WO1996004887A1

WO1996004887A1 - Foaming detergent mixtures

Info

Publication number: WO1996004887A1
Application number: PCT/EP1995/003123
Authority: WO
Inventors: Jörg KAHRE; Hermann Hensen; Reinhard Müller; Holger Tesmann; Claudia Panzer
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1994-08-16
Filing date: 1995-08-07
Publication date: 1996-02-22
Also published as: DE4428823A1

Abstract

Detergent mixtures with improved foaming power contain (a) alkyl and alkenyl oligoglycosides having the general formula (I) R1O-[G]p, in which: R1 stands for an alkyl and/or alkenyl residue with 4 to 22 carbon atoms, G stands for a sugar residue with 5 or 6 carbon atoms and p equals 1 to 10; and (b) acyl glutamates having the formula (II), in which R2CO stands for a linear or branched acyl residue with 6 to 22 carbon atoms and 0, 1, 2 and/or 3 double bonds and X stands for hydrogen, an alkaline and/or alkaline-earth metal, ammonium, alkyl ammonium, alkanol ammonium or glucammonium.

Description

Foaming detergent mixtures

Field of the Invention

The invention relates to detergent mixtures with improved foaming power, containing alkyl glycosides and acylglutamates, surface-active agents which contain these mixtures and the use of the mixtures for the preparation of surface-active agents.

State of the art

Alkyl oligoglycosides, in particular alkyl oligoglucosides, are nonionic surfactants which are becoming increasingly important due to their excellent detergent properties and high ecotoxicological compatibility. The production and use of these substances have recently been described in a number of review articles, of which the publications by H.Hensen in Skin Care Forum, 1, (Oct. 1992), D.Balzer and N.Ripke in SeifenÖle- Fette waxes 118, 894 (1992) and B.Brancg in soap oils Fette waxes 118, 905 (1992) should be mentioned. Alkyl oligoglucosides are characterized by a foam strength that is otherwise only typical of anionic surfactants. This foam development can be increased in a synergistic manner by combination with other, preferably anionic, surfactants. From the large number of publications on this subject, representative and because of its fundamental importance, reference is made to European patent BP-B1 0070074 (Procter & Gamble), in which foaming detergent mixtures containing alkyl glycosides and anionic surfactants with carboxylate, sulfate and / or sulfonate structure be claimed.

Combinations of alkyl glucosides with acylated degradation products of vegetable or animal proteins, so-called protein fatty acid condensates, are also known. For example, the European patent applications EP-A1 0308189, EP-A1 0308190 and EP-A1 0309259 (Procter & Gamble) disclose toilet soaps which contain soap, cationic polymers and nonionic and anionic surfactants such as alkyl glucosides and protein fatty acid condensates.

From EP-A1 0521965 (Henkel), liquid personal cleansing agents are also known which also contain alkyl polyglucosides and protein fatty acid condensates.

European patent application EP-A1 0531650 (Kao) finally discloses hair shampoos based on anionic surfactants, cation polymers, polysiloxanes and vegetable protein fatty acid condensates, which may contain alkyl glucosides as an optional component. Combinations of alkyl glucosides with protein fatty acid condensates are distinguished by a particularly advantageous dermatological compatibility, but are unsatisfactory in terms of their foaming power. Accordingly, the object of the invention was to provide new detergent mixtures which are characterized by improved foaming power and at least equally good skin tolerance.

Description of the invention

The invention relates to foaming detergent mixtures comprising a) alkyl and alkenyl oligoglycosides of the general formula (I),

R ¹ 0- [G] _p (I) in which R ^{1 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10, and b ) Acylglutamates of the formula (II),

in which R ² CO represents a linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and X represents hydrogen, an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.

Surprisingly, it was found that mixtures of alkyl glucosides with acyl glutamates have very good dermatological compatibility and, compared to a combination with protein hydrolyzates, have improved foaming capacity with regard to both the base foam and the foam stability in the presence of water hardness.

Alkyl and / or alkenyl oligoglycosides

Alkyl and alkenyl oligoglycosides are known substances that can be obtained by the relevant methods of preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1 0301298 and WO 90/03977.

The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.

The index number p in the general formula (I) indicates the degree of oligomerization (DP degree), ie the distribution of mono and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3 are preferably used. From an application point of view, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.6 and in particular between 1.2 and 1.5.

The alkyl or alkenyl radical R ¹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxo synthesis. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP - 1.1 to 1.3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight. % C ₁₂ ^_ alcohol may be contaminated and alkyl oligoglucosides based on technical C9 / 11-oxo alcohols (DP = 1.1 to 1.3).

The alkyl or alkenyl radical R * can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1.1 to 1.6 are preferred.

Acylglutamates

Acyl glutamates are known anionic surfactants which can be obtained, for example, by Schotten-Baumann acylation of glutamic acid with fatty acids, fatty acid esters or chlorides. Sales products are available, for example, from Hoechst AG, Frankfurt / DE or Ajinomoto Co. Inc., Tokyo / JP. An overview of the production and properties of the acylglutamates is given by M.Takehara et al. in J.Am.Oil.Chem.Soc., 49, 143 (1972).

Formally, glutamic acid is one of the products that would be obtained by total hydrolysis of proteins. In fact, however, the hydrolysis of proteins leads to mixtures of oligopeptides which still have an average of 5 to 20 amino acid units. As a result, conventional protein fatty acid condensates represent acylation products of oligopeptides. Acylglutamates differ from these substances in that they represent "monomers" to a certain extent.

Typical examples of suitable acylglutamates which are considered as component (b) in the context of the invention are anionic surfactants which are derived from fatty acids having 6 to 22, preferably 12 to 18, carbon atoms, such as, for example, C12 / 14- or C12 / 18 -coconut fatty acid, lauric acid, myristine acid, palmitic acid and / or stearic acid. Sodium N-cocoyl and sodium N-stearoyl-L-glutamate are particularly preferred

The detergent mixtures according to the invention can contain the alkyl and / or alkenyl oligoglucosides and the acyl glutamates in a weight ratio of 1:99 to 99: 1, preferably 10:90 to 90:10 and in particular 80:20 to 50:50.

Surfactants

For the purposes of the invention, the surfactant mixtures according to the invention can be combined with further anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants.

Typical examples of anionic surfactants are alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, Glycerol ether, Hydroxymischethersulfate, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and Dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, acyl lactylates, alkyl oligoglucoside sulfates and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, fatty acid N-alkylglucamides, polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.

Typical examples of cationic surfactants are quaternary ammonium compounds and ester gates, in particular guatemated fatty acid trialkanolamine ester salts.

Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.

The surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example, J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), "Catalysts, Tenside und Mineralöladditive ", Thieme Verlag, Stuttgart, 1978, pp. 123-217.

The detergent mixtures according to the invention can have a proportion of the above-mentioned further surfactants from 0 to 90, preferably 5 to 15 and in particular 10 to 25% by weight, based on the solids content of the mixtures. Industrial applicability

The detergent mixtures according to the invention are notable for improved foaming power, a property which is important in the development of a large number of surface-active agents:

Further objects of the invention therefore relate to surface-active agents which have a content of these detergent mixtures and which are defined in more detail below: o Powdery universal detergents containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives . Liquid universal detergents containing 10 to 70% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Liquid mild detergent, containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives. o softening agents containing 10 to 50% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Hand dishwashing detergent, containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives. o rinse aid, containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Liquid cleaning agents and disinfectants, containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention, as well as customary auxiliaries and additives. o Bar soaps of the Kαmbibar type, containing 1 to 2% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Syndet soaps containing 1 to 2% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Hair shampoos containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Hair rinses containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Hair colorants containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Hair waving compositions containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Bubble baths containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Facial cleansing agent, containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Textile and fiber auxiliaries, containing 1 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Leather greasing agent, containing 1 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Flotation auxiliaries containing 1 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives. o Aids for dewatering of solids, containing 1 to 30% by weight, based on the agent, of the detergent mixtures according to the invention, and customary auxiliaries and additives. Auxiliaries and additives

Washing, rinsing, cleaning and conditioning agents based on the detergent mixtures according to the invention can contain - in addition to the surfactants already mentioned - other auxiliaries and additives, for example, builders, salts, bleaching agents, bleach activators, optical brighteners, graying inhibitors, solubilizers and enzymes.

Common builders are sodium aluminum silicates (zeolites), phosphates, phosphonates, ethylenediaminetetraacetic acid, nitrilotriacetate, citric acid and / or polycarboxylates. Suitable salts or adjusting agents are, for example, sodium sulfate, sodium carbonate or sodium silicate (water glass). Typical individual examples for further additives are sodium borate, starch, sucrose, polydextrose, TAED, stilbene compounds, methyl cellulose, toluenesulfonate, cumene sulfonate, long-chain soaps, silicones, misethers, lipases and proteases.

Hair shampoos, hair lotions or bubble baths can contain emulsifiers such as alkoxylated fatty alcohols or sorbitan esters as further auxiliaries and additives, in addition to the surfactants already mentioned. Substances such as polyethoxylated lanolin derivatives, lecithin derivatives and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers. Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol colmono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone as well as electrolytes such as table salt and ammonium chloride. Biogenic active substances are understood to mean, for example, plant extracts and vitamin complexes. Common film formers are, for example, chitosan, microcrystalline chitosan, guaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, guaternary cellulose derivatives and similar compounds. Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentadiol or sorbic acid. Suitable pearlizing agents are, for example, glycol distearic acid esters such as ethylene glycol distearate, but also fatty acid monoglycol esters. The dyes which can be used are the substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes" by the Dye Commission of the German Research Foundation, published by Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.

The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight, based on the composition.

A last subject of the invention finally relates to the use of the detergent mixtures according to the invention for the production of liquid or solid surface-active agents, in which they are present in amounts of 1 to 99 and preferably 10 up to 90 wt .-% - based on the solids content of the agent - may be included.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples

I. A set surfactant

A1) C _8/16 alkyl oligoglucoside

(PLANTAREN ^(R) APG 2000, Henkel KGaA, Düsseldorf / FRG)

B1) Sodium cocoyl L-glutamate

(Acylglutamate CS 11, Ajinomoto Co. Inc., Tokyo / JP) B2) Protein fatty acid condensate

(LAMEPON ^(R) S, Henkel KGaA, Düsseldorf / FRG)

B3) sodium lauryl ether sulfate

(TEXAPON (R) NSO, Henkel KGaA, Düsseldorf / FRG)

II. Foaming power

The foaming power was examined in accordance with Götte in accordance with DIN 53902, Part 1 (1 g AS / 1 at 15 ° d with 0.1 g Sebum according to Bey. The results for base foam and foam breakdown are summarized in Table 1 (percentages as% by weight) :

The examples and comparative examples show that a combination of alkyl oligoglucoside and acyl glutamate offers foaming power, which is achieved only when mixed with ether sulfates (albeit with lower dermatological compatibility). Mixing alkyl oligoglucoside with protein fatty acid condensates, on the other hand, leads to a lowering of the foam values to the level of pure protein fatty acid condensates. III. Recipe examples

The trade names are explained in Table 2 on the basis of their CTFA registration.

Claims

claims

1. Foaming detergent mixtures containing a) alkyl and alkenyl oligoglycosides of the general formula (I),

^R10 - [G] _p (I) in which R ^{1 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10, and b) acylglutamates of the formula (II),

2. Detergent mixtures according to claims 1 to 5, characterized in that they contain the alkyl and / or alkenyl oligoglucosides and the acyl glutamates in a weight ratio of 1:99 to 99: 1.

3. Detergent mixtures according to claims 1 and 2, characterized in that they further contain anionic surfactants which are selected from the group consisting of alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, oxomethyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol sulfate ethersulfates , Monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid arcosinates, fatty acid taurides, alkyl sulfate, acyl lactate, acyl lactate, acyl lactate / or protein fatty acid condensates are formed on an animal or vegetable basis.

4. Detergent mixtures according to claims 1 and 2, characterized in that they further contain non-ionic surfactants which are selected from the group consisting of fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, - alkoxylated triglycerol acid, fatty acid eniglycerol acid, fatty acid enol glycerol, fatty acid enol glycerol, fatty acids -Nalkylglucamiden, polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and protein hydrolyzates on an animal or preferably vegetable basis is formed.

5. Detergent mixtures according to claims 1 and 2, characterized in that they further contain cationic surfactants which are selected from the group formed by quaternary ammonium compounds and ester fuels, in particular quaternized difatty acid trialkanolamine ester salts.

6. Detergent mixtures according to claims 1 and 2, characterized in that they further contain amphoteric or zwitterionic surfactants which are selected from the group consisting of alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.

7. Powdered universal detergent containing 10 to 30% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

8. Liquid universal detergents containing 10 to 70% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

9. Liquid mild detergent containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

10. Hand dishwashing detergent, containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

11. Rinse aid, containing 10 to 50% by weight, based on the detergent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

12. Liquid detergents and disinfectants containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

13. Bar soaps of the combibar type, containing 1 to 2% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

14. Syndet soaps containing 1 to 2% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

15. Hair shampoos containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

16. Hair rinses containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

17. Hair colorants containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

18. Hair waving compositions containing 10 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

19. Bubble baths containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

20. Facial cleansing agent containing 10 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

21. Textile and fiber auxiliaries containing 1 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

22. Leather greasing agent, containing 1 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

23. Flotation auxiliaries containing 1 to 30% by weight, based on the composition, of the detergent mixtures according to the invention and customary auxiliaries and additives.

24. Aids for dewatering of solids, containing 1 to 30% by weight, based on the agent, of the detergent mixtures according to the invention and customary auxiliaries and additives.

25. Use of the detergent mixtures according to claim 1 for the production of surface-active agents.