CA2237839A1 - Polymer compositions - Google Patents
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- CA2237839A1 CA2237839A1 CA002237839A CA2237839A CA2237839A1 CA 2237839 A1 CA2237839 A1 CA 2237839A1 CA 002237839 A CA002237839 A CA 002237839A CA 2237839 A CA2237839 A CA 2237839A CA 2237839 A1 CA2237839 A1 CA 2237839A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/06—Other polishing compositions
- C09G1/14—Other polishing compositions based on non-waxy substances
- C09G1/16—Other polishing compositions based on non-waxy substances on natural or synthetic resins
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
Polymer compositions which are useful in floor polish compositions as wax replacements are disclosed. The compositions provide improved repair properties in floor polishes and provide a non-slippery floor polish.
Description
. ' 1 Polvmer Compositions This invention relates to polymer compositions, more specifically this invention relates to polymer compositions which are useful in floor polish compositions.
Floor polish compositions typically contain wax to enhance resistance properties cmd maintenance response. As a floor coated with wax-cont~ining polish is ex]posed to walking traffic, the polish becomes scuffed and develops black heel marks. Repair of the damaged polish is typically attempted through the use of a bllrni.~hing mal~hine. It is hoped that the repair will accomplish removal of scuffs and black marks, increase the gloss of the polish, and not scratch the polish. Although wax-containing floor polishes can be repaired through the process of burni~hing, there is a continuing need for floor polish compositions that provide improved repair properties.
Floor polish compositions which contain wax may be slippery. The slippery swrface may result in injuries due to slips and falls. There is a continuing need for non-slippery floor polish compositions. It is believed that the addition of a soft, hydrophobic emulsion polymer composition with pseudo-crystallinity to a floor polish composition will improve the repair properties of the floor polish and make the floor polish less slippery. Soft hydrophobic emulsion polymer compositions with pseudo-crystallinity have been difficult 1;o prepare due to the hydrophobicity of the monomers necessary to prepare the polymers.
U.S. Pat. No. 5,521,266 discloses a method for forming polymers from hydrophobic monomers. The disclosed method utilizes macromolecular organic compounds which have a hydrophobic cavity to complex monomers which have low water solubility. This enables the formation of polymers from low water solubility monomers by emulsion polymerization. Suitable monomers for use in the method for forming polymers include lauryl methacrylate.
Despite the disclosure of the prior art, there is a continuing need for a soft hydrophobic emulsion polymer composition with pseudo-crystallinity for use in floor polish compositions.
. ' 2 We have surprisingly found that the use of the polymer compositions of this invention aLLows a reduction in the amount of wax in fLoor polish compositions, while improving the repair properties for the fLoor polish, and m~king the ~Loor polish less slippery.
The present invention pro~,ides a. polymer composition comprising as polymerizecL units:
a) from 9.5 to 100 parts by weight of at least one C16 to C40 aLkyl ester of (meth)acrylic acid;
b) from 0 to 90 parts by weight of at least one ethylenicaLLy unsaturated monomer;
c) from 0 to 90 parts by weight of at least one ethylenicaLLy unsaturated acid cont~ining monomer or saLts thereof, and d) from 0 to 60 parts by weight of at least one aLkali soluble resin.
In an.other embodiment, the present invention provides a method for making a floor polish composition comprising:
a(lmi xin g a) from 10 to 90 parts by weight of a polymer composition comprising as polymerized units:
from 9.5 to 100 parts by weight of at least one Cl6 to Go aLkyl ester of (meth)acrylic acid;
from 0 to 90 parts by weight of at least one ethylenicaLly unsaturated monomer;
from 0 to 90 parts by weight of at least one ethylenically unsaturated acid cont~ining ]monomer or saLts thereof; and from 0 to 60 parts by weight of at least one alkali soluble resin; with b) from 0 to 90 parts by weight aLkali soluble resin;
c) from 10 t,o 90 parts by weight emulsion polymer floor finish vehicle; and d) from 10 to 80 parts by weight water.
The present invention also provides a floor polish composition comprising:
from 10 to 90 parts by weight emulsion polymer floor finish vehicle, from 0 to 90 parts by weight aLkali soluble resin, from 10 to 90 parts by weight polymer composition comprising as polymerized units:
from 9.5 to 100 parts by weight of at least one Cl6 to C40 alkyl ester of 'meth)acryliic acid;
from 0 to 90 parts by weight of at least one ethylenically unsaturated rnonomer;
from 0 to 90 parts by weight of at; least one ethylenic~lly unsaturated acid c ont~ining monomer or salts thereof;
from 0 to 60 parts by weight of at; least one alkali soluble resin; and from 10 to 80 parts by weight water.
The compositions of this invention may be prepared by a single stage or ~multi-stage process. The process may be an emulsion polym~ri7~tion such as the ]process described in U S. Pat. No. 5,521,266. The process may also be solution ]polymerization followed by em~ ific~tion as described in U.S. Pat. No.
,5,539,021, nnini-emulsion polymerization, or micro-emulsion polymerization.
:Emulsion polymerization is preferred. In the process utilized for preparing thesamples within this application, a first stage was prepared by adding a monomer ,emulsion and sodium persulfate to a solution cont~ining methyl-,~-cyclodextrin l("CD"), deionized water, and surfactant. The first stage was reacted at 85~C. Asecond stage was prepared by ms~king a second monomer emulsion and feeding the second monomer emulsion and a sodium persulfate solution to the reacted Eirst stage. The second stage was reacted at 85~C.
The polymer compositions of this invention are compositions which contain as polymerized units from 0 to lO0 parts by weight, preferably from 40 to 99 parts by weight, more preferably 90 to 98 parts by weight of at least one Cl6 to Go alkyl esl;er of (meth)acrylic acid. It is preferred that the alkyl ester of l(meth)acryl:ic acid be a Cl6 to C30 alkyl ester of (meth)acrylic acid. It is more ]preferred that the alkyl ester of (meth)acrylic acid be a Cl6 to Cls alkyl ester of (meth)acryl:ic acid. Suitable alkyl esters of (meth)acrylic acid include cetyl (meth)acryl;ate, stearyl (meth)acrylate, behenyl (meth)acrylate, and eicosyl l(meth)acryl;ate. Beneficial properties in floor polishes may be obtained by utilizing mc,re than one Cl6 to C40 alkyl ester of (meth)acrylic acid.
CA 02237839 1998-0~
The polymer composition of this invention also contains as polymerized units from () to 90 parts by weight, preferably 0 to 50 parts by weight, more preferably 1 to 20 parts by weight of at least one ethylenically unsaturated monomer. Suitable ethylenically unsaturated monomers for use in the preparation of the polymer compositions of this invention include, but are not limited to (meth)acrylic ester monomers including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, and hydroxypropyl acrylate; acrylamide or substituted acrylamides; styrene or substituted styrene; vinyl acetate or other vinyl esters; vinyl monomers such asvinyl chloride, vinylidene chloride, N-vinyl pyrolidone; and acrylonitrile or methacrylonitrile. Butyl acrylate, methyl methacrylate, and styrene are preferred. More preferred are butyl acrylate and methyl methacrylate.
