CN1320010C - Multi-purpose polymers, methods and compositions - Google Patents

Abstract

The present invention discloses a multipurpose polymer which is the polymerization reaction product of a monomer mixture comprising: at least one amino-substituted vinyl monomer; at least one nonionic vinyl monomer; at least one olefinic monomer; at least one semihydrophobic vinyl surfactant monomer; and, optionally, one or more hydroxyl-substituted nonionic vinyl monomers, crosslinking monomers, chain transfer agents or polymer stabilizer. These vinyl addition polymers have a combination of substituents including amino substituents that provide cationic properties at low pH, hydrophobic substituents, hydrophobically modified polyoxyalkylene substituents, and hydrophilic polyoxyalkylene substituents. Alkyl substituent. The polymers surprisingly provide beneficial rheological properties in acidic aqueous compositions and are compatible with cationic materials. The multipurpose polymer can be used in a variety of products for personal care, healthcare, household care, institutional and industrial care, and industrial applications.

Description

Multipurpose polymers, methods and compositions

Cross References to Related Applications

This application claims priority to U.S. Provisional Application Serial No. 60/410,697 (filed September 13, 2002, which is hereby incorporated by reference).

Technical Field of the Invention

The present invention relates to the field of polymers, and in particular to cationic polymers and associative polymers.

Background of the invention

Formulations having an acidic pH (ie, <7) comprising cationic components, such as cationic surfactants and their salts or active acidic components, are often referred to as "low pH" formulations. Stable low pH viscous emulsion and gel formulations are difficult to obtain. The most commonly used thickeners are synthetic associative thickeners, which tend to be anionic and thus are generally incompatible with cationic components, especially quaternary ammonium salts, or are ineffective thickeners at low pH.

Formulators of low pH compositions, especially emulsions, are therefore limited in their choice of nonionic thickeners, such as nonionic surfactants, or cationic thickeners. Nonionic thickeners are uncharged and thus presumably less reactive, but nonionic thickeners tend to inactivate preservatives and in some cases promote microbial growth. Although some cationic polymeric rheology modifiers, such as hydrophobically modified aminoacrylate copolymers, are commercially available, their rheological properties are unpredictable or aesthetically unsatisfactory.

Accordingly, there is a continuing need or desire for a cationic compatible polymeric rheology modifier for low pH formulations.

Summary of the invention

The present invention provides multipurpose polymers with generally cationic and associative characters.

The polymers of the present invention are multifunctional vinyl addition polymers having amino substituents for providing hydrophilic and cationic properties at low pH, hydrophobic substituents for attenuating hydrophilicity for providing association A combination of hydrophobically modified polyoxyalkylene substituents for improved performance, and hydrophilic polyoxyalkylene substituents for attenuating association performance and providing beneficial rheological properties. The polymer is obtained by comprising at least one amino-substituted vinyl monomer; at least one hydrophobic nonionic vinyl monomer; at least one associative vinyl monomer; at least one semi-hydrophobic vinyl surfactant monomers; and, optionally, polymerization of monomer mixtures comprising one or more hydroxyl-substituted nonionic vinyl monomers, crosslinking monomers, chain transfer agents, polymer stabilizers, and the like become.

The polymer may swell upon acidification with mineral or organic acids, including amino acids, or upon alkylation, or upon simultaneous acidification and alkylation. The multipurpose polymers of the present invention can be used as thickeners, emulsifiers, stabilizers, suspending agents, film formers, conditioners, moisturizers, spreading aids and carriers for increasing chemically and physiologically active ingredients and cosmetics Potency, deposition or delivery of materials, and use as excipients for improving the psychosensory and aesthetic properties of formulations in which they are included. The cationic character of the polymers at low pH makes them useful as antistatic agents, and, under certain conditions, may also provide insecticidal, antimicrobial, or other preservative activity.

The polymers of the present invention can advantageously thicken acidic aqueous formulations to provide an aesthetically smooth textured product that flows smoothly and spreads easily. Polymer-containing products can be in the form of non-pourable, hard to soft gels, semi-solid pastes to essentially solid sticks or sticks, and aerosolized foams to squeezeable gels, as well as suitable pumpable Non-runny, but flowable products for spray or roll-on products and liquid lotions. The polymers of the present invention are surprisingly effective in thickening aqueous systems containing cationic ingredients (eg, quaternary ammonium compounds and amines), cationic conditioning agents, fabric softeners, surfactants, and the like.

Advantageously, the polymers of the present invention find use in, but are not limited to, personal care products, health care products, household care products, institutional and industrial (collectively "I&I") care products, and the like. The polymers are useful as film-forming modifiers, and for promoting the deposition of color cosmetics and polar and non-polar oils on the skin, hair, or both. In addition, polymers are used, for example, as rheology modifiers, emulsifiers, stabilizers, solubilizers, suspending agents, flocculants, as well as pigments and grinding additives in industrial chemical processes, textile finishing processes, printing, bonding Agent coating, and products in similar occasions.

Description of the preferred embodiment

The polymers of the present invention are generally basic, aqueous acid-swellable, or aqueous acid-soluble polymers and salts thereof, which contain at least one basic amino substituent which is cationic at low pH, at least one derived from A hydrophobically modified polyoxyalkylene substituent associated with a vinyl monomer, and at least one polyoxyalkylene substituent derived from a semihydrophobic vinyl surfactant monomer. The polymers of the present invention may also optionally contain substituents derived from other monomeric units, such as crosslinkable monomeric units, hydroxyl-substituted nonionic vinyl monomeric units, chain transfer agent units, polymer stabilizers, and the like group. The polymers of the invention generally have associative properties in aqueous solution. For convenience, the polymers of the present invention are generally referred to herein as "cationically associative polymers."

The term "low pH formulation" refers to a formulation having an acidic pH of from about 0.5 to not more than about 7, preferably to not more than about 6.5.

The term "aqueous" when applied to a formulation or medium means that water is present in an amount sufficient to at least swell or dissolve the cationic associative polymer in the composition in which it is included.

It has surprisingly been found that cationic associative polymers provide desirable rheological properties to low pH aqueous personal care, healthcare, household care, industrial and institutional care products. The cationic associative polymers are cationically compatible making them particularly useful as thickeners in products containing quaternary ammonium salts or amines. Cationic associative polymers are useful thickeners in products containing active acid components and are useful thickeners and emulsifiers in emulsions (creams, lotions). In addition to thickening, the cationic associative polymers are useful film formers, spreading aids and deposition aids for products containing colorants and emollient oils. Surprisingly, the cationic associative polymers are useful in compositions comprising relatively high concentrations (eg 10-40%) of anionic surfactants, as well as providing hair styling benefits.

The term "personal care product" as used herein includes, but is not limited to, cosmetics, toiletry products, medicated cosmetics and beauty aids, personal hygiene and cleansing products applied to the skin, hair, scalp, and nails of humans and animals. The term "health care product" as used herein includes, but is not limited to, pharmaceuticals, cosmetic drugs, oral care products (mouth, teeth), eye care products, ear care products and over-the-counter products and appliances such as patches, plasters, dressings and the like, and medical devices for external use on or in the body of humans and animals for the improvement of health-related or medical conditions, generally for the maintenance of hygiene or health, and for similar purposes. The term "body" includes keratinized (hair, nails) and non-keratinized skin areas of the entire body (face, trunk, extremities, hands and feet), tissues of body openings and eyes, and the term "skin" includes scalp and mucous membranes. The term "household care product" as used herein includes, but is not limited to, products used in the home for cleaning surfaces or for maintaining hygiene, such as insecticidal cleaning products in kitchens and bathrooms, and for fabric care and cleaning laundry products, and the like. The terms "institutional and industrial care" and "I&I" as used herein include, but are not limited to, products used for cleaning or maintaining hygiene in industrial and institutional settings, including hospitals and healthcare facilities, and the like.

The cationic associative polymers of the present invention are multipurpose polymers, preferably prepared by polymerizing a monomer mixture comprising: at least one basic, amino-substituted vinyl (ASV) monomer or salt thereof; at least one hydrophobic nonionic vinyl (HNV) monomer; at least one associative vinyl (AV) monomer; at least one semihydrophobic vinyl surfactant (SVS) monomer; and, optionally One or more hydroxyl substituted nonionic vinyl (HSNV) or crosslinkable (XL) monomers. The cationic associative polymers of the present invention can also be prepared from monomer mixtures containing chain transfer agents (CTAs) or other functional components commonly used in emulsion polymers and emulsion polymerization processes.

In a preferred embodiment, the multipurpose cationic associative polymers of the present invention are the polymerization product of a monomer mixture comprising, based on the total monomer mixture weight: (a) from about 10 to about 70 percent by weight of at least An ASV monomer or salt thereof; (b) about 20 to about 80% by weight of at least one HNV monomer; (c) about 0.01 to about 25% by weight of at least one AV monomer; (d) about 0.01 to about 25% by weight of at least one SVS monomer; (e) up to about 10% by weight of HSNV monomer; (f) up to about 5% by weight of XL monomer; (g) up to about 10% by weight of CTA; and (h ) up to about 2% by weight polymeric stabilizer.

In another preferred embodiment, the cationic associative polymer is the polymerization product of a monomer mixture comprising, based on the weight of the total monomer mixture: (a) from about 25 to about 60 percent by weight of at least one ASV monomer or salt thereof; (b) about 20 to about 70% by weight of at least one HNV monomer; (c) about 0.1 to about 15% by weight of at least one AV monomer; (d) about 0.1 to about 10% by weight % at least one SVS monomer; (e) about 0.1 to about 10 wt. % HSNV monomer; (f) about 0.001 to about 5 wt. % XL monomer; and (g) about 0.001 to about 5 wt. % CTA.

An especially preferred polymer of the present invention is a polymer that is the polymerization product of a monomer mixture comprising, based on the weight of the total monomer mixture: (a) from about 20 to about 50 percent by weight of at least one amino group - substituted vinyl monomers selected from: 3-(N,N-dimethylamino)propyl (meth)acrylate, and N'-(3-N,N-dimethylamino)propyl (meth)acrylamide. Most preferred are 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA), 2-(N,N-diethylamino)ethyl methacrylate (DEAEMA), methacrylic acid 2 -(tert-butylamino)ethyl ester (TBAEMA), 2-(N,N-dimethylamino)propyl methacrylamide (DMAPMAm), and 2-(N,N-dimethylamino)acrylate Neo Amyl ester (DMANPA).

(b) from about 50 to about 65% by weight of at least one hydrophobic nonionic vinyl monomer selected from the group consisting of C ₁ -C ₃₀ alkyl esters of acrylate, C ₁ -C ₃₀ alkyl esters of methacrylate, and mixture;

(c) from about 0.1 to about 10% by weight of at least one associative vinyl monomer selected from polyethoxylated cetyl methacrylate (CEM), polyethoxylated cetearyl methacrylate Ethyl ester (CSEM), polyethoxylated stearyl (meth)acrylate, polyethoxylated arachidyl (meth)acrylate, polyethoxylated behenyl methacrylate ( BEM), polyethoxylated lauryl methacrylate (LEM), polyethoxylated waxyl (meth)acrylate, polyethoxylated montanyl (meth)acrylate (monthanyl) ester, polyethoxylated Ethoxylated meliflora (meth)acrylate, polyethoxylated berydocyl (meth)acrylate, tristyrylphenol polyethoxylated methacrylate (TEM), hydrogenated castor oil polyethoxylated methacrylate (HCOEM), canola polyethoxylated (meth)acrylate, and cholesteryl polyethoxylated methacrylate (CHEM);

(d) from about 0.1 to about 10 percent by weight of at least one semihydrophobic vinyl surfactant monomer having one of the following general chemical formulas:

CH ₂ ＝CH—O(CH ₂ ) _a O(C ₃ H ₆ O) _b (C ₂ H ₄ O) _c H or

_CH2 = _CHCH2O ( _{C3H6O )d ( C2H4O} ) _{eH ;}

wherein a is 2, 3, or 4; b is an integer from 1 to about 10; c is an integer from about 5 to about 50; d is an integer from 1 to about 10; and e is an integer from about 5 to about 50;

(e) up to about 10% by weight hydroxy-substituted nonionic vinyl monomers;

(f) up to about 5% by weight of a crosslinking monomer;

(g) up to about 10% by weight chain transfer agent; and

(h) up to about 2% by weight polymeric stabilizer.

As used herein, the term "alkyl" refers to a substituted or unsubstituted aliphatic hydrocarbon moiety, including straight chain, branched chain and carbocycloalkyl moieties. The term "carbocycloalkyl" refers to an alkyl group comprising one or more carbocyclic rings ranging in size from 3 to about 12 carbon atoms and optionally including alkyl substituents on the carbocyclic rings. The term "aryl" includes substituted and unsubstituted phenyl and naphthyl moieties. A modifier of the form " _Cx - _Cy " indicates that the alkyl or carbocycloalkyl group has a molecular formula containing a total of x to y carbon atoms, where x and y are specified integers. The term "complex ester" as used herein and in the appended claims refers to a polyol having at least one hydroxyl group capable of being alkylated by a _C2 - _C7 alkylene oxide, such as a di-, tri-, or poly-ester. The term "complex ester" especially includes complex hydrophobes described in US Patent No. 5,639,841 to Jenkins et al., the relevant disclosure of which is hereby incorporated herein by reference.

As used herein, the terms "halogen-substituted", "hydroxy-substituted", "carboxy-substituted", "polyoxyalkylene-substituted", and the like when referring to alkyl or aryl groups, and the like Base-substituted", and "aryl-substituted" mean that at least one hydrogen atom on an alkyl, aryl, or similar group has been replaced by at least one halogen atom, hydroxyl group, carboxyl group, poly Oxyalkylene groups, alkyl groups, or aryl groups replace. The terms "poly(meth)acrylate" and "poly(meth)acrylamide" used herein refer to polyacrylic acid ester or polymethacrylate, and polyacrylamide or polymethacrylamide.

The following describes monomers suitable for use in preparing the cationic associative polymers of the present invention.

ASV monomer

Amino-substituted vinyl monomers suitable for use in preparing the cationic associative polymers of the present invention are basic, polymerizable ethylenically unsaturated monomers which preferably contain at least one amino functional group. These basic amino groups can be derived from mono-, di- or poly-aminoalkyl groups or nitrogen-containing heteroaromatic groups. Amino groups may contain primary, secondary or tertiary amines. The monomers can be used in amino form or in salt form as needed.

The polymers of the present invention preferably comprise ASV monomers selected from: mono(C ₁ -C ₄ )alkylamino(C ₁ -C ₈ )alkyl (meth)acrylates, di(C ₁ -C ₄ )alkylamino(C ₁ -C ₈ )alkyl esters, mono(C ₁ -C ₄ )alkylamino(C ₁ -C ₈ )alkyl(meth)acrylamides, di(C ₁ - C ₄ ) Alkylamino(C ₁ -C ₈ )alkyl (meth)acrylamides, nitrogen-containing heterocyclic (meth)acrylamides, nitrogen-containing heterocyclic (meth)acrylates, and mixtures thereof.

Examples of preferred ASV monomers include, but are not limited to: mono- or di-(C ₁ -C ₄ )alkylamino(C ₁ -C ₄ )alkyl (meth)acrylates such as 2- (N,N-Dimethylamino)ethyl ester, 3-(N,N-dimethylamino)propyl (meth)acrylate, 4-(N,N-dimethyl(meth)acrylate) Amino)butyl ester, (N,N-dimethylamino)-tert-butyl (meth)acrylate, 2-(N,N-diethylamino)ethyl (meth)acrylate, (meth)acrylate Base) 3-(N,N-diethylamino)propyl acrylate, 4-(N,N-diethylamino)butyl (meth)acrylate, 2-(N, N-dipropylamino)ethyl ester, 3-(N,N-dipropylamino)propyl (meth)acrylate, 4-(N,N-dipropylamino)butyl (meth)acrylate esters, and the like; mono- or di-(C ₁ -C ₄ )alkylamino(C ₁ -C ₄ )alkyl(meth)acrylamides such as N′-(2-N,N-dimethylamino ) ethylmethacrylamide, N'-(3-N,N-dimethylamino)propylacrylamide, and the like; and nitrogen-containing heterocyclic (meth)acrylamides or (meth)acrylates Such as N-(2-pyridyl)acrylamide, N-(2-imidazolyl)methacrylamide, 2-(4-morpholinyl)ethyl methacrylate, 2-(4-morpholinyl)acrylate Ethyl ester, N-(4-morpholinyl)methacrylamide, N-(4-morpholinyl)acrylamide, 2-vinylpyridine, 4-vinylpyridine, and the like.

Suitable salt forms of the monomers include, but are not limited to, salts of inorganic acids such as hydrochlorides, sulfates, and phosphates; and salts of organic acids such as acetates, maleates, and fumarates; and the like thing.

The foregoing monomers or salts thereof can be used alone or as a mixture of two or more as the amino-substituted vinyl monomer component of the cationic associative polymer of the present invention. Particularly preferred ASV monomers are 2-(N,N-dimethylamino)ethyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, and N'-(3-N,N-dimethylamino)propyl(meth)acrylamide. Most preferred are 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA), 2-(N,N-diethylamino)ethyl methacrylate (DEAEMA), methacrylic acid 2 -(tert-butylamino)ethyl ester (TBAEMA), 2-(N,N-dimethylamino)propyl methacrylamide (DMAPMAm), and 2-(N,N-dimethylamino)acrylate Neo Amyl ester (DMANPA).

The ASV monomer preferably comprises from about 10 to about 70 percent by weight of the total monomer mixture, more preferably from about 20 to about 50 percent by weight, and most preferably from about 30 to about 40 percent by weight, based on the total monomer mixture weight.

HNV monomer

Hydrophobic nonionic vinyl monomers suitable for use in preparing the cationic associative polymers of the present invention are copolymerizable, nonionic ethylenically unsaturated monomers having either of the following formulas (I) or (II):

(I) _CH2 =C(X)Z,

(II) _CH2 =CH-OC(O)R;

Wherein, in formulas (I) and (II), respectively, X is H or methyl; and Z is -C(O)OR ¹ , -C(O)NH ₂ , -C(O)NHR ¹ , -C (O)N(R ¹ ) ₂ , -C ₆ H ₄ R ¹ , -C ₆ H ₄ OR ¹ , -C ₆ H ₄ Cl, -CN, -NHC(O)CH ₃ , -NHC(O)H , N-(2-pyrrolidonyl), N-caprolactam, -C(O)NHC(CH ₃ ) ₃ , -C(O)NHCH ₂ CH ₂ -N-ethyleneurea, -SiR ₃ , -C (O)O(CH ₂ ) _x SiR ₃ , -C(O)NH(CH ₂ ) _x SiR ₃ , or -(CH ₂ ) _x SiR ₃ ; x is an integer from 1 to about 6; R is independently C ₁ -C ₃₀ alkyl; R ¹ are independently C ₁ -C ₃₀ alkyl, hydroxy-substituted C ₂ -C ₃₀ alkyl or halogen-substituted C ₁ -C ₃₀ alkyl.

Non-limiting examples of preferred hydrophobic nonionic vinyl monomers include C ₁ -C ₃₀ alkyl (meth)acrylates; C ₁ -C ₃₀ alkyl (meth)acrylamides; styrene; substituted benzene Ethylene such as vinyltoluene, (e.g., 2-methylstyrene), butylstyrene, isopropylstyrene, p-chlorostyrene, and the like; vinyl esters such as vinyl acetate, vinyl butyrate , vinylcaprolate (vinylcaprolate), vinyl pivalate, vinyl neodecanoate, and the like; unsaturated nitriles such as methacrylonitrile, acrylonitrile, and the like; and unsaturated silanes such as trimethyl Dimethylvinylsilane, Dimethylethylvinylsilane, Allyldimethylphenylsilane, Allyltrimethylsilane, 3-Acrylamidopropyltrimethylsilane, 3-Trimethacrylate Methylsilylpropyl Ester, and the like.

Particularly preferred nonionic vinyl monomers include C ₁ -C ₃₀ alkyl esters of acrylic acid and methacrylic acid and mixtures thereof, such as ethyl acrylate (EA), methyl methacrylate (MMA), methacrylic acid 3, 3,5-Trimethylcyclohexyl ester (TMCHMA), and mixtures thereof.

The HNV monomer preferably comprises from about 20 to about 80 percent by weight of the total monomer mixture, more preferably from about 30 to about 70 percent by weight, and most preferably from about 50 to about 65 percent by weight, based on the total monomer mixture weight.

AV monomer

The associative vinyl monomers suitable for use in the production of the cationic associative polymers of the present invention preferably have terminal ethylenically unsaturated moieties (i) for addition polymerization with other monomers of the system; Compounds of the polyoxyalkylene midsection moiety (ii) for imparting selective hydrophilic properties and hydrophobic end group moieties (iii) for imparting selective hydrophobic properties to the polymer.

Moieties (i) donating ethylenically unsaturated end groups are preferably derived from α,β-ethylenically unsaturated mono- or dicarboxylic acids or anhydrides thereof, more preferably _C3 or _C4 mono- or dicarboxylic acids or anhydrides thereof. Additionally, part (i) of the associative monomers may be derived from allyl ethers or vinyl ethers; nonionic vinyl-substituted urethane monomers such as disclosed in US Republished Patent No. 33,156 or US Pat. No. 5,294,692; or vinyl-substituted urea reaction products, such as disclosed in US Patent No. 5,011,978; the relevant disclosures are incorporated herein by reference, respectively.

The middle portion (ii) is preferably _{a polyoxyalkylene segment having from about 5 to about 250, more preferably from about 10 to about 120, and most preferably from about 15 to about 60 repeating C2-C7 alkylene} oxide units. Preferred middle segment (ii) comprises from about 5 to about 150, more preferably from about 10 to about 100, and most preferably from about 15 to about 60 ethylene oxide, propylene oxide or butylene oxide units, and ethylene oxide, propylene oxide and Or random or non-random sequences of polyoxyethylene, polyoxypropylene, and polyoxybutylene segments of oxybutylene units.

The hydrophobic end group moiety (iii) of the associative monomer is preferably a hydrocarbon moiety belonging to one of the following hydrocarbon classes: C ₈ -C ₄₀ linear alkyl, aryl-substituted C ₂ -C ₄₀ alkyl, C ₂ -C ₄₀ alkyl-substituted phenyl, C ₈ -C ₄₀ branched alkyl, C ₈ -C ₄₀ carbocycloalkyl; and C ₈ -C ₈₀ complex esters.

Non-limiting examples of suitable hydrophobic end group moieties (iii) of the associative monomers are straight or branched chain alkyl groups having from about 8 to about 40 carbon atoms such as octyl (C ₈ ), isooctyl Cetyl (branched C ₈ ), decyl (C ₁₀ ), lauryl (C ₁₂ ), myristyl (C ₁₄ ), cetyl (C ₁₆ ), cetearyl (C ₁₆ -C ₁₈ ) , stearyl (C ₁₈ ), isostearyl (branched C ₁₈ ), arachidyl (C ₂₀ ), behenyl (C ₂₂ ), tetracosyl (C ₂₄ ), wax ( C ₂₆ ), lignanyl (C ₂₈ ), meliflonyl (C ₃₀ ), docosyl (C ₃₂ ), and the like.

Examples of straight and branched chain alkyl groups having from about 8 to about 40 carbon atoms derived from natural sources include, but are not limited to, those derived from hydrogenated peanut oil, soybean oil, and canola oil (all predominantly C ₁₈ ), hydrogenated tallow oil (C ₁₆ -C ₁₈ ), and the like; and hydrogenated C ₁₀ -C ₃₀ terpene alcohols, such as hydrogenated geraniol (branched C ₁₀ ), hydrogenated farnesol (branched C ₁₅ ), hydrogenated phytol (branched C ₂₀ ), and the like.

Non-limiting examples of suitable _C2 - _C40 alkyl-substituted phenyl groups include octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, hexadecylphenyl , octadecylphenyl, isooctylphenyl, sec-butylphenyl, and the like.

Suitable C ₈ -C ₄₀ carbocycloalkyl groups include, but are not limited to, groups derived from sterols from animal sources such as cholesterol, lanosterol, 7-dehydrocholesterol, and the like ; from plant sources, such as phytosterols, stigmasterol, campesterol, and the like; and from yeast sources, such as goersterol, mycosterol, and the like. Other carbocycloalkyl hydrophobic end groups useful in the present invention include, but are not limited to, cyclooctyl, cyclododecyl, adamantyl, decahydronaphthyl, and those derived from natural carbocyclic materials such as pinene, Hydrogenated groups of retinol, camphor, isobornyl alcohol, and the like.

Exemplary aryl-substituted C ₂ -C ₄₀ alkyl groups include, but are not limited to, styryl (e.g., 2-phenylethyl), distyryl (e.g., 2,4-diphenyl butyl), tristyryl (e.g., 2,4,6-triphenylhexyl), 4-phenylbutyl, 2-methyl-2-phenylethyl, tristyrylphenol, and analog.

Non-limiting examples of suitable _C8 - _C80 complex esters include hydrogenated castor oil (mainly triglycerides of 12-hydroxystearic acid); 1,2-diacylglycerols such as 1,2-distearylglycerol; , 1,2-dipalmitylglycerol, 1,2-dimyristylglycerol, and the like; di-, tri-, or poly-esters of sugars such as 3,4,6-tristearyl glucose, 2 , 3-dilauryl fructose, and the like; and sorbitan esters such as those disclosed in US Patent No. 4,600,761 (Ruffner et al., the relevant disclosure of which is incorporated herein by reference).

Useful associative monomers can be prepared by any method known in the art. See, for example; U.S. Patent Nos. 4,421,902 (Chang et al); No. 4,384,096 (Sonnabend); No. 4,514,552 (Shay et al); No. 4,600,761 (Ruffner et al); (Barron et al); No. 5,292,843 (Jenkins et al); No. 5,770,760 (Robinson); and No. 5,412,142 (Wilkerson, III et al); the relevant disclosures of which are incorporated herein by reference.

Examples of preferred associative vinyl monomers include those having the following formula (III):

Wherein, R ² is independently H, methyl, -C(O)OH, or -C(O)OR ³ ; R ³ is C ₁ -C ₃₀ alkyl; A is -CH ₂ C(O)O -, -C(O)O-, -O-, -CH ₂ O-, -NHC(O)NH-, -C(O)NH-, -Ar-(CE ₂ ) _z -NHC(O)O -, -Ar-(CE ₂ ) _z -NHC(O)NH-, or -CH ₂ CH ₂ NHC(O)-; Ar is a divalent aryl group; E is H or methyl; z is 0 or 1; k is an integer from 0 to about 30, and m is 0 or 1, with the proviso that if k is 0, then m is 0, and if k is 1 to about 30, then m is 1; (R ⁴ -0) _n is Polyoxyalkylene, which is a homopolymer, random copolymer, or block copolymer of C ₂ -C ₄ oxyalkylene units, wherein R ⁴ is C ₂ H ₄ , C ₃ H ₆ , C _{4 H8} , or a mixture thereof, and n is an integer from about 5 to about 250, preferably from about 5 to about 100, more preferably from about 10 to about 80, and most preferably from about 15 to about 60; Y is ^-R4O- , -R ⁴ NH-, -C(O)-, -C(O)NH-, -R ⁴ NHC(O)NH-, or -C(O)NHC(O)-; and R ⁵ is selected from C ₈ -C ₄₀ straight chain alkyl, C ₈ -C ₄₀ branched alkyl, C ₈ -C ₄₀ carbocycloalkyl, C ₂ -C ₄₀ alkyl-substituted phenyl, aryl-substituted C ₂ - C ₄₀ alkyl, and C ₈ -C ₈₀ complex ester substituted or unsubstituted alkyl; wherein R ⁵ alkyl group optionally contains one or more selected from hydroxyl group, alkoxy group, and Substituents for halogen groups.

Particularly preferred associative vinyl monomers of formula (III) include polyethoxylated cetyl methacrylate (CEM), polyethoxylated cetearyl methacrylate (CSEM), Polyethoxylated stearyl (meth)acrylate, polyethoxylated arachidyl (meth)acrylate, polyethoxylated behenyl methacrylate (BEM), polyethoxylated Lauryl Methacrylate (LEM), Polyethoxylated Waxyl (Meth)acrylate, Polyethoxylated Montanyl (Meth)acrylate, Polyethoxylated (Meth)Acrylic Acid Melissa, Polyethoxylated Tricodecyl (Meth)acrylate, Tristyrylphenol Polyethoxylated Methacrylate (TEM), Hydrogenated Castor Oil Polyethoxylated Methyl Acrylates (HCOEM), canola polyethoxylated (meth)acrylates, and cholesteric polyethoxylated methacrylates (CHEM), where the polyethoxylated portion of the monomer contains about 5 to about 100, preferably about 10 to about 80, and more preferably about 15 to about 60 ethylene oxide repeat units.

Preferably, the AV monomer component in the monomer mixture comprises from about 0.001 to about 25 percent by weight of the monomer mixture, more preferably from about 0.01 to about 15 percent by weight, most preferably from about 0.1 to about 10 percent by weight, based on the total monomer mixture weight %.

SVS monomer

It has been surprisingly found that semihydrophobic vinyl surfactant (SVS) monomers comprising polyoxyalkylene chains moderate the association properties of cationic associative polymers comprising them, thus resulting in highly desirable texture and rheological properties of hydrogel. Without wishing to be bound by theory, it is believed that the polyoxyalkylene groups of the SVS monomer block or shield non-specific associations between the hydrophobic groups of the associative monomers in the polymer and thus weaken the polymer's Association properties. These SVS monomers can adjust the thickening efficiency of the resulting polymer to tailor the rheological properties of the polymer to the needs of the chosen application. Most surprisingly, it was found that SVS monomers impart desirable rheological and aesthetic properties to hydrogels, providing softer, smoother and more spreadable gels than cationic associative polymers without SVS monomers.

Surprisingly, the incorporation of SVS monomers into cationic associative polymers can greatly reduce or eliminate viscosity drop at low shear stress and can provide shear thinning properties, ie smooth flow.

As used herein, the terms "semihydrophobic vinyl surfactant monomer" and "SVS monomer" refer to compounds having two moieties: (i) a moiety for addition polymerization with other monomers of the reaction mixture. Ethylenically unsaturated end group moieties, and (ii) polyoxygen for weakening the association between hydrophobic groups of the polymer or hydrophobic groups derived from other materials in the composition comprising the polymer Alkylene moiety. SVS monomers are structurally similar to associative monomers, but have substantially non-hydrophobic end group moieties and thus do not impart any associative properties to the polymer.

The unsaturated end group moiety (i) which supplies vinyl or other ethylenically unsaturated end groups for addition polymerization is preferably derived from an α,β-ethylenically unsaturated mono- or dicarboxylic acid or an anhydride thereof, preferably _C3 Or C ₄ mono or dicarboxylic acid, or its anhydride. Alternatively, the terminal moiety (i) may be derived from allyl ether, vinyl ether or nonionic unsaturated urethane.

The polymerizable unsaturated end group moiety (i) may also be derived from a C ₈ -C ₃₀ unsaturated fatty acid group comprising at least one free carboxyl-functional group. The C ₈ -C ₃₀ group is part of the unsaturated end group moiety (i) and is distinct from the hydrophobic group pendant from the associative monomer, which is specifically associated with the associative monomer through a hydrophilic "spacer" moiety. separated by the unsaturated end groups of the monomers.

The polyoxyalkylene moiety (ii) in particular comprises long chain polyoxyalkylene segments substantially similar to the hydrophilic portion of the associative monomer. Preferred polyoxyalkylene moieties (ii) include polyoxyethylene, polyoxypropylene, and polyoxybutylene containing from about 5 to about 250, and preferably from about 10 to about 100, oxyalkylene units unit. If the SVS monomer contains more than one type of oxyalkylene unit, then these units can be arranged in a random, non-random, or block sequence.

Preferred SVS monomers include those having either of the following structural formulas (IV) or (V):

Wherein, in each structural formula (IV) and (V), R ⁶ is independently H, C ₁ -C ₃₀ alkyl, -C(O)OH, or -C(O)OR ⁷ ; R ⁷ is C ₁ -C ₃₀ alkyl; A is -CH ₂ C(O)O-, -C(O)O-, -O-, -CH ₂ O-, -NHC(O)NH-, -C(O )NH-, -Ar-(CE ₂ ) _Z -NHC(O)O-, -Ar-(CE ₂ ) _Z -NHC(O)NH-, or -CH ₂ CH ₂ NHC(O)-; Ar is Divalent aryl; E is H or methyl; z is 0 or 1; p is an integer from 0 to about 30, and r is 0 or 1, provided that if p is 0, r is 0, and if p is 1 to about 30, then r is 1; (R ⁸ -O) _V is a polyoxyalkylene, which is a homopolymer, random copolymer or block copolymer of C ₂ -C ₄ oxyalkylene units , wherein R ⁸ is C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , or a mixture thereof, and v is an integer from about 5 to about 250, preferably from about 5 to about 100, more preferably from about 10 to about 80, and most preferably from about 15 to about 60; R ⁹ is H or C ₁ -C ₄ alkyl; and D is C ₈ -C ₃₀ unsaturated alkyl, or carboxy-substituted C ₈ -C ₃₀ unsaturated alkyl.

Particularly preferred SVS monomers include monomers of the formula:

CH ₂ ＝CH—O(CH ₂ ) _a O(C ₃ H ₆ O) _b (C ₂ H ₄ O) _c H or

_{CH2 =} CH- _CH2O ( _C3H6O ) _d ( _C2H4O ) _{eH ;}

Wherein a is preferably 2, 3, or 4; b is preferably an integer from 1 to about 10, more preferably from about 2 to about 8, most preferably from about 3 to about 7; c is preferably an integer from about 5 to about 50, more preferably From about 8 to about 40, most preferably from about 10 to about 30; d is preferably an integer from 1 to about 10, more preferably from about 2 to about 8, most preferably from about 3 to about 7; and e is preferably from about 5 to about 50 An integer, more preferably from about 8 to about 40.

Examples of preferred SVS monomers include those available under the tradenames EMULSOGEN ^(R ) R109, R208, R307, RAL109, RAL208, and RAL307 from Clariant Corporation; BX-AA-E5P5 from Bimax, Inc.; and MAXEMUL ^(R) 5010 and 5011 polymerizable emulsifiers available from Uniqema; and combinations thereof. Especially preferred SVS monomers include EMULSOGEN ^(R) R208, R307, and RAL307.

According to the manufacturer: EMULSOGEN ^® R109 is a randomly ethoxylated/propoxylated 1,4-butanediol vinyl ether with the empirical formula CH ₂ =CH—O(CH ₂ ) ₄ O(C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₁₀ H; EMULSOGEN ^® R208 is a randomly ethoxylated/propoxylated 1,4-butanediol vinyl ether with the empirical formula: CH ₂ =CH- O(CH ₂ ) ₄ O(C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₂₀ H; EMULSOGEN ^® R307 is a random ethoxylated/propoxylated 1,4-butanediol vinyl Ether, empirically: CH ₂ =CH—O(CH ₂ ) ₄ O(C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₃₀ H; EMULSOGEN ^® RAL 109 is random ethoxylation/propoxylation has the empirical formula CH ₂ =CHCH ₂ O(C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₁₀ H; EMULSOGEN ^® RAL 208 is a randomly ethoxylated/propoxylated ene Propyl ether with the empirical formula _CH2 = _CHCH2O ( _C3H6O ) ₄ ( _C2H4O ) _{20H ;} EMULSOGEN ⁽ R) RAL307 _is a random ethoxylated/propoxylated allyl group ethers with the empirical formula CH ₂ =CHCH ₂ O(C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₃₀ H; MAXEMUL ^® 5010 is a carboxyl-functional C ₁₂ -C ₁₅ alkenyl hydrophobe surrounded by about 24 34 ethylene oxide units ethoxylated; MAXEMUL ^(R) 5011 is a carboxy-functional C ₁₂ -C ₁₅ alkenyl hydrophobe ethoxylated with about 34 ethylene oxide units; and BX-AA-E5P5 is a random ethoxylated Oxylated/propoxylated allyl _{ethers having} the empirical formula _CH2 = _CHCH2O ( _C3H6O ) ₅ ( _C2H4O ) _5H .

The amount of SVS monomer used to prepare the cationic associative polymers of the present invention can vary widely and depends inter alia on the desired final rheological properties of the polymer. If employed, the monomer reaction mixture preferably comprises at least about 0.01 wt. % of one or more SVS monomers, more preferably at least about 0.1 wt. %, based on the weight of the total monomer mixture. The monomer mixture preferably contains no more than about 25% by weight SVS monomer, more preferably no more than about 10% by weight, based on the total monomer mixture weight.

HSNV monomer

The cationic associative polymers of the present invention can optionally be made from monomer mixtures comprising hydroxy-substituted nonionic vinyl monomers. HSNV monomers are ethylenically unsaturated monomers containing one or more hydroxyl substituents.

Examples of suitable HSNV monomers include, but are not limited to, hydroxy-substituted (C ₁ -C ₄ )alkyl (meth)acrylates such as 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate Esters (2-HEA), 3-hydroxypropyl acrylate, and the like; hydroxy-substituted (C ₁ -C ₄ ) alkyl (meth)acrylamides such as N-(2-hydroxyethyl)methacrylamide , N-(2-hydroxyethyl)acrylamide, N-(3-hydroxypropyl)acrylamide, N-(2,3-dihydroxypropyl)acrylamide, and the like. Other useful HSNV monomers include allyl alcohol, glycerol monoallyl ether, 3-methyl-3-buten-1-ol, and vinyl alcohol precursors and equivalents, such as vinyl acetate.

If employed, the monomer reaction mixture preferably comprises one or more HSNV monomers in an amount of up to about 10 weight percent based on the weight of the total monomer mixture. In a preferred embodiment, the amount of HSNV monomer in the mixture is from about 0.01 to about 10 percent by weight, more preferably from about 1 to about 8 percent by weight, most preferably from about 1 to about 5 percent by weight, based on the weight of the total monomer mixture .

XL monomer

The cationic associative polymers of the present invention can be prepared from monomer mixtures containing one or more crosslinkable monomers for introducing branching and controlling molecular weight. Suitable polyunsaturated crosslinkers are well known in the art. Monounsaturated compounds that carry reactive groups that enable the formed copolymer to be crosslinked before, during, or after polymerization can also be used. Other useful crosslinking monomers include polyfunctional monomers containing multiple reactive groups such as epoxide groups, isocyanate groups, and hydrolyzable silane groups. A variety of polyunsaturated compounds can be used to generate partially or substantially crosslinked three-dimensional networks.

Examples of suitable polyunsaturated crosslinkable monomer components include, but are not limited to, polyunsaturated aromatic monomers such as divinylbenzene, divinylnaphthalene, and trivinylbenzene; polyunsaturated cycloaliphatic Monomers such as 1,2,4-trivinylcyclohexane; difunctional esters of phthalic acid such as diallyl phthalate; polyunsaturated aliphatic monomers such as dienes, trienes , and tetraenes, including isoprene, butadiene, 1,5-hexadiene, 1,5,9-decatriene, 1,9-decadiene, 1,5-heptadiene; and analog.

Other suitable polyunsaturated crosslinking monomers include polyalkenyl ethers such as triallylpentaerythritol, diallylpentaerythritol, diallylsucrose, octaallylsucrose, and trimethylolpropanediene Propyl ether; polyunsaturated esters of polyols or polyacids such as 1,6-hexanediol di(meth)acrylate, tetramethylene tri(meth)acrylate, allyl acrylate, itaconic Diallyl Fumarate, Diallyl Fumarate, Diallyl Maleate, Trimethylolpropane Tri(meth)acrylate, Trimethylolpropane Di(meth)acrylate , and polyethylene glycol di(meth)acrylates; alkylenebisacrylamides, such as methylenebisacrylamide, propylenebisacrylamide, and the like; hydroxyl and carboxyl groups of methylenebisacrylamide Derivatives, such as N, N'-bismethylol methylenebisacrylamide; polyethylene glycol di(meth)acrylate, such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate base) acrylate, and triethylene glycol di(meth)acrylate; polyunsaturated silanes such as dimethyldivinylsilane, methyltrivinylsilane, allyldimethylvinylsilane, diene Propyldimethylsilane, and tetravinylsilane; polyunsaturated stannanes, such as tetraallyltin, and diallyldimethyltin; and the like.

Useful monounsaturated compounds bearing reactive groups include N-methylolacrylamide; N-alkoxy(meth)acrylamide, wherein the alkoxy group is C ₁ -C ₁₈ alkoxy; and Unsaturated hydrolyzable silanes such as triethoxyvinylsilane, triisopropoxyvinylsilane, and 3-triethoxysilyl methacrylate; and the like.

Useful polyfunctional crosslinking monomers containing multiple reactive groups include, but are not limited to, hydrolyzable silanes such as ethyltriethoxysilane and ethyltrimethoxysilane; epoxy substituted hydrolyzable silanes, Such as 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane; polyisocyanates such as 1,4-diisocyanatobutane , 1,6-diisocyanatohexane, 1,4-phenylene diisocyanate, and 4,4'-oxybis(phenylisocyanate); unsaturated epoxides such as glycidyl methacrylate esters and allyl glycidyl ethers; polyepoxides such as diglycidyl ether, 1,2,5,6-dioxirane, and ethylene glycol diglycidyl ether; and the like.

Especially useful are those derived from ethoxylated polyols, such as ethoxylated with about 2 to about 100 moles of ethylene oxide per mole of hydroxyl functionality and polymerizable unsaturated groups such as vinyl ether, allyl ether, Acrylate, methacrylate, and similar polyunsaturated crosslinkers for blocked diols, triols, and bisphenols. Examples of these crosslinkers include bisphenol A ethoxylated dimethacrylate; bisphenol F ethoxylated dimethacrylate, ethoxylated trimethylolpropane trimethacrylate, and the like things. Other ethoxylated crosslinkers useful in the cationic associative polymers of the present invention include the ethoxylated polyvalent crosslinkers disclosed in U.S. Patent No. 6,140,435 (Zanotti-Russo, the relevant disclosure of which is incorporated herein by reference). Alcohol derived crosslinker.

Examples of particularly preferred XL monomers are acrylate and methacrylate esters of polyols having at least two acrylate or methacrylate groups, such as trimethylolpropane triacrylate (TMPTA), trimethylolpropane propane dimethacrylate, triethylene glycol dimethacrylate (TEGDMA), ethoxylated (30) bisphenol A dimethacrylate (EOBDMA), and the like.

If employed, the crosslinking monomer is preferably present in the monomer reaction mixture in an amount up to about 5% by weight, based on the total monomer mixture weight. In a preferred embodiment, the XL monomer is present in an amount of about 0.01 to about 3 wt. % based on the total monomer mixture weight, more preferably about 0.05 to about 2 wt. %, most preferably about 0.1 to about 2 wt. 1% by weight.

chain transfer agent

The cationic associative polymers of the present invention can optionally be prepared from a monomer mixture comprising one or more chain transfer agents well known in the polymer art.

Chain transfer agents suitable for use in the present invention are selected from (but not limited to) various thio- and disulfide-containing compounds such as C ₁ -C ₁₈ alkyl mercaptans, mercapto carboxylic acids, mercapto carboxylates, thio Esters, C ₁ -C ₁₈ alkyl disulfides, aryl disulfides, polyfunctional mercaptans, and the like; phosphites and hypophosphites; halogenated alkyl compounds such as carbon tetrachloride, bromotrichloro methane, and the like; and unsaturated chain transfer agents such as alpha-methylstyrene.

Multifunctional thiols include trifunctional thiols such as trimethylolpropane-tris(3-mercaptopropionate), tetrafunctional thiols such as pentaerythritol-tetrakis(3-mercaptopropionate), pentaerythritol-tetra(3-mercaptopropionate), glycolate), and pentaerythritol-tetrakis(thiolactate); hexafunctional thiols, such as dipentaerythritol-hexa(thioglycolate); and the like.

Alternatively, the chain transfer agent may be any catalytic chain transfer agent used to reduce the molecular weight of the addition polymer during free radical polymerization of vinyl monomers. Examples of catalytic chain transfer agents include, for example, cobalt complexes (eg, cobalt (II) chelates). Catalytic chain transfer agents can generally be used at lower concentrations relative to thiol-based CTAs.

Examples of preferred chain transfer agents include octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan (ODM), 3-mercaptopropane Isooctyl thioglycolate (IMP), butyl 3-mercaptopropionate, 3-mercaptopropionic acid, butyl thioglycolate, isooctyl thioglycolate, dodecyl thioglycolate , and analogs. The chain transfer agent can preferably be added to the monomer reaction mixture in an amount up to about 10% by weight of the polymerizable monomer mixture based on the weight of the total monomer mixture. If present, the chain transfer agent preferably comprises at least about 0.1% by weight, based on total monomer weight.

The cationic associative polymers of the present invention can be prepared by conventional polymerization techniques, such as emulsion polymerization, as known in the polymer art. The polymerization reaction can be carried out as a simple batch process, as a metered-in process, or the reaction can be started with small batches and large quantities of monomer can then be metered continuously into the reactor (seed process). Typically the polymerization process is carried out at a reaction temperature of from about 20 to about 80°C, although higher or lower temperatures can be used. To facilitate emulsification of the monomer mixture, the emulsion polymerization is carried out in the presence of at least one surfactant. Preferably the emulsion polymerization is carried out in the presence of from about 1 to about 10 weight percent, more preferably from about 3 to about 8, most preferably from about 5 to about 7 weight percent surfactant, based on the total emulsion weight. The emulsion polymerization reaction mixture also includes one or more free radical initiators, preferably in an amount of from about 0.01 to about 3 weight percent based on total monomer weight. The polymerization reaction can be carried out in an aqueous medium or an aqueous alcoholic medium at a pH of not lower than 7, preferably at a neutral to moderately alkaline pH.

In a typical polymerization reaction, the monomer mixture is added to an emulsifying surfactant, such as a nonionic surfactant, preferably a linear or branched chain alcohol ethoxylate, or a nonionic surfactant in a suitable reactor with mixing and stirring. A solution of a mixture of surfactants and anionic surfactants, such as fatty alcohol sulfates or alkylsulfonates, in a suitable amount of water to prepare monomer emulsions. The emulsion is deoxygenated by any suitable method, such as by sparging with nitrogen, and the polymerization is subsequently initiated by adding a polymerization catalyst (initiator) such as sodium persulfate, or any other suitable addition polymerization catalyst, which is the emulsion well known in the art of polymerization reactions. The reaction system is stirred until the polymerization reaction is complete, which usually takes about 4 to about 16 hours. The monomer emulsion can be heated to a temperature of from about 20 to about 80°C as desired prior to adding the initiator. Unreacted monomer can be eliminated by adding more catalyst, as is well known in the emulsion polymerization art. The resulting polymer emulsion product can then be discharged from the reactor and packaged for storage or use. If desired, the pH or other physical and chemical properties of the emulsion can be adjusted before exiting the reactor. Typically, the product emulsion has a total solids content of from about 10 to about 40% by weight. Typically, the total polymer content of the product emulsion is at least 15% by weight, preferably from about 15 to about 35% by weight, and generally not more than about 25% by weight.

Surfactants suitable for promoting emulsion polymerization include nonionic, anionic, amphoteric, cationic surfactants, and mixtures thereof. Most commonly nonionic and anionic surfactants or mixtures thereof are used. The physical properties of the neutralizing polymer (e.g., viscosity, spreadability, clarity, texture, and the like) can be varied by proper selection of the hydrophobic and hydrophilic properties of the emulsifying surfactant, as is well known in the art of.

Nonionic surfactants suitable for facilitating emulsion polymerization are well known in the polymer art and include, but are not limited to, linear or branched chain alcohol ethoxylates, C ₈ -C ₁₂ alkylphenol alkoxylates , such as octylphenol ethoxylates, polyoxyethylene polyoxypropylene block copolymers, and the like. Other useful nonionic surfactants include polyoxyethylene glycol C ₈ -C ₂₂ fatty acid esters, mono- and diglycerides, sorbitan esters and ethoxylated sorbitan esters, C ₈ -C ₂₂ fatty acid di- Alcohol esters, block copolymers of ethylene oxide and propylene oxide having an HLB value greater than about 15, ethoxylated octylphenols, and combinations thereof.

Preferred alkylphenol alkoxylate surfactants include octylphenol sold by Rhodia, Inc. under the tradename IGEPAL ^(R) CA-897. Preferred linear alcohol alkoxylates include cetearyl alcohol (a mixture of cetyl and stearyl alcohols) sold by BASFCorp under the tradenames PLURAFAC ^(R) C-17, PLURAFAC ^(R) A-38 and PLURAFAC ^(R) A-39. ) of polyethylene glycol ether. Preferred polyoxyethylene polyoxypropylene block copolymers include those sold by BASF Corp under the tradenames PLURONIC ^(R) F127, and PLURONIC ^(R) L35.

Other preferred nonionic surfactants include ethoxylated (50) linear fatty alcohols such as DISPONIL ^(R) A 5060 (Cognis), branched alkyl ethoxylates such as GENAPOL ⁽ R) X1005 (Clariant Corp.), secondary C ₁₂ - _C14 alcohol ethoxylates such as TERGITOL ^(R) S15-30 and S15-40 (Dow Chemical Co.), ethoxylated octylphenol-based surfactants such as TRITON ⁽ R) X-305, X-405 and X-705 (Dow Chemical Co.), IGEPAL ⁽ R) CA 407, 887, and 897 (Rhodia, Inc.), ICONOL ⁽ R) OP 3070 and 4070 (BASF Corp.), SYNPERONIC ^(R) OP 30 and 40 (Uniqema), ethylene oxide and propylene oxide block copolymers such as PLURONIC ^(R) L35 and F127 (BASF Corp.), and secondary _C11 alcohol ethoxylates such as EMULSOGEN ^(R) EPN 407 (Clariant Corp.). Many other suppliers are found in the commercial literature.

Anionic surfactants suitable for promoting emulsion polymerization are well known in the polymer art and include sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium dioctyl sulfosuccinate, di-sec-butylene naphthalene Sodium sulfonate, disodium dodecyl diphenyl ether sulfonate, disodium n-octadecyl sulfosuccinate, and the like.

Polymer stabilizers (also known as protective colloids) suitable for use in the emulsion polymerization process of the present invention are water-soluble polymers including, for example, synthetic polymers such as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyvinyl Pyrrolidones, polyacrylamides, polymethacrylamides, carboxylate-functional addition polymers, polyalkylvinyl ethers and similar; water-soluble natural polymers such as gelatin, pectin, alginates, casein, Starch, and the like; and modified natural polymers, such as methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, allyl-modified hydroxyethylcellulose, and the like. In some cases it may be advantageous to use a mixture of synthetic and natural protective colloids, for example a mixture of polyvinyl alcohol and casein. Other suitable natural polymers are mixed ethers such as methylhydroxyethylcellulose and carboxymethylmethylcellulose. