N R R R CA^", wherein R and R⁴⁶, and R⁴⁷, independently, are selected from hydrogen and linear and branched Ci- C₂4 alkyl, and CA^" represents an counter anion suitable to balance the cationic charge on the nitrogen atom; R⁴³ is selected from Ci-Cio alkyl and phenyl; R⁴⁴ is - (CH₂)30(EO)x(PO)y(EO)_z-H, where EO is an ethylene oxide residue, e.g., - (CH₂CH₂0)-; PO is a propylene oxide residue, e.g., -(CH₂CH(CH₃)0)-; in this formula a is an integer from 0 to 200, b is an integer from 0 to 200, and c is an integer from 1 to 200; in this formula x, y and z are integers and are independently selected from 0 to 20. In one aspect, the counter anion CA^" represents an anion selected from chloride, bromide, iodide, sulfate, methylsulfate, sulfonate, nitrate, phosphate, and acetate.

[0327] Other suitable water soluble silicones are amine substituted silicone copolyols represented by the formula:

wherein R is selected from -NH(CH₂)_nNH₂ or -(CH₂)_nNH₂; in this formula n is an integer from 2 to 6; and x, is n integer from 0 to 20; where EO is an ethylene oxide residue, e.g., -(CH₂CH₂0)-; PO is a propylene oxide residue, e.g., -(CH₂CH(CH₃)0)-; in this formula a is an integer from 0 to 200, b is an integer from 0 to 200, and c is an integer from 1 to 200; in this formula x, y and z are integers and are independently selected from 0 to 20.

[0328] Still other water soluble silicones can be selected from non-ionic silicone copolyols (dimethicone copolyols) represented by the formula: (R⁴⁹)₃Si(OSiR⁴⁶R⁴⁷)_x(OSi)_yOSi(R⁴⁹)₃

I

CH₉

I ²

CH₉

I ²

CH₂

O -(EO)_a(PO)_b(EO)_c-H

wherein R , independently, represents a radical selected from C 1 -C30 alkyl, C₆-Ci4 aryl, and C2-C20 alkenyl; R⁵⁰ represents a radical selected from C 1-C30 alkyl, C₆-Ci4 aryl, and C2-C20 alkenyl; EO is an ethylene oxide residue, e.g., -(CH₂CH₂0)-; PO is a propylene oxide residue, e.g., -(CH₂CH(CH₃)0)-; in this formula a, b, and c are, independently, 0 to 100; in this formula x is 0 to 200; and y is 1 to 200.

[0329] In another embodiment, water soluble silicones can be selected from non- ionic silicone copolyols represented by the formula:

HO-(EO)_c(PO)_b(EO)_c(CH₂)₃Si(OSiR5i R52)_nOSi(CH₂)₃O(EO)_a(PO)_b(EO)_c-H

51 52

wherein R and R , independently, represent a radical selected from C 1 -C30 alkyl, C₆-Ci4 aryl, and C2-C20 alkenyl; EO is an ethylene oxide residue, e.g.,

-(CH₂CH₂0)-; PO is a propylene oxide residue, e.g., -(CH₂CH(CH₃)0)-; in this formula a, b, and c are independently 0 to 100; and in this formula n is 0 to 200.

[0330] In the formulas set forth above, the EO and PO residues can be arranged in random, in nonrandom, or in blocky sequences.

[0331] Water soluble silicones are disclosed in U.S. Patent Nos. 5, 136,063 and 5, 180,843, the disclosures of which are incorporated herein by reference. Such silicones are commercially available under the Silsoft^® and Silwet^® trade names from Momentive Performance Materials. Specific product designations include, but are not limited to, Silsoft product designations 430, 440, 475, 805, 810, 840, 870, 875, 880, 895, 900, and 910; Silwet product designation L-7604. Other commercially available products include Dow Corning^® 5103 and 5329; Abil^® product designations B 88183, B 8843, Evonik Goldschmidt, and Silsense™ dimethicone copolyols, such as Silsense Copolyol-1 and Silsense Copolyol-7, available from Lubrizol Advanced Materials, Inc, Cleveland, OH.

[0332] The concentration of the silicone agents described above can range from about 0.01% to about 10%, by weight of the composition in which it is included. In another aspect, the amount of silicone agent ranges from about 0.1% to about 8%, from about 0.1% to about 5% in still another aspect, and from about 0.2% to about 3% by weight in a further aspect, all based on the total weight of the composition. Liquid Fatty Acid Soap Based Cleansers

[0333] In one aspect, a personal care composition in which the sulfonic polymers are useful is a fatty acid soap based cleanser. Typical components of a fatty acid based soap cleanser, in addition to the polymer thickener are: at least one fatty acid salt; an optional surfactant or mixture of surfactants; a sufficient pH adjusting agent (base and/or acid) to attain a pH of above 7 in one aspect, from about 7.5 to about 14 in another aspect, from about 8 to about 12 in still another aspect, and from about 8.5 to about 10 in a further aspect; and optional ingredients selected from the adjuvants, additives and benefit agents discussed above, and mixtures thereof, including benefit agents selected from silicones, humectants, pearlizing agents, vitamins, oils, fragrances, dyes, preservatives, botanicals, anti-dandruff agents, exfoliating agents, insoluble gas bubbles, liposomes, microsponges, cosmetic beads and flakes.

[0334] In one aspect, the fatty acid soaps are selected from at least one the fatty acid salt (e.g., sodium, potassium, ammonium) containing from about 8 to about 22 carbon atoms. In another aspect the liquid soap composition contains at least one fatty acid salt containing from about 12 to about 18 carbon atoms. The fatty acids utilized in the soaps can be saturated and unsaturated and can be derived from synthetic sources, as well as from the saponification of fats and natural oils by a suitable base (e.g., sodium, potassium and ammonium hydroxides). Exemplary saturated fatty acids include but are not limited to octanoic, decanoic, lauric, myristic, pentadecanoic, palmitic, margaric, steric, isostearic, nonadecanoic, arachidic, behenic, and the like, and mixtures thereof. Exemplary unsaturated fatty acids include but are not limited to the salts (e.g., sodium, potassium, ammonium) of myristoleic, palmitoleic, oleic, linoleic, linolenic, and the like, and mixtures thereof. The fatty acids can be derived from animal fat such as tallow or from vegetable oil such as coconut oil, red oil, palm kernel oil, palm oil, cottonseed oil, olive oil, soybean oil, peanut oil, corn oil, and mixtures thereof. The amount of fatty acid soap that can be employed in the liquid cleansing compositions of this embodiment ranges from about 1% to about 50% by weight in one aspect, from about 10%> to about 35%> by weight in another aspect, and from about 12% to 25% by weight in a further aspect, based on the weight of the total composition.

[0335] An optional anionic surfactant can be present in the soap composition in an amount ranging from about 1 % to about 25% by weight in one aspect, from about 5%> to about 20%) by weight in another aspect, and from 8%> to about 15%> by weight in a further aspect, based on the weight of the total weight of the soap composition. Mixtures of anionic and amphoteric surfactants can be used. The ratio of anionic surfactant to amphoteric surfactant can range from about 1 : 1 to about 10: 1 in one aspect, from about 2.25 : 1 to about 9: 1 in another aspect, and from about 4.5 : 1 to about 7: 1 in a further aspect.

[0336] In the foregoing soap embodiments, the amount of polymer can range from about 0.5%) to about 5%> by weight in one aspect, from about 1%> to about 3%> by weight in another aspect, and from about 1.5% to about 2.5% by weight in a further aspect, based on the total weight of the soap composition.

[0337] The liquid fatty acid soap based cleanser embodiments with the sulfonic polymers can be formulated as body washes, bath gels, shower gels, liquid hand soaps, body scrubs; bubble baths, facial scrubs, and foot scrubs, 2-in-l shampoos, baby shampoos, conditioning shampoos, bodifying shampoos, moisturizing shampoos, temporary hair color shampoos, 3-in-l shampoos, anti-dandruff shampoos, hair color maintenance shampoos, acid (neutralizing) shampoos, anti- dandruff shampoos, medicated shampoos, and salicylic acid shampoos, and the like. Natural and Synthetic Waxes

[0338] The natural and synthetic wax agents that can suitably be employed in the compositions of the technology, include, but are not limited to, carnauba wax, hydrolyzed carnauba wax, carnauba acid wax, ethoxylated carnauba wax (e.g., PEG- 12 carnauba wax), candelila wax, hydrolyzed candelilla wax, hydrogenated castor wax, bayberry wax, alfa wax, paraffin wax, ozokerite wax, olive wax, ouricury wax, palm kernel wax, rice wax, hydrogenated jojoba wax, bees wax, modified bees wax, e.g., oxidized beeswax, ethoxylated beeswax (e.g., PEG-6 beeswax, PEG-8 beeswax, PEG- 12 beeswax, PEG-20 beeswax), dimethicone copolyol beeswax esters and dimethiconol beeswax ester (e.g., bis-hydroxyethoxypropyl dimethicone beeswax esters, dimethicone PEG-8 beeswax, and dimethiconol beeswax available from Lubrizol Advanced Materials, Inc. under the Ultrabee^® trademark), cerabellina wax, marine waxes, lanolin and derivatives thereof, and polyolefin waxes, e.g., polyethylene wax; and mixtures thereof. The amount of natural and synthetic wax can range from about 1 wt.% to about 40 wt.% in one aspect, from about 3 wt.% to about 20 wt.% in another aspect, and from about 5 wt.% to about 10 wt.% in a further aspect, based on the weight of the total composition.

Moisturizers

[0339] Another ingredient which may be formulated with the hair styling and personal care compositions of the present technology is a moisturizer. As used herein, a "moisturizer" is an ingredient which promotes the retention of water to the surface area of the human body, including hair and scalp. Moisturizers that may used in accordance with the present technology include, without limitation, polyhydroxy alcohols, including butylene glycol, hexylene glycol, propylene glycol, sorbitol and the like; lactic acid and lactate salts, such as sodium or ammonium salts; C₃ and C₆ diols and triols including hexylene glycol, 1 ,4 dihydroxyhexane, 1 ,2,6-hexane triol; aloe vera in any of its forms, for example, aloe vera gel; sugars and starches; sugar and starch derivatives, for example alkoxylated glucose; hyaluronic acid; lactamide monoethanolamine; acetamide monoethanolamine; glycolic acid; alpha and beta hydroxy acids (e.g. lactic, glycolic and salicylic acid); glycerine; pantheol; patothenic acid, urea; vaseline; natural oils; oils and waxes (see the emollients section herein) and mixtures thereof. Moisturizers are generally recognized in the art of personal care, hair care, and skin care and in principle any moisturizer may be formulated into the compositions of the present technology.

[0340] The moisturizer will generally comprise from about 0.1 wt.% to about 15 wt. % in one aspect, from about 1 wt. % to about 10 wt. % in another aspect, and from 3 wt. % to about 8 wt. % in a further aspect, based on the total weight of the composition. Although the ingredients mentioned herein are generally defined as moisturizers, they may also possess other properties such as emolliency or other conditioning properties.

Opacifying/Pearlescent Materials

[0341 ] Some formulations are often opacified by deliberately incorporating pearlescent materials therein to achieve a cosmetically attractive pearl-like appearance, known as pearlescence. An opacifier often is included in a composition to mask an undesirable aesthetic property, such as to improve the color of a composition that is darkened due to the presence of a particular ingredient, or to mask the presence of particulate matter in the composition. Opacifiers also are included in aqueous compositions to improve the aesthetics and consumer acceptance of an otherwise esthetically unpleasing composition. For example, an opacifier can impart a pearlescent appearance to a clear composition, thereby communicating an appearance of creaminess, mildness and body to the consumer. Persons skilled in the art are aware of problems faced by formulators in consistently preparing a stable pearlescent formulation. A detailed discussion is found in the article "Opacifiers and pearling agents in shampoos" by Hunting, Cosmetic and Toiletries, Vol. 96, pages 65-78 (July 1981), incorporated herein by reference.

[0342] The opacifying or pearlescent material includes ethylene glycol mono- stearate, ethylene glycol distearate, polyethylene glycol distearate, stearic alcohol, bismuth oxychloride coated mica, mica coated metal oxides (e.g., titanium dioxide, chromium oxide, iron oxides), myristyl myristate, guanine, glitter (polyester or metallic), and mixtures thereof. Other pearlescent materials can be found in U.S.

Patent No. 4,654,207, U.S. Patent No. 5,019,376, and U.S. Patent No. 5,384, 1 14, which are herein incorporated by reference.

[0343] In one aspect, the amount of the pearlescent material can be used in amounts ranging from about 0.05% to about 10% by weight, and from about 0.1% to about 3%) by weight in another aspect, based upon the total weight of the stabilized composition.

Opacifiers

[0344] An opacifier is an ingredient included in a composition to reduce or eliminate the clear or transparent appearance of the composition. In addition, an opacifier also can impart other advantageous properties to a composition, such as thickening, suspending and emulsifying properties. [0345] An opacifier can be selected from a number of different chemical classes including inorganic compounds, e.g., various aluminum and magnesium salts, and organic compounds, like fatty alcohols, fatty esters and various polymers and copolymers. A representative listing of opacifiers is found in the CTFA Cosmetic Ingredient Handbook, J. Nikitakis, ed., The Cosmetic, Toiletry and Fragrance Association, Inc., Washington, D.C., 1988, at page 75.

Particulates

[0346] Numerous other substantially insoluble compounds and components which require stabilization and/or suspension can be utilized in the compositions with the sulfonic polymers. Examples of such other insoluble compounds include pigments, exfoliants, and anti-dandruff agents.

[0347] Exemplary pigments are metal compounds or semi-metallic compounds and may be used in ionic, non-ionic or oxidized form. The pigments can be in this form either individually or in admixture or as individual mixed oxides or mixtures thereof, including mixtures of mixed oxides and pure oxides. Examples are the titanium oxides (e.g., Ti0₂), zinc oxides (e.g., ZnO), aluminum oxides (for example, AI₂O₃), iron oxides (for example, Fe₂0₃), manganese oxides (e.g., MnO), silicon oxides (e.g., Si0₂), silicates, cerium oxide, zirconium oxides (e.g., Zr0₂), barium sulfate (BaS0₄), and mixtures thereof.

[0348] Other examples of pigments include D&C Red No. 30, D&C Red No. 36, D&C Orange No. 17, Green 3 Lake, Ext. Yellow 7 Lake, Orange 4 Lake, Red 28 Lake, the calcium lakes of D&C Red Nos. 7, 1 1 , 31 and 34, the barium lake of D&C Red No. 12, the strontium lake D&C Red No. 13, the aluminum lakes of FD&C Yellow No. 5 and No. 6, the aluminum lakes of FD&C No. 40, the aluminum lakes of D&C Red Nos. 21 , 22, 27, and 28, the aluminum lakes of FD&C Blue No. 1 , the aluminum lakes of D&C Orange No. 5, the aluminum lakes of D&C Yellow No. 10; the zirconium lake of D&C Red No. 33, iron oxides, thermochromic dyes that change color with temperature, calcium carbonate, aluminum hydroxide, calcium sulfate, kaolin, ferric ammonium ferrocyanide, magnesium carbonate, carmine, barium sulfate, mica, bismuth oxychloride, zinc stearate, manganese violet, chromium oxide, titanium dioxide nanoparticles, barium oxide, ultramarine blue, bismuth citrate, hydroxyapatite, zirconium silicate, carbon black particles and the like. Other suitable particulates include various optical modifiers as described in US Patent No. 7,202, 199.

[0349] Numerous cosmetically useful particulate exfoliating agents are known in the art, and the selection and amount is determined by the exfoliating effect desired from the use of the composition, as recognized by those skilled in the cosmetic arts. Useful exfoliating agents include, but are not limited to, natural abrasives, inorganic abrasives, synthetic polymers, and the like, and mixtures thereof. Representative exfoliants include, but are not limited to, ground or powdered pumice, stone, zeolites, nut shells (e.g., almond, pecan, walnut, coconut, and the like), nut meals (e.g., almond, and the like), fruit pits (e.g., apricot, avocado, olive, peach, and the like), hulls, seed and kernel (e.g., oat bran, corn meal, rice bran, grape seed, kiwi seed, wheat, jojoba seed, loofah seed, rose hip seed, and the like), plant matter (e.g., tea tree leaves, corn cob, fruit fibers, seaweed, loofah sponge, microcrystalline cellulose, and the like), bivalve shells (oyster shell, and the like), calcium carbonate, dicalcium pyrophosphate, chalk, silica, kaolin clay, silicic acid, aluminum oxide, stannic oxide, sea salt (e.g., Dead Sea salt), talc, sugars (e.g., table, brown, and the like), polyethylene, polystyrene, microcrystalline polyamides (nylons), microcrystalline polyesters, polycarbonates, and stainless steel fibers. The foregoing exfoliants can be used in the form of granules, powders, flours, and fibers.

[0350] Other generally insoluble components suitable for use in the present compositions include clay, swellable clay, laponite, gas bubbles, liposomes, microsponges, cosmetic beads and flakes. Cosmetic beads, flakes and capsules can be included in a composition for aesthetic appearance or can function as micro- and macro-encapsulants for the delivery of benefit agents to the skin and hair. Exemplary bead components include, but are not limited to, agar beads, alginate beads, jojoba beads, gelatin beads, Styrofoam™ beads, polyacrylate, polymethylmethacrylate (PMMA), polyethylene beads, Unispheres^™ and Unipearls™ cosmetic beads (Induchem USA, Inc., New York, NY), Lipocapsule™, Liposphere™, and Lipopearl™ microcapsules (Lipo Technologies Inc., Vandalia, OH), and Confetti II™ dermal delivery flakes (United-Guardian, Inc., Hauppauge, NY).

[0351 ] Any suitable anti-dandruff agent can be employed in the compositions with the sulfonic polymers. Exemplary anti-dandruff agents include, but are not limited to, sulfur, zinc pyrithione, zinc omadine, miconazole nitrate, selenium sulfide, piroctone olamine, N, N- bis(2- hydroxyethyl)undecenamide, cade oil, pine tar, Allium cepa extract Picea abies extract, and Undecyleneth-6, and the like, and mixtures thereof.

[0352] In one aspect, the amount of particulate component can range from about 0.1% to about 10% by weight based on the total weight of the composition.

Oxidizing and Reducing Agents

[0353] The compositions of the technology can include oxidizing and/or reducing agents. The oxidizing agent can be selected from the hydrogen peroxide, urea peroxide, alkali metal bromates, ferricyanides, persalts, and redox enzymes, optionally with their respective donor or cofactor. The reducing agent can be selected from thiols, like cysteine, thioglycolic acid, thiolacetic acid, their salts and esters, cysteamine, and its salts or sulfites. In the case of compositions intended for bleaching, ascorbic acid, its salts and its esters, erythorbic acid, its salts and its esters, and sulfinates, such as, sodium hydroxymethanesulfinate. The amount of oxidizing and/or reducing agent can range from about 0.01 wt.% to about 30 wt.% in one aspect, from about 0.05 wt.% to about 20 wt.% in another aspect, and from about 0.1 wt.% to about 5 wt.% in a further aspect, based on the total weight of the composition.

Pharmaceutical and Cosmeceutical Actives

[0354] The compositions of the present technology can be formulated with a pharmaceutical and/or a cosmeceutical active to deliver a desired effect. Examples of such active ingredients include, but are not limited to, caffeine, anti-stretch mark compounds, astringents (e.g., alum, oatmeal, yarrow, witch hazel, bayberry, and isopropyl alcohol), draining compounds, depilatories (e.g., calcium and sodium hydroxide, calcium or sodium thioglycolate, or mixtures thereof), hair growth promoting compounds (e.g., monoxidil), skin and hair nourishing compounds (e.g., bioquinones), skin and hair protecting compounds, self-tanning compounds (e.g., mono- or polycarbonyl compounds such as, for example, isatin, alloxan, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, tyrosine, tyrosine esters, and dihydroxyacetone), skin lighteners (e.g., kojic acid, hydroquinone, arbutin, fruital, vegetal or plant extracts, such as lemon peel extract, chamomile, green tea, paper mulberry extract, and the like, ascorbyl acid derivatives, such as ascorbyl palmitate, ascorbyl stearate, magnesium ascorbyl phosphate, and the like), lip plumping compounds, anti-aging, anti-cellulite, and anti-acne compounds (e.g., acidic agents such as alpha-hydroxy acids (AHAs), beta-hydroxy acids (BHAs), alpha amino-acids, alpha-keto acids (AKAs), acetic acid, azelaic acid, and mixtures thereof), anti-inflammatory compounds (e.g., aspirin, ibuprofen, and naproxen), analgesics (e.g., acetaminophen), antioxidant compounds, antiperspirant compounds (e.g., aluminum halides, aluminum hydroxyhalides, aluminum sulfate, zirconium (zirconyl) oxyhalides, zirconium (zirconyl) hydroxyhalides, and mixtures or complexes thereof), deodorant compounds (e.g., 2-amino-2-methyl-l-propanol (AMP), ammonium phenolsulfonate; benzalkonium chloride; benzethonium chloride, bromochlorophene, cetyltrimethylammonium bromide, cetyl pyridinium chloride, chlorophyllin-copper complex, chlorothymol, chloroxylenol, cloflucarban, dequalinium chloride, dichlorophene, dichloro-m-xylenol, disodium dihydroxy ethyl sulfosuccinylundecylenate, domiphen bromide, hexachlorophene, lauryl pyridinium chloride, methylbenzethonium chloride, phenol, sodium bicarbonate, sodium phenolsulfonate, triclocarban, triclosan, zinc phenolsulfonate, zinc ricinoleate, and mixtures thereof), anti-dandruff agents (e.g., sulfur, zinc pyrithione, zinc omadine, miconazole nitrate, selenium sulfide, piroctone olamine, N, N- bis(2- hydroxyethyl)undecenamide, cade oil, pine tar, Allium cepa extract Picea abies extract, and Undecyleneth-6, and mixtures thereof); and mixtures of any of the above.

[0355] The pharmaceutical and cosmeceutical actives can be present in an amount sufficient to deliver a pharmaceutical or cosmeceutical effect, the specific amount of which can readily be determined by one skilled in the pharmaceutical and cosmeceutical art. In one aspect, the amount of pharmaceutical and/or cosmeceutical active component can range from about 0.01 wt.% to about 15 wt.% in one aspect, from about 0.5 wt.% to about 10 wt.% in another aspect, and from about 1 wt.% to about 5 wt.% in a further aspect, based of the total weight of the composition.

Pigments and Colorants

[0356] Exemplary pigments are metal compounds or semi-metallic compounds and may be used in ionic, nonionic or oxidized form. The pigments can be in this form either individually or in admixture or as individual mixed oxides or mixtures thereof, including mixtures of mixed oxides and pure oxides. Examples are the titanium oxides (e.g., Ti0₂), zinc oxides (e.g., ZnO), aluminum oxides (for example, AI₂O₃), iron oxides (for example, Fe₂0₃), manganese oxides (e.g., MnO), silicon oxides (e.g., Si0₂), silicates, cerium oxide, zirconium oxides (e.g., Zr0₂), barium sulfate (BaS0₄), and mixtures thereof.

[0357] Other examples of pigments include D&C Red No. 30, D&C Red No. 36, D&C Orange No. 17, Green 3 Lake, Ext. Yellow 7 Lake, Orange 4 Lake, Red 28 Lake, the calcium lakes of D&C Red Nos. 7, 1 1 , 31 and 34, the barium lake of D&C Red No. 12, the strontium lake D&C Red No. 13, the aluminum lakes of FD&C Yellow No. 5 and No. 6, the aluminum lakes of FD&C No. 40, the aluminum lakes of D&C Red Nos. 21 , 22, 27, and 28, the aluminum lakes of FD&C Blue No. 1 , the aluminum lakes of D&C Orange No. 5, the aluminum lakes of D&C Yellow No. 10; the zirconium lake of D&C Red No. 33, iron oxides, thermochromic dyes that change color with temperature, calcium carbonate, aluminum hydroxide, calcium sulfate, kaolin, ferric ammonium ferrocyanide, magnesium carbonate, carmine, barium sulfate, mica, bismuth oxychloride, zinc stearate, manganese violet, chromium oxide, titanium dioxide nanoparticles, barium oxide, ultramarine blue, bismuth citrate, hydroxyapatite, zirconium silicate, carbon black particles and the like. Other suitable particulates include various optical modifiers as described in U.S. Patent No. 7,202, 199.

[0358] Mixtures of pigments and colorants to achieve a desired product color and the amount of each pigment and colorant to utilize is up to the formulator and is well within the skill in the formulation art. In one aspect the amount of pigment and/or colorant utilized in the compositions of the technology range from about 1 wt.% to about 20 wt.%, based on the total weight of the composition.

Plasticizers

[0359] One or more plasticizers can be added to the compositions of the present technology. A plasticizer is any material that will contribute to making the hair styling composition or film former less brittle and more flexible when applied to the hair, skin and nails. The plasticizers that can be used in the composition include, for example, dimethicone copolyol(s), polyols, polycarboxylic acids, polyesters, phthalate esters, benzoate esters, ethyoxylated lanolin alcohols; and mixtures thereof.

[0360] Exemplary dimethicone copolyols include, but are not limited to, PEG-1 Dimethicone, PEG-7 Dimethicone, PEG-8 Dimethicone, PEG- 12 Dimethicone, PEG- 14 Dimethicone, PEG-33 Dimethicone, PEG/PPG-15/15 Dimethicone, PEG/PPG- 18/18 Dimethicone, PPG- 12 Dimethicone; and mixtures thereof. Silsense™ dimethicone copolyols, such as Silsense Copolyol-1 and Silsense Copolyol-7, available from Lubrizol Advanced Materials, Inc. are examples of commercially available dimethicone copolyols.

[0361 ] Exemplary polyols include, but are not limited to, glycerin, glycols containing 2 to 5 carbon atoms (e.g. ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol), polyalkylene glycols (e.g., polyethylene and polypropylene glycols containing 2 to 100 repeating units), sugar alcohols such as sorbitol, manitol, maltitol, lactitol, mono-,di- and oligosaccharides such as fructose, glucose, sucrose, maltose, lactose, and combinations thereof.

[0362] Exemplary polycarboxylic acids include, but are not limited to, citric acid, maleic acid, succinic acid, polymaleic acid; and mixtures thereof.

[0363] Exemplary polyesters include, but are not limited to, glycerol triacetate, acetylated-monoglyceride, tri ethyl citrate, tributyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, diethylhexyl adipate, heptyl nonyl adipate, diisodecyl adipate, dicapryl adipate, dimethyl azelate, 2,2,4-trimethyl-l ,3-pentanediol diisobutyrate, methyl (or ethyl, or butyl) phthalyl ethyl glycolate, dibutyl fumarate, 2,2,4-trimethyl- 1 ,3-pentanediol diisobutyrate, di-n-butyl maleate, tricapryl trimellitate, heptyl nonyl trimellitate, triisodecyl trimellitate, triisononyl trimellitate, dimethyl sebacate, diethyl succinate, the butyl phenylmethyl ester of 1 ,2-benzenedicarboxylic acid; and mixtures thereof.

[0364] Exemplary phthalate esters include, but are not limited to, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, di-2-ethylhexyl phthalate, octyl decyl phthalate, diisodecyl phthalate, heptyl nonyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, butyl benzyl phthalates such as the n-butylbenzyl ester of o-phthalic acid, isodecyl benzyl phthalate, alkyl (C7/C9) benzyl phthalate, dimethoxy ethyl phthalate, 7- (2,6,6,8-tetramethyl-4-oxa-3-oxo-nonyl) benzyl phthalate; and mixtures thereof.

[0365] Exemplary benzoate esters include, but are not limited to, diethylene glycol dibenzoate and dipropylene glycol dibenzoate (such as the K-Flex® esters from Lubrizol Advanced Materials, Inc.), polyethylene glycol dibenzoate, 2,2,4- trimethyl-l ,3-pentanediol monoisobutyrate benzoate; and mixtures thereof. [0366] Other examples of plasticizers include, but are not limited to, the mineral oils, vegetable oils, triglycerides, lanolins and their derivatives, unsaturated fatty acids and their derivatives disclosed above, lactates (including but not limited to sodium, ammonium, and potassium salts), Sorbeth-30; urea, sodium pyrrolidone carboxylic acid (PCA); liposomes, serine, chitosan PCA, sodium hyaluronate, hyaluronic acid, soluble collagen, protein, modified protein, monosodium L- glutamate, lecithins and phospholipids and their derivatives; alpha and beta hydroxy acids such as glycolic acid, lactic acid, citric acid, maleic acid and salicylic acid; polysaccharides and their derivatives, and polyquaterniums, amino acids such as glutamic acid, aspartic acid, and lysine; and mixtures thereof.

[0367] Plasticizers will be present in a plasticizing effective amount. In one aspect, the plasticizer can be present in the formulation in an amount from about 0.05 wt.% to about 10 wt.%), from about 0.10 wt.% to about 5 wt.% in another aspect, and from about 0.5 wt. % to about 3 wt.% in a further aspect, based upon total weight of the hair styling composition.

Preservatives

[0368] Any preservative suitable for use in personal care products, can be used in the compositions of the present technology. In one aspect, suitable preservatives include polymethoxy bicyclic oxazolidine, methyl paraben, propyl paraben, ethyl paraben, butyl paraben, benzyltriazole, DMDM hydantoin (also known as 1 , 3 -dimethyl-5, 5 -dimethyl hydantoin), imidazolidinyl urea, phenoxyethanol, phenoxyethylparaben, methylisothiazolinone, methylchloroisothiazolinone, benzoisothiazolinone, triclosan, and suitable polyquaternium compounds disclosed above (e.g., Polyquaternium- 1).

[0369] In another aspect, acid based preservatives are useful in the compositions of the present technology. In one aspect, the acid preservative is a carboxylic acid

53 53

compound represented by the formula: R C(0)OH, wherein R represents hydrogen, a saturated and unsaturated hydrocarbyl group containing 1 to 8 carbon

53

atoms or C₆ to C₁₀ aryl. In another aspect, R is selected from hydrogen, a Ci to C₈ alkyl group, a C₂ to C₈ alkenyl group, or phenyl. Exemplary acids are, but are not limited to, formic acid, acetic acid, propionic acid, sorbic acid, caprylic acid, and benzoic acid, and mixtures thereof. [0370] In another aspect, suitable acids include but are not limited to, oxalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, maleic acid, fumaric acid, lactic acid, glyceric acid, tartronic acid malic acid, tartaric acid, gluconic acid, citric acid, ascorbic acid, salicylic acid, phthalic acid, mandelic acid, benzilic acid, and mixtures thereof.

[0371 ] Salts of the foregoing acids are also useful as long as they retain efficacy at low pH values. Suitable salts include the alkali metal (e.g., sodium, potassium, calcium) and ammonium salts of the acids enumerated above. An example of a suitable alkali metal salt preservative is sodium benzoate.

[0372] The acid based preservatives and/or their salts can be used alone or in combination with non-acidic preservatives typically employed in personal care, home care, health care, and institutional and industrial care products.

[0373] The preservatives typically comprise from about 0.01 wt.% to about 3.0 wt.% in one aspect, from about 0.1 wt.% to about 1 wt. % in another aspect, and from about 0.3 wt.% to about 1 wt.% by weight in a further aspect, based on the total weight of the compositions of the present technology.

Propellants

[0374] Where desired, any known aerosol propellant can be utilized to deliver the personal care, home care, health care, and institutional care compositions containing the sulfonic polymers in combination with one or more of the foregoing active ingredients and/or with the one or more additives and/or adjuvants, conventionally or popularly included in such products. Exemplary propellants include, but are not limited to, lower boiling hydrocarbons such as C3-C6 straight and branched chain hydrocarbons. Exemplary hydrocarbon propellants include propane, butane, isobutene, and mixtures thereof. Other suitable propellants include ethers, such as, dimethyl ether, hydro fluorocarbons, such as, 1 , 1-difluoroethane, and compressed gasses, such as air and carbon dioxide.

[0375] In one aspect, these compositions can contain from about 0.1% to about 60% by weight of a propellant, and from about 0.5 to about 35% by weight in another aspect, based on the total weight of the composition.

[0376] The sulfonic polymers can be utilized in any personal care, home care, health care, and institutional and industrial care composition requiring rheology and/or aesthetic property modification. In a given composition or application, the sulfonic polymers can, but need not, serve more than one function, such as a thickener, stabilizer, emulsifier, film former, carrier a deposition aid, and the like. The amount of polymer that can be employed depends upon the purpose for which they are included in a formulation and can be determined by person skilled in the formulation arts. Thus, as long as the physicochemical and functional properties of a desired product are achieved, a useful amount of polymer on a total composition weight basis, typically can vary in the range of from about 0.01 % to about 25% by weight in one aspect, from about 0.1 % to about 15% by weight in another aspect, from about 0.5% to about 10% by weight in a further aspect, and from about 1% to about 5% by weight in a still further aspect, but is not limited thereto.

[0377] The personal care, home care, health care, and institutional and industrial care compositions comprising the sulfonic polymers can be packaged and dispensed from containers such as jars, tubes, sprays, wipes, roll-ons, sticks and the like, without limitation. There is no limitation as to the form of the product in which these polymers can be incorporated, so long as the purpose for which the product is used is achieved. For example, personal and health care products containing the polymers can be applied to the skin, hair, scalp, and nails, without limitation in the form of gels, sprays (liquid or foams), emulsions (creams, lotions, pastes), liquids (rinses, shampoos), bars, ointments, suppositories, and the like.

[0378] In one personal care aspect, the sulfonic polymers are suitable for preparation of personal care (cosmetics, toiletries, cosmeceuticals), including, without limitation, hair care products (shampoos, combination shampoos, such as "two-in-one" conditioning shampoos), post-shampoo rinses, setting and style maintenance agents (including setting aids, such as gels and sprays, grooming aids such as pomades, conditioners, perms, relaxers, hair smoothing products, and the like), skin care products (facial, body, hands, scalp and feet), such as creams, lotions and cleansing products, antiacne products, antiaging products (exfoliant, keratolytic, anticellulite, antiwrinkle, and the like), skin protectants (sun care products, such as sunscreens, sunblock, barrier creams, oils, silicones and the like), skin color products (whiteners, lighteners, sunless tanning accelerators and the like), hair colorants (hair dyes, hair color rinses, highlighters, bleaches and the like), pigmented skin colorants (face and body make-ups, foundation creams, mascara, rouge, lip products, and the like) bath and shower products (body cleansers, body wash, shower gel, liquid soap, soap bars, syndet bars, conditioning liquid bath oil, bubble bath, bath powders, and the like), nail care products (polishes, polish removers, strengtheners, lengtheners, hardeners, cuticle removers, softness, and the like).

[0379] Toiletries and beauty aids containing the sulfonic polymers can include, without limitation, hair-removal products (shaving creams and lotions, epilators, after-shaving skin conditioner, and the like), hair growth promoting products, deodorants and antiperspirants, oral care products (mouth, teeth, gums), such as mouth wash, dentifrice, such as toothpaste, tooth powder, tooth polishes, tooth whiteners, breath fresheners, denture adhesives, and the like; facial and body hair bleach and the like. Other beauty aids that can contain the sulfonic polymers and include, without limitation, sunless tanning applications containing artificial tanning accelerators, such as dihydroxyacetone (DHA), tyrosine, tyrosine esters and the like: skin depigmenting, whitening and lightening, formulations containing such active ingredients as kojic acid, hydroquinone, arbutin, fruital, vegetable or plant extracts, (lemon peel extract, chamomile, green tea, paper mulberry extract, and the like), ascorbyl acid derivatives ascorbyl palmitate, ascorbyl stearate, magnesium ascorbyl phosphate and the like).

[0380] The sulfonic polymers are useful as suspending agents for particulates making them suitable for dermal cleansing products containing particulates, insoluble benefit agents, microabrasives, and abrasives and combinations thereof. Dermal cleansing products include shampoos, body washes, shower gels, bath gels, masks and skin cleansers.

[0381 ] Proteins

[0382] Any desired proteins, hydrolyzed proteins, protein derivatives, peptides, amino acids, and mixtures thereof (hereafter referred to as proteins for brevity) can be included in the compositions of the technology as a benefit agent to effect a desired benefit to the hair, skin, and scalp. Suitable proteins include, but are not limited to, natural structural hair and skin proteins, such as keratin, elastin, collagen, and reticulin, silk proteins, and the like. Suitable hydrolyzed proteins and protein derivatives include, but are not limited to, cocodimonium hydroxypropyl hydrolyzed casein, cocodimonium hydroxypropyl hydrolyzed collagen, cocodimonium hydroxypropyl hydrolyzed hair keratin, cocodimonium hydroxypropyl hydrolyzed rice protein, cocodimonium hydroxypropyl hydrolyzed silk, cocodimonium hydroxypropyl hydrolyzed soy protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed silk amino acids, hydroxypropyl trimonium hydrolyzed collagen, hydroxypropyl trimonium hydrolyzed keratin, hydroxypropyl trimonium hydrolyzed silk, hydroxypropyl trimonium hydrolyzed rice bran, hydroxypropyl trimonium hydrolyzed soy protein, hydroxypropyl trimonium hydrolyzed vegetable protein, hydroxypropyl trimonium hydrolyzed wheat protein, soyethyldimonium ethosulfate, soyethyl morpholinium ethosulfate, and the like. Suitable amino acids include wheat amino acids and those disclosed in U.S. Patent No. 4,201 ,235 and U.S. Patent No. 7,572,933 which are incorporated herein be reference.

[0383] The amount of protein(s) suitable for use in the present compositions can be easily determined by the artisan of ordinary skill depending upon the intended therapeutic or cosmeceutical purpose. In one aspect, the amount of protein(s) can range from about 0.01 wt.% to about 10 wt.%, from about 0.1 wt.% to about 5 wt.% in another aspect, and from about 0.5 wt.% to about 3 wt.% in a further aspect, based on the total weight of the composition.

Sheen Enhancing Agents

[0384] Sheen enhancing agents also known as glossifiers improve the sheen of fixative films when applied to a hair style. An exemplary sheen enhancer suitable for use in the hair styling compositions of the technology include the non-volatile arylsilicone fluids such as, for example, Phenyl Trimethicone and Diphenyl Dimethicone marketed by Dow Corning as Dow Corning^® 556, and Rhodia, Inc. as Mirasil^® DPDM, respectively. The Guerbet esters described herein also function as sheen or gloss enhancers. Guerbet esters are commercially available from Lubrizol Advanced Materials, Inc. under product designations G-20, G-36, G-38, and G-66. Murumuru butter also can be utilized as a sheen enhancing agent. In one aspect, the sheen enhancing agent, alone or in combination, typically comprises from about 1 wt.% to about 20 wt.% of the hair styling composition, from about 2 wt.% to about 15 wt.% in another aspect , and from about 3 wt. % to about 10 wt. % in a further aspect, based on the total weight of the hair styling composition.

Sunscreen Agents

[0385] A wide variety of sunscreen actives are useful herein. The exact amount and type of sunscreen that is used depends on the level of photo protection that is desired. Generally, any agent offering protection against ultraviolet radiation by absorbing, scattering or reflecting the ultraviolet radiation may be used herein. The sunscreen agents used herein may offer protection against one or more of the following forms of sunlight radiation UVA, UVB, UVC, visible light and infrared radiation. Generally, the sun protection factor (SPF) in the final formulation varies between 2 and 30, although products with SPFs up to 100 may be formulated. The sunscreen used herein may offer chemical or physical photo protection.

[0386] Sunscreens which can be used in accordance with the present technology include those selected from amino benzoic acid and derivatives, such as para-amino benzoic acid (PABA), glyceryl-PABA (Lisadimate), Padimate O, Roxadimate; anthrinalates, including methylanthrynilate; benzophenones, including dioxybenzone, oxybenzone and sulisobenzone, 3-benzophenone (Uvinul M40) 4-N,N- dimethylaminobenzoic acid ester with 2,4-dihydroxybenzophenone; camphor derivatives including 3-(4-methylbenzylidene) camphor, 3-benzylidene camphor; cinnamates including DEA-p-methoxycinnamate, ethyl-hexyl p-methoxy cinnamate, octocrylene, octyl methoxy cinnamate (Parasol MCX), dibenzoyl methanes including butylmethoxydibenzoylmethane (Parsol 1789), salicylates including, homomenthyl salicylate, octyl salicylate, trolamine methyl salicylate; metal oxides including titanium dioxide, zinc oxide and iron oxide; 2-phenylbenzimidazole-5-sulfonic acid; 4,4-methoxy-t-butyldibenzoylmethane; and mixtures thereof.

[0387] The amount of sunscreen agent employed in the composition can range from about 0.5 wt.% to about 30 wt.% in one aspect, from about 1 wt.% to about 25 wt.% in another aspect, and from about 2 wt.% to about 15 wt.% in a further aspect of the technology (based upon the weight of the total sunscreen composition). The exact amounts can vary depending on the UV absorbing agent(s) chosen and the desired SPF value of the composition.

Vitamins

[0388] Vitamin actives which may be used in accordance with the present technology include vitamin A and derivatives, including retinoic acid, retinyl aldehyde, retin A, retinyl palmitate, adapalene, and beta-carotene; vitamin B (panthenol, B3, provitamin B5, panthenic acid, vitamin B complex factor); vitamin C (ascorbic acid and salts thereof) and derivatives such as ascorbyl palmitate; vitamin D including calcipotriene (a vitamin D3 analog) vitamin E including its individual constituents alpha-, beta-, gamma-, delta-tocopherol and cotrienols and mixtures thereof and vitamin E derivatives including vitamin E palmitate, vitamin E linolate and vitamin E acetate; vitamin K and derivatives; vitamin Q (ubiquinone) and mixtures thereof.

[0389] Vitamins can be present in an effective amount necessary to deliver the intended therapeutic effect. In another aspect, the vitamin agent can be present in the formulation in an amount from about 0.001wt.% to about 5 wt.%, from about 0.10 wt.% to about 3 wt.% in another aspect, and from about 0.5 wt. % to about 2 wt.% in a further aspect, based upon total weight of the composition.

[0390] A process for making a high active, high bulk density detergent composition as well as the composition itself, the process comprising the steps of (i) introducing a binder component, comprising a neutralized or partially neutralized surfactant, surfactant precursor, sulfonic polymer, and/or its salts and a solid component of initial particle size from submicron to 500 μιη into a high shear mixer to thereby form a particulate mixture and (ii) subjecting said mixture to high shear mixing and thereby granulating 'the components to form granules of a size within the range of from 1 to 1200 μιη. Preferably after this mixing a coating agent such as zeolite is added to the mixer.

[0391 ] The detergent composition is suitably a complete detergent composition. The term "complete" is used to refer to a detergent composition comprising sufficient surfactant, builder, and alkalinity source to function as an effective fabric washing powder. Alkalinity source refers to soda ash or phosphates. The term "complete" does not restrict the addition of certain minor components in conventional amounts for example at weights of less than 5%>. Such minor components include enzymes, bleach, perfume, anti-deposition agent, or dye, to enhance the performance of the washing powder.

[0392] The particulate detergent composition may, if desired, be used as a feedstock in a detergent production process. For example, a liquid component surfactant such as nonionic surfactant may be sprayed onto the composition and it may then be coated with for example zeolite. If the detergent composition is used as a feedstock, it is preferred that it be the direct product. That is, additional components are not incorporated into the detergent particles prior to their use as a feedstock. However, if desired, the particles may be admixed with separate particles comprising other materials. This provides the advantage of allowing the detergent composition to be produced at one location by a single-step process and optionally admixture with separate particles and then transported to a remote location for storage or further processing as desired.

[0393] As a result of this viscosity increase, the process appears to be more easily controlled resulting in better powder properties for the detergent composition.

[0394] Examples of such viscosity raising components are water and, particularly, fatty acid in combination with a stoichiometric amount of alkaline material (such as caustic soda) sufficient to neutralize the fatty acid which obviously results in the formation of soap.

[0395] In the process a solid component, which can comprise detergency builders such as water-soluble alkaline inorganic materials (for example sodium carbonate seeded with calcium carbonate), zeolite, sodium tripolyphosphate, other water-soluble inorganic materials, for example, sodium bicarbonate or silicate, fluorescers, polycarboxylate polymers, anti-redeposition agents and fillers, is mixed with a binder component which in addition to a neutralized or partially neutralized surfactant can comprise water, silicate solution, liquid polymer components, polyethylene glycols, perfumes, fatty acids and other materials. The term binder component includes any component which is plastically deformable under conditions encountered during the process.

[0396] Examples of materials which may be postdosed to the composition include enzymes, bleaches, bleach precursors, bleach stabilizers, lather suppressors, perfumes and dyes. Liquid or pasty ingredients may conveniently be absorbed on to solid porous particles, generally inorganic, which may then be postdosed to the composition obtained.

[0397] The process is very flexible with respect to the chemical composition of the starting materials. Phosphate as well as zeolite built compositions may be made. The process is also suitable for preparing calcite/carbonate containing compositions.

[0398] The particulate solid component has an initial particle size of 0.1 to 500 μιη, preferably 1 to 350 μιη, more preferably from 0.1 to 300 μιη. The solid component preferably comprises from 5 to 95% of detergent builders, more preferably from 10 to 80%), most preferably from 20 to 60%> by weight. [0399] Preferably the binder component also comprises the sulfonic polymers and / or its salts. Preferably the binder component comprises a mixture of neutralized or partially neutralized, or unneutralized surfactants for example a mixture of linear or primary alkylbenzene sulfonate or sulfonic acid containing from 1 1 to 14 carbon atoms and a C₁₂ to C₁₅ primary alcohol ethoxylated with 3 to 7 moles of ethylene oxide per mole of alcohol in a weight ratio of anionic to nonionic of 3 to 1 or a mixture of a C 14 to Ci7 primary or secondary alcohol sulphate with a C₁₂ to C₁₅ primary alcohol ethoxylated with 3 to 7 moles of ethylene oxide per mole of alcohol in a weight ratio of 2 to 1.

[0400] The high shear mixer advantageously used to carry out the process is preferably a Littleford (TM) FM 130D mixer. This apparatus consists essentially of a large, static hollow cylinder with its longitudinal axis horizontal. Along this axis is a rotating shaft with several different types of blades mounted thereon. Preferably, when used to carry out the process the shaft tip speed is between 1 m/sec and 20 m/sec, more preferably 1 m/sec and 12 m/sec. The mixer can be equipped with one or more high speed cutters and preferably these are operated at tip speeds from 15 m/sec to 80 m/sec, more preferably from 20 m/sec to 70 m/sec. Other suitable mixers for the process are the Lodige™, Eirich™ RV02, Powrex™ VG100, Zanchetta™ , Schugi™ and Fukae™ .

[0401 ] In the process, the solid component is fed into the mixer followed by the binder component which is either sprayed on to the solid component or pumped into the mixer. The components are mixed for a total residence time preferably of from 0.2 to 8 minutes, more preferably of from 0.25 to 5 minutes. Optimally after this mixing time a coating agent such as zeolite can be added to the mixer and the mixer operated with only the main shaft for 20 to 60 seconds. The granules made by the process preferably have a bulk density of from 600 g/liter to 1 150 g/liter and a particle size (measured by Rosin-Rammler) of from 300 to 1 ,200 μιη more preferably from 400 to 800 μπι.

[0402] The ratio of binder component to solid component is preferably in a weight ratio of from 3:2 to 2:3, more preferably 1 : 1 to 2:3.

[0403] The process is operated at a temperature from ambient to 60°C, more preferably from ambient to 40°C. [0404] An aqueous alkaline laundry detergent slurry comprising: water, alkyl benzene sulphonate, sodium silicate; sulfonic polymer (e.g., acrylic/itaconic acid copolymer), sodium sulphate, sodium carbonate, magnesium sulphate, and other optional ingredients is prepared. This aqueous slurry is sprayed into a counter current spray drying tower and spray-dried to produce spray-dried laundry detergent powder.

[0405] In other embodiments, a hair fixative composition containing the sulfonic polymer may be in the form of an aerosol or non-aerosol spray, a mousse or a hair- setting lotion. The compositions may be aqueous, i.e., they are substantially free of organic solvents, or non-aqueous, although aqueous hair fixative compositions are preferred. The compositions may contain up to 40 weight percent, preferably up to 35 weight percent, of propellants, such as ethers, compressed gases, halogenated hydrocarbons and hydrocarbons. Exemplary propellants are dimethyl ether, propane, butane and 1 , 1-difluoroethane. Non-aerosol hair fixative compositions may further include solvents such as ethanol, isopropanol, acetone, dimethoxymethane and methyl ethyl ketone. In one aspect, the solvent in such non-aerosol compositions can be present in an amount ranging from 10 wt. to about 70 wt.%, from about 20 wt.% to about 60 wt. % in another aspect, and from about 25 wt.% to 50 wt. % in a further aspect, based on the total weight of the composition. Such propellants, solvents and materials or additives are commonly used in hair fixative compositions known heretofore.

[0406] Mousses according to the present technology comprise an amount of the polymer which is effective to impart hair fixative properties to the mousse, similar to gel fixatives. The mousses further comprise from about 0.25 to 6 weight percent, preferably 0.25 to 3 weight percent, of an emulsifier. The emulsifier may be nonionic, cationic, anionic or amphoteric. Exemplary nonionic emulsifiers include Tergitol® NP 15 (INC1 designation: Nonoxynol 15) and Brij 97 (INC1 designation: Oleth 10). The mousses also comprise from about 2.5 to 25 weight percent, preferably 5 to 15 weight percent, of a propellant as discussed above. The mousses may comprise additional ingredients as discussed above, with the balance of the mousse comprising water.

[0407] If desired, the clarity and appearance of the hair styling gel or personal care compositions of the technology can be adjusted. The clarity of the gel may vary from substantially transparent with little visual haze where insoluble component additives such as beads, air bubbles, pearlizing agents, are clearly visible to visually opaque. Visually distinct, multiple phase compositions where one phase is clear and another phase is opaque are also envisioned. In one embodiment of the hair gel, a pattern comprising phases that are visually distinct from each other may be formed by mixing clear and opaque components. The visual distinction between the phases can be in color, texture or the type of insoluble component contained therein. The specific pattern can be chosen from a wide variety of patterns, including, but not limited to striping, marbling, geometries, spirals, and combinations thereof. Compositions of this technology demonstrate excellent stability with time in suspending insoluble components and stabilizing visually distinct phases.

[0408] The polymers of the technology in addition to the hair fixative applications can usefully be employed for cosmetic purposes as film formers, skin barriers, skin protectants (e.g., sunscreens, sun block, barrier creams), pigmented skin colorants (e.g., face and body makeups, foundation creams, mascara, rouge, lip products, and the like), and can be formulated with any of the ingredients disclosed herein as well as with other ingredients known to the cosmetic industry and registered under CTFA International Cosmetic Ingredients Dictionary and Handbook.

[0409] The amount of each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated. However, unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, byproducts, derivatives, and other such materials which are normally understood to be present in the commercial grade.

[0410] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include: (i) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring); (ii) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); (iii) hetero substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms and encompass substituents as pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. In general, no more than two, or no more than one, non- hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; alternatively, there may be no non-hydrocarbon substituents in the hydrocarbyl group. In some embodiments the hydrocanyl groups described herein are alkyl groups.

[041 1 ] It is known that some of the materials described above may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. For instance, metal ions (of, e.g., a detergent) can migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the products formed upon employing the composition of the present invention in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses the composition prepared by admixing the components described above.

[0412] The disclosed technology may be better understood with reference to the following examples.

EXAMPLES

Example 1 - Monomer preparations

[0413] 2 -acrylamidododecane-l -sulfonic acid (CnAMPS) - Acrylonitrile (4,414 g) and 1-dodecene (3,366 g) were charged to a 12 liter resin kettle flask equipped with a Teflon stirring blade, thermowell, and condenser. Oleum (sulfuric acid with 20% free SO3) (2,276 g) was added dropwise over 5 hours at 5°C. The ratio of acrylonitrile, 1-dodecene, and oleum was 4.16: 1 : 1.16 by mole. The reaction was stirred overnight and C_HAMPS (1 ,020 g) was formed as a white precipitate. This solid was slowly settled, filtered, washed with acrylonitrile, and dried in vacuum. [0414] 2 -acrylamidohexadecane-l -sulfonic acid (C_HAMPS) - C_HAMPS (1 ,275 g) was prepared in the same manner as the above example with the exception that 1 - hexadecene was added instead of 1 -dodecene. The molar ratio of 1 -hexadecene compared to the other ingredients was the same as that of 1 -dodecene.

[0415] 2 -acrylamidooctadecane-1 -sulfonic acid (CigAMPS) - C_HAMPS is prepared in the same manner as the above two examples with the exception that 1 - octadecene is added instead of 1 -dodecene. The molar ratio of 1 -octadecene compared to the other ingredients is the same as that of 1 -dodecene.

Example 2 - Precipitation Copolymer preparations

[0416] Comparative copolymers as well as inventive polymers were prepared using a four neck flask fitted with a nitrogen inlet and thermocouple on one neck and a half moon stirrer on another, a condenser on another, and a stopper on another. A monomer mixture of 2-acrylamido-2-methylpropane-l -sulfonic acid (AMPS™2404) and the desired co-monomers was added to the reactor. The total monomer amount is 60.5g. Tertiary butanol (350g), and ammonium hydroxide 30 wt% aqueous solution (15.4g) were added to the reactor. The mixture was placed under nitrogen at about 0.5 CFH and the slurry heated in a water bath set at about 60°C under stirring. The mixture began clearing then slowly became hazy then milky. After 30 min, dilauryl peroxide (0.75 g) was added. The reaction was held at about 60°C for about an hour and refluxed at about 75 °C for about three hours. Dilauryl peroxide (0.75g) was added and the reaction was held at 75°C for three more hours. The mixture was then cooled to room temperature and the solid was filtered off with vacuum. The wet cake was dried at about 80°C in a vacuum drying oven for about 24 hrs giving a white powder. The compositions prepared by the foregoing method are shown in Table 1 below.

Table 1

2

Polymer AMPS™ 2404/CieAMPS = 83.2: 16.8 650

3

Comp 2 AMPS™ 2404/acrylamide = 80:20 41.5

Polymer AMPS™ 2404/acrylamide/Ci₆AMPS = 43.5

4 70:20: 10

Polymer AMPS™ 2404/Ci₈AMPS = 90: 10 18

5 rpm.

Example 3 - UV polymerization Co-polymer preparations

[0417] 50 g of 2-acrylamido-2-methylpropanesulfonic acid (AMPS ^11V1 2404), 75.47g of acrylamide (53% in water), and 10 g of C_HAMPS were dissolved in 64.53g of water. 0.05 g of 2-Hydroxy-2-methyl-l-phenyl-propane-l -one (Darocur® 1 173) was added. The total solids were 50%> by weight in water. The monomer solution was purged with nitrogen for 10 min and then transferred to petri dishes where the thickness of the monomer solution was around 1.5 mm. The polymerization took place using a Fusion UV 300S instrument by passing the Petri dish through the instrument twice using a belt speed of 20 ft/min. The polymer was placed in a vacuum oven, dried, and ground into a fine white powder. The viscosity of polymer solution in water (1 %) was 14, 150 mPa.s. Example 4 - Solution polymerization Co-polymer preparations

[0418] Polymer Example 6 - Into an agitator equipped reactor containing 237.5 grams of deionized water (D.I.), 175 grams of itaconic acid, 55 grams of acrylic acid and 75 grams of 20% C_HAMPS are added under nitrogen atmosphere and mixed at 300 rpms. The contents of the reactor are heated to about 75°C with mixing agitation (300 rpm) under a nitrogen atmosphere. When the contents of the reactor reaches a temperature of approximately 75°C, 35 grams of Bruggolite^®FF6 M solution (7.4% in water by weight) and 26.1 gram sodium persulfate solution (38 % in water by weight) are injected into the heated monomer mixture in 10 minutes interval. The reaction temperature is maintained at 75°C for two hours. Concurrently, sodium persulfate solution (26.1 % in water by weight) is also metered at 0.44 mL/minute into the reaction mixture for 120 minutes. The temperature of the reaction is maintained at about 75 °C for an additional four hours to complete the polymerization. The resulting terpolymer of itaconic acid, acrylic acid and C_HAMPS product is cooled to room temperature and adjusted the product pH to 2.5 with 50% NaOH before discharging from the reactor.

[0419] Polymer Example 7 - Into an agitator equipped reactor containing 170 grams of deionized water (D.I.) and 142.5 grams of itaconic acid are added under nitrogen atmosphere and mixed at 300 rpms. The contents of the reactor are heated to about 60°C with mixing agitation (300 rpm) under a nitrogen atmosphere for 30 minutes. When the contents of the reactor reaches a temperature of approximately 60°C, 35.5 grams of Bruggolite^®FF6 M solution (7.04%> in water by weight) and 26.25 gram sodium persulfate solution (38 % in water by weight) are injected into the heated IA solution in 10 minutes interval. After 30 minutes, the reaction temperature is raised to 75 °C. When the contents of the reactor reaches a temperature of approximately 75°C, sodium persulfate solution (28.5 % in water by weight) is also metered at 0.44 mL/minute into the reaction mixture for 75 minutes. Concurrently, the comonomer solutions, of 122.41 grams of sodium salt of 2- acrylamido-2-methylpropane sulfonic acid (50% in water, AMPS™ 2403) and 50 grams of 30 wt% C_HAMPS, are also gradually metered into the reactor over a period of about 60 minutes to react with IA. The temperature of the reaction is maintained at about 75 °C for an additional two to four hours to complete the polymerization. The resulting terpolymer of itaconic acid/ AMPS-Na/ C 12AMPS product is cooled to room temperature and adjusted the product pH to 2.5 with 50%> NaOH before discharging from the reactor.

[0420] Polymer Example 8 - A terpolymer of itaconic acid/ AMPS-Na/ C16AMPS product is also polymerized from the components set forth in Table below. The polymer is synthesized as set forth in Polymer 6, except that it contains C_HAMPS instead of C_HAMPS. Table 2

Example 5 - Calcium Binding Capacity of Terpolymers:

[0421 ] The calcium binding capacities of the terpolymers and benchmark chelators are tested by preparing a l OOmL of a 1 wt% solution of calcium chelating polymer in water and adding to a burette. The solution is titrated against lOOmL of a standard 0.01M CaC12 solution. A Ca selective electrode is used to measure the Ca ion signal present in solution (not bound to the polymer) until the electrode measures 0.00. Based on the number of Ca ions added to the solution, a back-calculation can be performed to determine the Ca binding capacity of the polymer. The results are shown in table below. Higher calcium binding capacity numbers are preferred for the chelation application.

Table 3

[0422] Each of the documents referred to above is incorporated herein by reference, including any prior applications, whether or not specifically listed above, from which priority is claimed. The mention of any document is not an admission that such document qualifies as prior art or constitutes the general knowledge of the skilled person in any jurisdiction. Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word "about." It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements.

[0423] As used herein, the transitional term "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, un-recited elements or method steps. However, in each recitation of "comprising" herein, it is intended that the term also encompass, as alternative embodiments, the phrases "consisting essentially of and "consisting of," where "consisting of excludes any element or step not specified and "consisting essentially of permits the inclusion of additional un-recited elements or steps that do not materially affect the basic and novel characteristics of the composition or method under consideration.

[0424] While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention. In this regard, the scope of the invention is to be limited only by the following claims.

Claims

What is claimed is:

1. A polymer comprising units derived from:

(A) a first monomer composition comprising an ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomer, where the monomer includes at least one alkyl group containing 5 to 30 carbon atoms, or salts thereof;

(B) a second monomer composition comprising one or more ethylenically unsaturated polymerizable monomers, or salts thereof;

wherein the second monomer composition (B) is different from the first monomer composition (A).

2. The polymer of claim 1, wherein (B) the second monomer composition comprises at least one of:

(i) one or more ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomers where the monomers of free of any alkyl groups containing more than 4 carbon atoms or salts thereof;

(ii) one or more carboxylic acid monomers or partial esters, or salts thereof;

(iii) one or more amide monomers;

(iv) one or more alkoxylated hydrophobically modified associative monomers;

(v) one or more phosphonic acid monomers or partial esters, or salts therof;

(vi) one or more vinyl monomers; or

(vii) any combination thereof. 3. The polymer of any of the claims 1 to 2 wherein (B) comprises one or more ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomers where the monomers are free of any alkyl groups containing more than 4 carbon atoms.

4. The polymer of any of the claims 1 to 3 wherein (B) comprises a compound having the structure:

where R⁴ is an alkyl group containing 1 to 4 carbon atoms; R⁵ is hydrogen or an alkyl group containing from 1 to 4 carbon atoms; and R⁶ is an alkyl group containing 1 to 4 carbon atoms; and R⁷ is hydrogen or a methyl group; or a metal, ammonium, or alkyla- mine salt thereof.

5. The polymer of any of the claims 1 to 4 wherein (B) comprises 2-acrylamido- 2-methypropane-l -sulfonic acid, a mono or multivalent metal of one or more thereof, an ammonium salt or one or more thereof, an alkylamine salt of one or more thereof or a combination thereof.

6. The polymer of any of the claims 1 to 5 wherein (B) comprises one or more ethylenically unsaturated polymerizable carboxylic acid monomers, or salts and/or esters thereof.

7. The polymer of any of the claims 1 to 6 wherein (B) comprises acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid or salts and/or esters thereof. 8. The polymer of any of the claims 1 to 7 wherein (B) comprises one or more acrylamide monomers.

9. The polymer of any of the claims 1 to 8 wherein (B) comprises one or more ethylenically unsaturated amido functional monomers selected from acrylamide, methyl acrylamide, methyl methacrylamide, N-alkylmethacrylamide, N,N-dialkylmethacrylamide, N-alkylacrylamide, and N,N-dialkylacrylamide.

10. The polymer of any of the claims 1 to 9 wherein the polymer further comprises units derived from: (C) a third monomer composition comprising one or more monomer that includes an alkyl group containing 1 to 18 carbon atoms comprising a simple ester, a vinyl ester, an mono-ally! ether, or salts thereof, or any combination thereof.

The polymer of any of the claims 1 to 10 wherein (A) comprises a compound I the structure:

where R 1 is an alkyl group containing from 5 to 30 carbon atoms; R 2 is hydrogen or an alkyl group containing from 1 to 30 carbon atoms; and R is an alkyl group containing 1 to 4 carbon atoms; and R⁷ is hydrogen or a methyl group;

or a metal, ammonium, or alkylamine salt thereof.

12. The polymer of any of the claims 1 to 11 wherein (A) comprises 2- acrylamidododecane-1 -sulfonic acid, 2-acrylamidohexadecane-l -sulfonic acid, 2- acrylamidooctadecane-1 -sulfonic acid, 2-acrylamidodecane-l -sulfonic acid, 2- acrylamidooctane-1 -sulfonic acid, 2-acrylamido-2,4,4-trimethylpentane-l -sulfonic acid, 2- acrylamidoheptadecane-1 -sulfonic acid, 2-acrylamidopentadecane-l -sulfonic acid, 2- acrylamido-2-octyldecane-l -sulfonic acid, 2-methacrylamidododecane-l -sulfonic acid, 2- methacrylamidohexadecane-1 -sulfonic acid, 2-methacrylamidooctadecane-l -sulfonic acid, 2-methacrylamidodecane-l -sulfonic acid, 2-methacrylamidooctane-l -sulfonic acid, 2- methacrylamido-2,4,4-trimethylpentane- 1 -sulfonic acid, 2-methacrylamidoheptadecane- 1 - sulfonic acid, 2-methacrylamidopentadecane-l -sulfonic acid, 2-methacrylamido-2- octyldecane-1 -sulfonic acid, an alkali metal of one or more thereof, an ammonium salt or one or more thereof, an alkylamine salt of one or more thereof, or a combination thereof.

13. The polymer of any of the claims 1 to 12 wherein the polymer is made up of:

0.1 to 50 percent by weight of monomer units derived from (A); and

1 to 99.9 percent by weight of monomer units derived from (B).

14. The polymer of any of the claims 2 to 12 wherein the polymer is made up of: 0.1 to 50 percent of monomer units derived from (A);

1 to 98.9 percent by weight units derived from (B); and

1 to 49 percent by weight units derived from (C).

15. The polymer of any of the claims 1 to 14 where the polymer is free of units derived from an alkylene glycol monomer.

16. The polymer of any of the claims 1 to 15 where the polymer units derived from the compounds of (A) have the following structures:

R¹ -R²

R³

SO3H

wherein:

R¹ is an alkyl group containing from 5 to 24 carbon atoms;

R is hydrogen or an alkyl group containing from 1 to 10 carbon atoms;

R is an alkyl group containing 1 to 4 carbon atoms;

R⁷ is hydrogen or a hydrocarbyl group;

or an alkali metal or ammonium salt thereof.

A process of making a polymer comprising the steps of:

(I) reacting:

(A) a first monomer composition comprising an ethylenically unsaturated hydrocarbylamidoalkanesulfonic acid monomer, where the monomer includes at least one alkyl group containing 5 to 30 carbon atoms, or salts thereof;

(B) a second monomer composition comprising one or more ethylenically unsaturated polymerizable monomers, or salts thereof; wherein the second monomer composition (B) is different from the first monomer composition (A).

18. The process of claim 17 wherein step (I) further comprises reacting: (C) a third monomer composition comprising one or more monomers that include an alkyl group containing 1 to 18 carbon atoms comprising a simple ester, a vinyl ester, an mono-allyl ether, or any combination thereof; with (A) and (B).

19. The use of the polymer of any of the claims 1 to 16 as a detergent builder and/or a thickening agent in an aqueous composition.