The polymer composition of this invention also contains as polymerized units from 0 to 90 parts by weight, preferably 0 to 50 parts by weight, more preferably L to 15 parts by weight ethylenically unsaturated acid containing monomer or salts thereof. Suitable ethylenically unsaturated acid cont~ining monomers include, but are not limited to acrylic acid, methacl~lic acid, crotonic acid, phosp:hoethyl methacrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid, sodium vinyl sulfonate, itaconic acid, film~ric acid, maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate, and maleic anhydride.
Acrylic acid and methacrylic acid are preferred. Methacrylic acid is more preferred.
The polymer composition of this invention also contains as polymerized units from 0 to 60 parts by weight, preferably 0 to 40 parts by weight, more preferably 1) to 20 parts by weight alkali soluble resin. Alkali soluble resins useful in this invention are those typically with a weight average molecular below 500,000, preferably below 100,000, more preferably below 50,000.
The polymer compositions of this invention are useful in floor polish compositions. Floor polish compositions typically are emulsions which contain an emulsion polymer floor finish vehicle, water, alkali soluble resin, biocide, polyethylen.e wax, polypropylene wax, and coalescent solvents. The compositions of this invention are also useful in applications such as architectural and industrial coatings including paints, wood coatings, inks; adhesives; mastics;
plastics; pla,stic additives; petroleum additives and the like.
The polymer compositions of this invention are typically used in floor ~polish compositions by a(lmi~ing from ]0 to 90 parts by weight polymer composition of this invention by weight with a floor polish composition. It is preferred that from 10 to 50 parts by weight polymer composition of this invention b y weight be admixed with the floor polish composition. It is more preferred that from 15 to 26 parts by weight polymer composition of this invention by weight be admixed with the floor polish composition.
The emulsion polymer floor finish vehicle may be prepared by single stage or multi-stage emulsion polymerization. Emulsion polymeri7.~qtion processes are known in the art and are disclosed, for example in U.S. Pat. No. 5,346,954.
Multi-stage polymer processes are also known in the art and are disclosed, for example, in U.S. Pat. No. 4,325,856, 4,654,397, and 4,814,373 Suitable monomers for use in the preparation of the emulsion polymer floor finish vehicleinclude, bul; are not limited to acrylic ester monomers including methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate; acrylamide or substituted acrylamides; styrene or substituted styrene; vinyl acetate or other vinyl esters; vinyl monomers such as vinyl chloride, vinylidene chloride, N-vinyl pyrolidone; and acrylonitrile or methacrylonitrile.
Low levels of copolymerized ethylenically unsaturated acid monomers such as, for example, 0.1% - 10%, by weight based on the weight of the emulsion-polymerized polymer, acrylic acid, methacrylic acid, itaconic acid, film~ric acid, maleic acid and maleic anhydride may also be used in the emulsion polymer floor finish vehicle.
Chain transfer agents may be used to control the molecular weight of the emulsion polymer floor finish vehicle. Suitable chain transfer agents are mercaptan~, such as, for example, dodecylmercaptan. The chain transfer agent may be used at from 0.1% to 10% based on the total weight of the polymeric compositlon,.
CA 02237839 1998-0~
Conventional cros.~linking agents such as, for example, a polyaziridine, polyisocyanate, polycarbodiimide, polyamine and a polyva]Lent metal compound ]may be used in the emulsion polymer fLoor finish vehicle, providing that the cros~linkin~ agent does not inhibit fi]Lm formation. TypicaLLy, from 0.05% to 26%
of the cros.~linking agent is used, based on the weight of the polymer solids.
Emulsion polymer fLoor finish vehicles such as Rhoplex(~1421, .~crysol~644, and Acrysol(~Plus are typicaLLy used in fLoor po]Lish compositions to ]provide hard films with impact resistance. The range of emu]Lsion polymer fLoorfiinish vehic:Le typicaLLy uti]Lized in fLoor poLishes is from 10 to 90 parts by weight.
:[t is preferred that from 50 to 90 parts by weight of emuLsion polymer fLoor finish vehic'Le be utilized in the fLoor poliish. It is more preferred that from 70 to 90 ]parts by weight of emulsion polymer fLoor finish vehicle be ut;ili7.ed in the floor ]polish.
Alkali soluble resins are disclosed in U.S. Pat. No. 3,037,952. By a]Lkali soluble resin is meant a resin typica~Ly with a weight average molecular below ;00,000, preferably below 100,000, more preferably below 50,000. The a]Lkali soluble resin contains an acid functional group which typicaLLy is present at greater than 10% of the resin on a weight basis. The a]Lkali soluble resin forms a clear to translucent solution typicaLLy at a range of from pH 6 to pH 10. The ,alkali soluble resin may be prepared by the same process and with the same ]materia]Ls as the emulsion polymer fLoor finish vehicle described above.
The range of alkali soluble resin typically utilized in floor polishes is from O to 90 part.s by weight. It is preferred that from 5 to 50 parts by weight of alkali soluble resin be utilized in the iEloor polish. It is more preferred that from 10 to 30 parts by weight of alkali soluble resin be utilized in the floor polish.
Coale!scents are typically used to aid film formation in floor polishes.
Suitable coc~escents include diethylene glycol ethyl ether and tripropylene glycol ]methyl ether. Coalescents are typically utilized in floor polish compositions at from 0.1 to 10 parts by weight.
A biocide such as Kathon(~CG/ICP may be added to the floor polish composition to preserve the composition while in the bottle. Biocides are typically utilized in floor polish compositions at from 0.01% to 0.2% by weight.
CA 02237839 1998 - 0 j -1 j Wax emulsions such as EpoleneCR)E-43N and A-C 325N are typically used :in floor polish compositions to provide scuff and black mark resistance. Wax ~emulsions are typically uti~ized iII floor polish compositions at from 10 to 90parts by we:ight on a solids basis. It is preferred that from 10 to 50 parts by weight on a solids basis of wax emulsion be utilized in the floor polish. It is more preferred th.at from 10 to 20 parts by weight on a solids basis of wax emulsion be -utilized in the floor polish.
When the polymer compositions of this invention are incorporated into floor polish compositions, the resulting floor polish has improved repair properties and slip resistance.
The f'ollowing abbreviations are used throughout this patent application:
LMA = lauryl methacrylate SMA = stearyl methacrylate St = styrene ~MMA = methyl methacrylate BA = butyl acrylate MAA = methacrylic acid IBOMA = ic;obornyl methacrylate nDDM = n-dodecyl mercaptan Id. = sample identification number CD = methyl-,B-cyclodextrin g = grams ~C = degrees centigrade NH40H = aqueous ammonia J-678 = Joncryl(~) -678 Comp = Cornparative BMR = Black Mark Resistance SR = Scuff Resistance LC = long c]hain ~meth)acrylate = methacrylate and acrylate The f'ollowing Table lists some of the materials used in this patent application and their sources:
Material Function Source Triton@~ 45S anionic surfactant Union Carbide Pluronic~)L31 surfactant BASF
Joncrylt~)-6'78 alkali soluble resin SC Johnson Siponate(~I)S-4 surfactant Rhone-Poulenc Rhoplex(~1421 polymer Rohm andHaas Acrysol(~644 polymer Rohm andHaas Acrysol(~3)Plus polymer Rohm andHaas Kathon(~)CG/ICP biocide Rohm andHaas PolyEmulsion(~ 325N35 wax ChemCor Epolene@~)E-43N wax ChemCor CA 02237839 1998-0~
:Fluorad(~) FC-129 surfactant 3M Company SE-21 silicone Wacker Silicones Corporation F',x~mr)le 1 For stage 1, 400 g deionized water, Triton(~) XN-45S anionic surfactant (T~1), and 28.6 g CD were introduced into a 4-liter round bottom flask with fournecks equipped with a melh~nic~l stirrer, temperature control device, condenser, monomer and initiator feed lines, and a nitrogen inlet at room temperature. The contents were heated to 85~C while stirred under a nitrogen purge. A monomer emulsion of 31.3 g deionized water, 0.4 g Triton(~) XN-45S
anionic suri'actant, 33.8 g LMA, 7.5 g BA, 33 g MMA, and 0.75 g MAA was prepared separately. Solutions of 0.35% by weight sodium carbonate (based on the total monomer weight in stage 1 and stage 2) in 25 g deionized water and 0.35% by weight sodium persulfate (based on the total monomer weight in stage 1 and stage 2) in 30 g deionized water were introduced into the reaction kettle.The monomer emulsion was fed over a period of 20 minutes together with an initiator solution of 0.05% sodium persulfate (based on the total monomer weightin stage 1 and stage 2) in 210 g deionized water.
For stage 2, a monomer emulsion was prepared using 625 g deionized water, 7.8 g Triton(~ XN-45S anionic surfactant, and monomers according to Table 1. Im.mediately after the end of the stage 1 monomer emulsion feed, the stage 2 mon omer emulsion was fed over a period of 3 hours together with the sodium persulfate initiator solution.
Table 1 Id.Ll~![A SMA A MMA _ IBOMA nDDM MAA T~l 0 1395 0 75 0 0 0 30 11.9 2 0 1395 0 75 0 0 7.5 30 11.9 3 0 975 0 510 0 0 0 15 11.9 4 705 690 0 75 0 0 0 30 11.9 10'70 375 0 75 0 0 0 30 11.9 6 0 780 0 705 0 0 0 15 11.9 7 0 675 150 660 0 0 0 15 24.5 CA 02237839 1998-0~
8 0 525 150 150 660 0 0 15 24.5 9 0 600 150 150 585 0 0 15 24.5 0 675 150 150 510 0 0 15 24.5 11 0 750 150 150 435 0 0 15 24.5 12 0 675 0 150 0 650 0 15 24.5 13* 13'35 0 0 75 0 0 0 30 11.9 * = Comparative 3 for testing purposes (LMA) ~~,x~ml~le 2 A second set of samples to be tested in floor polishes was prepared by combining vvater, surfactant, J-678, CD, and NH40H in a kettle. To the kettle was then ad~ded a solution of ~mmonium persulfate in water. Finally, a ]monomer ernulsion cont~ining water, surfactant, and SMA and an ammonium ]persulfate solution in water were added to the kettle. The monomers were :reacted at 85~C.
Usingr the same equipment set UI) as Example 1, 543 g deionized water was introduced into the reaction flask at room temperature. The contents were heated to 55~C while stirred under a nitrogen purge. At 55~C, NH40H as set :Eorth in Table 2, CD as set forth in Tab]e 2, J-678 as set forth in Table 2, and 16 g Pluronic(~ L31 were introduced into the reaction flask. The contents were stirred for 2 hours at 55~C and heated to 85~C. A monomer emulsion cont~ining 104 g deionized water, 2.8 g of a 23% solution of siponate(~ DS-4, SMA as set iEorth in Table 2, and 16 g Pluronic L31 was prepared separately. A solution of 7 g ammonium persulfate in 25 g deionized water was added to the kettle. The ]monomer ernulsion was then added to the kettle at a rate of 5.5 g per minute.
An initiator solution of 7 g ammonium persulfate in 165 g deionized water was c o-fed at a rate of 1 g per minute.
Table 2 Id. (28%) (50%) J-678 SMA
14 37.1 0 160 640 92.8 14.9 400 400 16 37.1 14.9 160 640 F.xi~ml~le 3 - Floor Polish Applicat;ion And Testin~
Floor polishes were prepared according to the following formulation:
Material In Order Of Addition Percent By Wei~ht ~Tater 30 73 Kathon(~CG/ICP 0.03 ~crysol@~)644 (42%) 5.52 Fluorad@~ FC- 129 (50~/o) 0.02 I)iethylene Glycol Ethyl Ether 5.78 l'ripropylene Glycol Methyl Ether1.02 Rhoplex(~)1421 (38%) 45.76 E,polene~E-43N (40%) 4.35 Poly Emulsion(~) 325N35(35%) 4.97 ';E-21 0.02 The sample above is Compiarative 2 for testing purposes. For samples of the invention, an equal weight of the polymer composition of the invention was substituted for Epolene~)E-43N and Poly Emulsion~9 325N35. For samples of the invention with alkali soluble resin, an equal weight of Acrysol(~) Plus was substituted for Acrysol@~)644. For the no-wax control sample (Comparative 1 for testing purposes), the Rhoplex(~) 1421 level was increased on an equal weight basis to account for the removal of Epolene@~E-43N and Poly Emulsion 325N35.
The floor polishes were tested for wear in a corridor having a vinyl asbestos tile floor. The corridor was first stripped of residual polish. The floor was then repolished as follows:
The stripped floor was divided into equal sections perpendicular to the normal direction of corridor flow. To each section was applied a coat of the polish to be tested. The polish was applied with a mohair applicator at a rate of approximately 186 square meters / 3.8 liters. Three additional coats of polish were applied after allowing one hour for the previous coat to dry.
The polished tile floor was ,subjected to a daily traffic load of 800 to 1,200 passes. The overall durability of the polishes in terms of scuff and black heel mark resist,mce after being subjected to traffic was rated at weekly intervals on a 1 to 10 scale in ascending order of improving performance. Scuff was rated based on the number, size, and depth of the scuff marks. Black mark rating was based on the number, size, and darkness of the black marks. The polishes were then burnished at high speed with a propane powered bllrni.~hing machine operating a1; approximately 2,100 rotations per minute to repair the traffic damage. Repair was subjectively rated in terms of overall gloss increase, scuff and black mLark removal, and scratching as a result of the high speed burni~hing. Results of the tests with non alkali soluble resin cont~ining floor polishes are listed in Table 3. Results of the tests with alkali soluble resin cont~ining floor polishes are listed in Table 4.
Table 3 Sample SR BMR Repair LC Methacrvlate Comp 1 4 6 fair none Comp 2 7 9 good none Comp 3 6 7 fair LMA
7 9 very good SMA
3 6 8 very good SMA
4 8 9 excellent SMA / LMA
The above data demonstrat;es that the compositions of this invention can be substituted for wax in alkali soluble resin-free floor polishes without losing performance in terms of scuff resistance and black mark resistance. Floor polishes prepared with the compositions of this invention have better repair properties than wax cont~ining conventional floor polishes.
Table 4 Sample SR BMR Repair LC Methacrylate Comp 1 5 5 poor none Comp 2 7 8 fair none 16 8 8 fair SMA
9 8 good SMA
The above data demonstrates that the compositions of this invention can be substitu1;ed for wax in alkali soluble resin cont~ining floor polishes without losing performance in terms of scuff resistance and black mark resistance. Floorpolishes prepared with the compositions of this invention have better repair properties than wax cont~ining conventional floor polishes.
The samples were also tested for slip resistance. Three vinyl composition tiles were coated with ~loor polish by applying a 4 ml quantity of the polish in a puddle in *le center of the area to be coated. A Johnson and Johnson 2 inch by 2inch 12-ply gauze was allowed to absorb as much of the polish as possible. The polish was dispersed evenly over the surface of the tile with the saturated gauze pad, first by up and down and then by crosswise strokes. No pressure was used in applying the test polish to the tile. After the polish had dried at 70 degrees Fahrenheit / 55% relative humidity constant conditions, a second coat was applied in the same manner as the first. After the tiles had dried overnight, testing was performed.
The test was performed on the James friction testing machine. Slip resistance was reported as the static coefficient of friction which is a number between 0.00 and 1.00. The number is the average of four det~rtnin~tions run on the polish, the tile having been rotated 90~ between each determination. The closer the number is to 1.00, the less slippery the polish. The results of the tests are shown in Table 5.
Table 5 Id. Slip Resistance Comp 2 0.63 Comp 1 >o.g 3 0.85 0.81 The a~bove results demonstrate that the compositions of this invention provide floor polishes with better slip resistance than wax cont~ining floor polishes.
Floor polish compositions typically contain wax to enhance resistance properties cmd maintenance response. As a floor coated with wax-cont~ining polish is ex]posed to walking traffic, the polish becomes scuffed and develops black heel marks. Repair of the damaged polish is typically attempted through the use of a bllrni.~hing mal~hine. It is hoped that the repair will accomplish removal of scuffs and black marks, increase the gloss of the polish, and not scratch the polish. Although wax-containing floor polishes can be repaired through the process of burni~hing, there is a continuing need for floor polish compositions that provide improved repair properties.
Floor polish compositions which contain wax may be slippery. The slippery swrface may result in injuries due to slips and falls. There is a continuing need for non-slippery floor polish compositions. It is believed that the addition of a soft, hydrophobic emulsion polymer composition with pseudo-crystallinity to a floor polish composition will improve the repair properties of the floor polish and make the floor polish less slippery. Soft hydrophobic emulsion polymer compositions with pseudo-crystallinity have been difficult 1;o prepare due to the hydrophobicity of the monomers necessary to prepare the polymers.
U.S. Pat. No. 5,521,266 discloses a method for forming polymers from hydrophobic monomers. The disclosed method utilizes macromolecular organic compounds which have a hydrophobic cavity to complex monomers which have low water solubility. This enables the formation of polymers from low water solubility monomers by emulsion polymerization. Suitable monomers for use in the method for forming polymers include lauryl methacrylate.
Despite the disclosure of the prior art, there is a continuing need for a soft hydrophobic emulsion polymer composition with pseudo-crystallinity for use in floor polish compositions.
. ' 2 We have surprisingly found that the use of the polymer compositions of this invention aLLows a reduction in the amount of wax in fLoor polish compositions, while improving the repair properties for the fLoor polish, and m~king the ~Loor polish less slippery.
The present invention pro~,ides a. polymer composition comprising as polymerizecL units:
a) from 9.5 to 100 parts by weight of at least one C16 to C40 aLkyl ester of (meth)acrylic acid;
b) from 0 to 90 parts by weight of at least one ethylenicaLLy unsaturated monomer;
c) from 0 to 90 parts by weight of at least one ethylenicaLLy unsaturated acid cont~ining monomer or saLts thereof, and d) from 0 to 60 parts by weight of at least one aLkali soluble resin.
In an.other embodiment, the present invention provides a method for making a floor polish composition comprising:
a(lmi xin g a) from 10 to 90 parts by weight of a polymer composition comprising as polymerized units:
from 9.5 to 100 parts by weight of at least one Cl6 to Go aLkyl ester of (meth)acrylic acid;
from 0 to 90 parts by weight of at least one ethylenicaLly unsaturated monomer;
from 0 to 90 parts by weight of at least one ethylenically unsaturated acid cont~ining ]monomer or saLts thereof; and from 0 to 60 parts by weight of at least one alkali soluble resin; with b) from 0 to 90 parts by weight aLkali soluble resin;
c) from 10 t,o 90 parts by weight emulsion polymer floor finish vehicle; and d) from 10 to 80 parts by weight water.
The present invention also provides a floor polish composition comprising:
from 10 to 90 parts by weight emulsion polymer floor finish vehicle, from 0 to 90 parts by weight aLkali soluble resin, from 10 to 90 parts by weight polymer composition comprising as polymerized units:
from 9.5 to 100 parts by weight of at least one Cl6 to C40 alkyl ester of 'meth)acryliic acid;
from 0 to 90 parts by weight of at least one ethylenically unsaturated rnonomer;
from 0 to 90 parts by weight of at; least one ethylenic~lly unsaturated acid c ont~ining monomer or salts thereof;
from 0 to 60 parts by weight of at; least one alkali soluble resin; and from 10 to 80 parts by weight water.
The compositions of this invention may be prepared by a single stage or ~multi-stage process. The process may be an emulsion polym~ri7~tion such as the ]process described in U S. Pat. No. 5,521,266. The process may also be solution ]polymerization followed by em~ ific~tion as described in U.S. Pat. No.
,5,539,021, nnini-emulsion polymerization, or micro-emulsion polymerization.
:Emulsion polymerization is preferred. In the process utilized for preparing thesamples within this application, a first stage was prepared by adding a monomer ,emulsion and sodium persulfate to a solution cont~ining methyl-,~-cyclodextrin l("CD"), deionized water, and surfactant. The first stage was reacted at 85~C. Asecond stage was prepared by ms~king a second monomer emulsion and feeding the second monomer emulsion and a sodium persulfate solution to the reacted Eirst stage. The second stage was reacted at 85~C.
The polymer compositions of this invention are compositions which contain as polymerized units from 0 to lO0 parts by weight, preferably from 40 to 99 parts by weight, more preferably 90 to 98 parts by weight of at least one Cl6 to Go alkyl esl;er of (meth)acrylic acid. It is preferred that the alkyl ester of l(meth)acryl:ic acid be a Cl6 to C30 alkyl ester of (meth)acrylic acid. It is more ]preferred that the alkyl ester of (meth)acrylic acid be a Cl6 to Cls alkyl ester of (meth)acryl:ic acid. Suitable alkyl esters of (meth)acrylic acid include cetyl (meth)acryl;ate, stearyl (meth)acrylate, behenyl (meth)acrylate, and eicosyl l(meth)acryl;ate. Beneficial properties in floor polishes may be obtained by utilizing mc,re than one Cl6 to C40 alkyl ester of (meth)acrylic acid.
CA 02237839 1998-0~
The polymer composition of this invention also contains as polymerized units from () to 90 parts by weight, preferably 0 to 50 parts by weight, more preferably 1 to 20 parts by weight of at least one ethylenically unsaturated monomer. Suitable ethylenically unsaturated monomers for use in the preparation of the polymer compositions of this invention include, but are not limited to (meth)acrylic ester monomers including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, and hydroxypropyl acrylate; acrylamide or substituted acrylamides; styrene or substituted styrene; vinyl acetate or other vinyl esters; vinyl monomers such asvinyl chloride, vinylidene chloride, N-vinyl pyrolidone; and acrylonitrile or methacrylonitrile. Butyl acrylate, methyl methacrylate, and styrene are preferred. More preferred are butyl acrylate and methyl methacrylate.
The polymer composition of this invention also contains as polymerized units from 0 to 90 parts by weight, preferably 0 to 50 parts by weight, more preferably L to 15 parts by weight ethylenically unsaturated acid containing monomer or salts thereof. Suitable ethylenically unsaturated acid cont~ining monomers include, but are not limited to acrylic acid, methacl~lic acid, crotonic acid, phosp:hoethyl methacrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid, sodium vinyl sulfonate, itaconic acid, film~ric acid, maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate, and maleic anhydride.
Acrylic acid and methacrylic acid are preferred. Methacrylic acid is more preferred.
The polymer composition of this invention also contains as polymerized units from 0 to 60 parts by weight, preferably 0 to 40 parts by weight, more preferably 1) to 20 parts by weight alkali soluble resin. Alkali soluble resins useful in this invention are those typically with a weight average molecular below 500,000, preferably below 100,000, more preferably below 50,000.
The polymer compositions of this invention are useful in floor polish compositions. Floor polish compositions typically are emulsions which contain an emulsion polymer floor finish vehicle, water, alkali soluble resin, biocide, polyethylen.e wax, polypropylene wax, and coalescent solvents. The compositions of this invention are also useful in applications such as architectural and industrial coatings including paints, wood coatings, inks; adhesives; mastics;
plastics; pla,stic additives; petroleum additives and the like.
The polymer compositions of this invention are typically used in floor ~polish compositions by a(lmi~ing from ]0 to 90 parts by weight polymer composition of this invention by weight with a floor polish composition. It is preferred that from 10 to 50 parts by weight polymer composition of this invention b y weight be admixed with the floor polish composition. It is more preferred that from 15 to 26 parts by weight polymer composition of this invention by weight be admixed with the floor polish composition.
The emulsion polymer floor finish vehicle may be prepared by single stage or multi-stage emulsion polymerization. Emulsion polymeri7.~qtion processes are known in the art and are disclosed, for example in U.S. Pat. No. 5,346,954.
Multi-stage polymer processes are also known in the art and are disclosed, for example, in U.S. Pat. No. 4,325,856, 4,654,397, and 4,814,373 Suitable monomers for use in the preparation of the emulsion polymer floor finish vehicleinclude, bul; are not limited to acrylic ester monomers including methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate; acrylamide or substituted acrylamides; styrene or substituted styrene; vinyl acetate or other vinyl esters; vinyl monomers such as vinyl chloride, vinylidene chloride, N-vinyl pyrolidone; and acrylonitrile or methacrylonitrile.
Low levels of copolymerized ethylenically unsaturated acid monomers such as, for example, 0.1% - 10%, by weight based on the weight of the emulsion-polymerized polymer, acrylic acid, methacrylic acid, itaconic acid, film~ric acid, maleic acid and maleic anhydride may also be used in the emulsion polymer floor finish vehicle.
Chain transfer agents may be used to control the molecular weight of the emulsion polymer floor finish vehicle. Suitable chain transfer agents are mercaptan~, such as, for example, dodecylmercaptan. The chain transfer agent may be used at from 0.1% to 10% based on the total weight of the polymeric compositlon,.
CA 02237839 1998-0~
Conventional cros.~linking agents such as, for example, a polyaziridine, polyisocyanate, polycarbodiimide, polyamine and a polyva]Lent metal compound ]may be used in the emulsion polymer fLoor finish vehicle, providing that the cros~linkin~ agent does not inhibit fi]Lm formation. TypicaLLy, from 0.05% to 26%
of the cros.~linking agent is used, based on the weight of the polymer solids.
Emulsion polymer fLoor finish vehicles such as Rhoplex(~1421, .~crysol~644, and Acrysol(~Plus are typicaLLy used in fLoor po]Lish compositions to ]provide hard films with impact resistance. The range of emu]Lsion polymer fLoorfiinish vehic:Le typicaLLy uti]Lized in fLoor poLishes is from 10 to 90 parts by weight.
:[t is preferred that from 50 to 90 parts by weight of emuLsion polymer fLoor finish vehic'Le be utilized in the fLoor poliish. It is more preferred that from 70 to 90 ]parts by weight of emulsion polymer fLoor finish vehicle be ut;ili7.ed in the floor ]polish.
Alkali soluble resins are disclosed in U.S. Pat. No. 3,037,952. By a]Lkali soluble resin is meant a resin typica~Ly with a weight average molecular below ;00,000, preferably below 100,000, more preferably below 50,000. The a]Lkali soluble resin contains an acid functional group which typicaLLy is present at greater than 10% of the resin on a weight basis. The a]Lkali soluble resin forms a clear to translucent solution typicaLLy at a range of from pH 6 to pH 10. The ,alkali soluble resin may be prepared by the same process and with the same ]materia]Ls as the emulsion polymer fLoor finish vehicle described above.
The range of alkali soluble resin typically utilized in floor polishes is from O to 90 part.s by weight. It is preferred that from 5 to 50 parts by weight of alkali soluble resin be utilized in the iEloor polish. It is more preferred that from 10 to 30 parts by weight of alkali soluble resin be utilized in the floor polish.
Coale!scents are typically used to aid film formation in floor polishes.
Suitable coc~escents include diethylene glycol ethyl ether and tripropylene glycol ]methyl ether. Coalescents are typically utilized in floor polish compositions at from 0.1 to 10 parts by weight.
A biocide such as Kathon(~CG/ICP may be added to the floor polish composition to preserve the composition while in the bottle. Biocides are typically utilized in floor polish compositions at from 0.01% to 0.2% by weight.
CA 02237839 1998 - 0 j -1 j Wax emulsions such as EpoleneCR)E-43N and A-C 325N are typically used :in floor polish compositions to provide scuff and black mark resistance. Wax ~emulsions are typically uti~ized iII floor polish compositions at from 10 to 90parts by we:ight on a solids basis. It is preferred that from 10 to 50 parts by weight on a solids basis of wax emulsion be utilized in the floor polish. It is more preferred th.at from 10 to 20 parts by weight on a solids basis of wax emulsion be -utilized in the floor polish.
When the polymer compositions of this invention are incorporated into floor polish compositions, the resulting floor polish has improved repair properties and slip resistance.
The f'ollowing abbreviations are used throughout this patent application:
LMA = lauryl methacrylate SMA = stearyl methacrylate St = styrene ~MMA = methyl methacrylate BA = butyl acrylate MAA = methacrylic acid IBOMA = ic;obornyl methacrylate nDDM = n-dodecyl mercaptan Id. = sample identification number CD = methyl-,B-cyclodextrin g = grams ~C = degrees centigrade NH40H = aqueous ammonia J-678 = Joncryl(~) -678 Comp = Cornparative BMR = Black Mark Resistance SR = Scuff Resistance LC = long c]hain ~meth)acrylate = methacrylate and acrylate The f'ollowing Table lists some of the materials used in this patent application and their sources:
Material Function Source Triton@~ 45S anionic surfactant Union Carbide Pluronic~)L31 surfactant BASF
Joncrylt~)-6'78 alkali soluble resin SC Johnson Siponate(~I)S-4 surfactant Rhone-Poulenc Rhoplex(~1421 polymer Rohm andHaas Acrysol(~644 polymer Rohm andHaas Acrysol(~3)Plus polymer Rohm andHaas Kathon(~)CG/ICP biocide Rohm andHaas PolyEmulsion(~ 325N35 wax ChemCor Epolene@~)E-43N wax ChemCor CA 02237839 1998-0~
:Fluorad(~) FC-129 surfactant 3M Company SE-21 silicone Wacker Silicones Corporation F',x~mr)le 1 For stage 1, 400 g deionized water, Triton(~) XN-45S anionic surfactant (T~1), and 28.6 g CD were introduced into a 4-liter round bottom flask with fournecks equipped with a melh~nic~l stirrer, temperature control device, condenser, monomer and initiator feed lines, and a nitrogen inlet at room temperature. The contents were heated to 85~C while stirred under a nitrogen purge. A monomer emulsion of 31.3 g deionized water, 0.4 g Triton(~) XN-45S
anionic suri'actant, 33.8 g LMA, 7.5 g BA, 33 g MMA, and 0.75 g MAA was prepared separately. Solutions of 0.35% by weight sodium carbonate (based on the total monomer weight in stage 1 and stage 2) in 25 g deionized water and 0.35% by weight sodium persulfate (based on the total monomer weight in stage 1 and stage 2) in 30 g deionized water were introduced into the reaction kettle.The monomer emulsion was fed over a period of 20 minutes together with an initiator solution of 0.05% sodium persulfate (based on the total monomer weightin stage 1 and stage 2) in 210 g deionized water.
For stage 2, a monomer emulsion was prepared using 625 g deionized water, 7.8 g Triton(~ XN-45S anionic surfactant, and monomers according to Table 1. Im.mediately after the end of the stage 1 monomer emulsion feed, the stage 2 mon omer emulsion was fed over a period of 3 hours together with the sodium persulfate initiator solution.
Table 1 Id.Ll~![A SMA A MMA _ IBOMA nDDM MAA T~l 0 1395 0 75 0 0 0 30 11.9 2 0 1395 0 75 0 0 7.5 30 11.9 3 0 975 0 510 0 0 0 15 11.9 4 705 690 0 75 0 0 0 30 11.9 10'70 375 0 75 0 0 0 30 11.9 6 0 780 0 705 0 0 0 15 11.9 7 0 675 150 660 0 0 0 15 24.5 CA 02237839 1998-0~
8 0 525 150 150 660 0 0 15 24.5 9 0 600 150 150 585 0 0 15 24.5 0 675 150 150 510 0 0 15 24.5 11 0 750 150 150 435 0 0 15 24.5 12 0 675 0 150 0 650 0 15 24.5 13* 13'35 0 0 75 0 0 0 30 11.9 * = Comparative 3 for testing purposes (LMA) ~~,x~ml~le 2 A second set of samples to be tested in floor polishes was prepared by combining vvater, surfactant, J-678, CD, and NH40H in a kettle. To the kettle was then ad~ded a solution of ~mmonium persulfate in water. Finally, a ]monomer ernulsion cont~ining water, surfactant, and SMA and an ammonium ]persulfate solution in water were added to the kettle. The monomers were :reacted at 85~C.
Usingr the same equipment set UI) as Example 1, 543 g deionized water was introduced into the reaction flask at room temperature. The contents were heated to 55~C while stirred under a nitrogen purge. At 55~C, NH40H as set :Eorth in Table 2, CD as set forth in Tab]e 2, J-678 as set forth in Table 2, and 16 g Pluronic(~ L31 were introduced into the reaction flask. The contents were stirred for 2 hours at 55~C and heated to 85~C. A monomer emulsion cont~ining 104 g deionized water, 2.8 g of a 23% solution of siponate(~ DS-4, SMA as set iEorth in Table 2, and 16 g Pluronic L31 was prepared separately. A solution of 7 g ammonium persulfate in 25 g deionized water was added to the kettle. The ]monomer ernulsion was then added to the kettle at a rate of 5.5 g per minute.
An initiator solution of 7 g ammonium persulfate in 165 g deionized water was c o-fed at a rate of 1 g per minute.
Table 2 Id. (28%) (50%) J-678 SMA
14 37.1 0 160 640 92.8 14.9 400 400 16 37.1 14.9 160 640 F.xi~ml~le 3 - Floor Polish Applicat;ion And Testin~
Floor polishes were prepared according to the following formulation:
Material In Order Of Addition Percent By Wei~ht ~Tater 30 73 Kathon(~CG/ICP 0.03 ~crysol@~)644 (42%) 5.52 Fluorad@~ FC- 129 (50~/o) 0.02 I)iethylene Glycol Ethyl Ether 5.78 l'ripropylene Glycol Methyl Ether1.02 Rhoplex(~)1421 (38%) 45.76 E,polene~E-43N (40%) 4.35 Poly Emulsion(~) 325N35(35%) 4.97 ';E-21 0.02 The sample above is Compiarative 2 for testing purposes. For samples of the invention, an equal weight of the polymer composition of the invention was substituted for Epolene~)E-43N and Poly Emulsion~9 325N35. For samples of the invention with alkali soluble resin, an equal weight of Acrysol(~) Plus was substituted for Acrysol@~)644. For the no-wax control sample (Comparative 1 for testing purposes), the Rhoplex(~) 1421 level was increased on an equal weight basis to account for the removal of Epolene@~E-43N and Poly Emulsion 325N35.
The floor polishes were tested for wear in a corridor having a vinyl asbestos tile floor. The corridor was first stripped of residual polish. The floor was then repolished as follows:
The stripped floor was divided into equal sections perpendicular to the normal direction of corridor flow. To each section was applied a coat of the polish to be tested. The polish was applied with a mohair applicator at a rate of approximately 186 square meters / 3.8 liters. Three additional coats of polish were applied after allowing one hour for the previous coat to dry.
The polished tile floor was ,subjected to a daily traffic load of 800 to 1,200 passes. The overall durability of the polishes in terms of scuff and black heel mark resist,mce after being subjected to traffic was rated at weekly intervals on a 1 to 10 scale in ascending order of improving performance. Scuff was rated based on the number, size, and depth of the scuff marks. Black mark rating was based on the number, size, and darkness of the black marks. The polishes were then burnished at high speed with a propane powered bllrni.~hing machine operating a1; approximately 2,100 rotations per minute to repair the traffic damage. Repair was subjectively rated in terms of overall gloss increase, scuff and black mLark removal, and scratching as a result of the high speed burni~hing. Results of the tests with non alkali soluble resin cont~ining floor polishes are listed in Table 3. Results of the tests with alkali soluble resin cont~ining floor polishes are listed in Table 4.
Table 3 Sample SR BMR Repair LC Methacrvlate Comp 1 4 6 fair none Comp 2 7 9 good none Comp 3 6 7 fair LMA
7 9 very good SMA
3 6 8 very good SMA
4 8 9 excellent SMA / LMA
The above data demonstrat;es that the compositions of this invention can be substituted for wax in alkali soluble resin-free floor polishes without losing performance in terms of scuff resistance and black mark resistance. Floor polishes prepared with the compositions of this invention have better repair properties than wax cont~ining conventional floor polishes.
Table 4 Sample SR BMR Repair LC Methacrylate Comp 1 5 5 poor none Comp 2 7 8 fair none 16 8 8 fair SMA
9 8 good SMA
The above data demonstrates that the compositions of this invention can be substitu1;ed for wax in alkali soluble resin cont~ining floor polishes without losing performance in terms of scuff resistance and black mark resistance. Floorpolishes prepared with the compositions of this invention have better repair properties than wax cont~ining conventional floor polishes.
The samples were also tested for slip resistance. Three vinyl composition tiles were coated with ~loor polish by applying a 4 ml quantity of the polish in a puddle in *le center of the area to be coated. A Johnson and Johnson 2 inch by 2inch 12-ply gauze was allowed to absorb as much of the polish as possible. The polish was dispersed evenly over the surface of the tile with the saturated gauze pad, first by up and down and then by crosswise strokes. No pressure was used in applying the test polish to the tile. After the polish had dried at 70 degrees Fahrenheit / 55% relative humidity constant conditions, a second coat was applied in the same manner as the first. After the tiles had dried overnight, testing was performed.
The test was performed on the James friction testing machine. Slip resistance was reported as the static coefficient of friction which is a number between 0.00 and 1.00. The number is the average of four det~rtnin~tions run on the polish, the tile having been rotated 90~ between each determination. The closer the number is to 1.00, the less slippery the polish. The results of the tests are shown in Table 5.
Table 5 Id. Slip Resistance Comp 2 0.63 Comp 1 >o.g 3 0.85 0.81 The a~bove results demonstrate that the compositions of this invention provide floor polishes with better slip resistance than wax cont~ining floor polishes.
Claims (5)
1. A polymer composition comprising as polymerized units:
a) from 9.5 to 100 parts by weight of at least one C16 to C40 alkyl ester of (meth)acrylic acid;
b) from 0 to 90 parts by weight of at least one ethylenically unsaturated monomer;
c) from 0 to 90 parts by weight of at least one ethylenically unsaturated acid containing monomer or salts thereof, and d) from 0 to 60 parts by weight of at least one alkali soluble resin.
a) from 9.5 to 100 parts by weight of at least one C16 to C40 alkyl ester of (meth)acrylic acid;
b) from 0 to 90 parts by weight of at least one ethylenically unsaturated monomer;
c) from 0 to 90 parts by weight of at least one ethylenically unsaturated acid containing monomer or salts thereof, and d) from 0 to 60 parts by weight of at least one alkali soluble resin.
2. A composition according to claim 1 wherein the composition comprises:
a) from 40 to 99 parts by weight of at least one C16 to C40 alkyl ester of (meth)acrylic acid, b) from 0 to 50 parts by weight of at least one monomer selected from the group consisting of methyl methacrylate and butyl acrylate; and c) from 0 to 50 parts by weight methacrylic acid.
a) from 40 to 99 parts by weight of at least one C16 to C40 alkyl ester of (meth)acrylic acid, b) from 0 to 50 parts by weight of at least one monomer selected from the group consisting of methyl methacrylate and butyl acrylate; and c) from 0 to 50 parts by weight methacrylic acid.
3. A composition according to claim 1 wherein the composition comprises:
a) from 90 to 98 parts by weight of stearyl (meth)acrylate, b) from 1 to 20 parts by weight of methyl methacrylate; and c) from 1 to 15 parts by weight methacrylic acid.
a) from 90 to 98 parts by weight of stearyl (meth)acrylate, b) from 1 to 20 parts by weight of methyl methacrylate; and c) from 1 to 15 parts by weight methacrylic acid.
4. A method for making a floor polish composition comprising:
admixing a) from 10 to 90 parts by weight of a polymer composition comprising as polymerized units:
from 9.5 to 100 parts by weight of at least one C16 to C40 alkyl ester of (meth)acrylic acid;
from 0 to 90 parts by weight of at least one ethylenically unsaturated monomer;
from 0 to 90 parts by weight of at least one ethylenically unsaturated acid containing monomer or salts thereof; and from 0 to 60 parts by weight of at least one alkali soluble resin; with b) from 0 to 90 parts by weight alkali soluble resin;
c) from 10 to 90 parts by weight emulsion polymer floor finish vehicle; and d) from 10 to 80 parts by weight water.
admixing a) from 10 to 90 parts by weight of a polymer composition comprising as polymerized units:
from 9.5 to 100 parts by weight of at least one C16 to C40 alkyl ester of (meth)acrylic acid;
from 0 to 90 parts by weight of at least one ethylenically unsaturated monomer;
from 0 to 90 parts by weight of at least one ethylenically unsaturated acid containing monomer or salts thereof; and from 0 to 60 parts by weight of at least one alkali soluble resin; with b) from 0 to 90 parts by weight alkali soluble resin;
c) from 10 to 90 parts by weight emulsion polymer floor finish vehicle; and d) from 10 to 80 parts by weight water.
5. A floor polish composition comprising:
from 10 to 90 parts by weight emulsion polymer floor finish vehicle, from 10 to 90 parts by weight alkali soluble resin, from 10 to 90 parts by weight polymer composition comprising as polymerized units:
from 9.5 to 99 parts by weight of at least one C16 to C40 alkyl ester of (meth)acrylic acid;
from 0 to 90 parts by weight of at least one ethylenically unsaturated monomer;
from 0 to 90 parts by weight of at least one ethylenically unsaturated acid containing monomer or salts thereof;
from 0% to 60% by weight of at least one alkali soluble resin; and from 10 to 80 parts by weight water.
from 10 to 90 parts by weight emulsion polymer floor finish vehicle, from 10 to 90 parts by weight alkali soluble resin, from 10 to 90 parts by weight polymer composition comprising as polymerized units:
from 9.5 to 99 parts by weight of at least one C16 to C40 alkyl ester of (meth)acrylic acid;
from 0 to 90 parts by weight of at least one ethylenically unsaturated monomer;
from 0 to 90 parts by weight of at least one ethylenically unsaturated acid containing monomer or salts thereof;
from 0% to 60% by weight of at least one alkali soluble resin; and from 10 to 80 parts by weight water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US4726197P | 1997-05-21 | 1997-05-21 | |
| US60/047,261 | 1997-05-21 |
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| Publication Number | Publication Date |
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| CA2237839A1 true CA2237839A1 (en) | 1998-11-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002237839A Abandoned CA2237839A1 (en) | 1997-05-21 | 1998-05-15 | Polymer compositions |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US6040409A (en) |
| EP (1) | EP0879852B1 (en) |
| JP (1) | JPH10330574A (en) |
| KR (1) | KR19980087148A (en) |
| CN (1) | CN1201806A (en) |
| AR (1) | AR012685A1 (en) |
| AU (1) | AU743666B2 (en) |
| BR (1) | BR9801658A (en) |
| CA (1) | CA2237839A1 (en) |
| DE (1) | DE69821052T2 (en) |
| ES (1) | ES2213876T3 (en) |
| ZA (1) | ZA983899B (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2336533C (en) | 1998-07-10 | 2004-11-09 | S.C. Johnson Commercial Markets, Inc. | Process for producing polymers by free radical polymerization and condensation reaction, and apparatus and products related thereto |
| CA2336447C (en) * | 1998-07-10 | 2007-08-21 | S.C. Johnson Commercial Markets, Inc. | Continuous bulk polymerization and esterification process and compositions including the polymeric product |
| EP1020502A1 (en) * | 1999-01-13 | 2000-07-19 | Rohm And Haas Company | The use of polymers as furniture polishes |
| DE60025361T2 (en) | 1999-07-14 | 2006-07-27 | Johnson Polymer, Inc., Sturtevant | METHOD FOR CONTINUOUS PRODUCTION OF EPOXY (METH) ACRYLIC STYRENE POLYMERS AND THEIR USE IN COATINGS |
| US6683129B1 (en) * | 2000-03-31 | 2004-01-27 | National Starch And Chemical Investment Holding Corporation | Salt sensitive aqueous emulsions |
| US6605681B1 (en) | 2000-07-12 | 2003-08-12 | Johnson Polymer, Inc. | Process for the continuous production of epoxylated addition polymers, and powder and liquid coating applications containing epoxylated addition polymers |
| EP1182235A1 (en) | 2000-08-24 | 2002-02-27 | Rohm And Haas Company | Exterior finishing composition, grout, and trowel paste |
| AU9133401A (en) * | 2000-11-28 | 2002-05-30 | Rohm And Haas Company | Hydrophobic absorbing polymers and process |
| EP1223202B1 (en) * | 2001-01-10 | 2004-04-07 | Rohm And Haas Company | Aqueous composition for wood stain |
| JP2002322391A (en) * | 2001-04-26 | 2002-11-08 | Jsr Corp | Aqueous coating composition and floor polishing composition |
| CA2390952C (en) * | 2001-07-02 | 2006-07-11 | Rohm And Haas Company | Compositions and process for retaining active ingredients comprising networked structured polymers |
| US7063895B2 (en) | 2001-08-01 | 2006-06-20 | National Starch And Chemical Investment Holding Corporation | Hydrophobically modified solution polymers and their use in surface protecting formulations |
| EP1448737B1 (en) * | 2001-11-15 | 2012-01-25 | Samsung Electronics Co., Ltd. | Slurry composition including an additive composition, and method of polishing an object using the slurry composition |
| JP4104931B2 (en) * | 2002-07-29 | 2008-06-18 | ジョンソンディバーシー株式会社 | Aqueous floor resin dispersion and floor polish composition using the same |
| JP2004091713A (en) * | 2002-09-03 | 2004-03-25 | Jsr Corp | Composition for polishing agent |
| WO2006058781A2 (en) | 2004-12-03 | 2006-06-08 | Proteosys Ag | Finasteride, dutasteride and related compounds for preventing/treating neurologically-associated disorders |
| DE102005034508A1 (en) * | 2005-05-30 | 2006-12-07 | wfk-Forschungsinstitut für Reinigungstechnologie e.V. | Process for the immobilization of contaminants on surfaces |
| KR101643554B1 (en) * | 2009-06-04 | 2016-07-29 | 닛신 가가꾸 고교 가부시끼가이샤 | Vinyl chloride-based resin emulsion, water-based ink and recording paper |
| US8680224B2 (en) * | 2010-02-01 | 2014-03-25 | Johns Manville | Formaldehyde-free protein-containing binder compositions |
| JP5697089B2 (en) * | 2011-02-22 | 2015-04-08 | 国立大学法人 長崎大学 | Method for producing long chain (meth) acrylate emulsion |
| CN102660197B (en) * | 2012-04-20 | 2014-11-05 | 上海皇宇科技发展有限公司 | Leather brightening agent and leather brightening wet wiper |
| CN102977790B (en) * | 2012-12-21 | 2015-01-07 | 青岛文创科技有限公司 | Polishing agent |
| EP2945994B1 (en) | 2013-01-18 | 2018-07-11 | Basf Se | Acrylic dispersion-based coating compositions |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1003363A (en) * | 1961-03-28 | 1965-09-02 | Rohm & Haas | Coating compositions |
| JPH01182338A (en) * | 1988-01-14 | 1989-07-20 | Nippon Oil & Fats Co Ltd | Polypropylene resin composition |
| US5246972A (en) * | 1990-04-06 | 1993-09-21 | Dow Corning Corporation | Polish containing highly adsorptive polymer |
| US5085695A (en) * | 1990-07-13 | 1992-02-04 | Minnesota Mining And Manufacturing Company | Protective furniture polish composition |
| JPH06234955A (en) * | 1993-02-09 | 1994-08-23 | Nippon Shokubai Co Ltd | Aqueous polishing agent |
| US5521266A (en) * | 1994-10-28 | 1996-05-28 | Rohm And Haas Company | Method for forming polymers |
| DE19533269A1 (en) * | 1995-09-08 | 1997-03-13 | Basf Ag | Process for the preparation of polymers in an aqueous medium |
-
1998
- 1998-05-07 US US09/074,062 patent/US6040409A/en not_active Expired - Fee Related
- 1998-05-08 ZA ZA983899A patent/ZA983899B/en unknown
- 1998-05-11 AR ARP980102180A patent/AR012685A1/en unknown
- 1998-05-12 DE DE69821052T patent/DE69821052T2/en not_active Expired - Fee Related
- 1998-05-12 EP EP98303684A patent/EP0879852B1/en not_active Expired - Lifetime
- 1998-05-12 ES ES98303684T patent/ES2213876T3/en not_active Expired - Lifetime
- 1998-05-12 AU AU64889/98A patent/AU743666B2/en not_active Ceased
- 1998-05-15 CA CA002237839A patent/CA2237839A1/en not_active Abandoned
- 1998-05-18 BR BR9801658-0A patent/BR9801658A/en not_active IP Right Cessation
- 1998-05-18 KR KR1019980017803A patent/KR19980087148A/en not_active Application Discontinuation
- 1998-05-20 CN CN98108858A patent/CN1201806A/en active Pending
- 1998-05-20 JP JP10138497A patent/JPH10330574A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ZA983899B (en) | 1998-11-13 |
| DE69821052D1 (en) | 2004-02-19 |
| EP0879852B1 (en) | 2004-01-14 |
| AR012685A1 (en) | 2000-11-08 |
| AU6488998A (en) | 1998-11-26 |
| JPH10330574A (en) | 1998-12-15 |
| BR9801658A (en) | 1999-10-05 |
| EP0879852A1 (en) | 1998-11-25 |
| CN1201806A (en) | 1998-12-16 |
| US6040409A (en) | 2000-03-21 |
| ES2213876T3 (en) | 2004-09-01 |
| AU743666B2 (en) | 2002-01-31 |
| DE69821052T2 (en) | 2004-10-28 |
| KR19980087148A (en) | 1998-12-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |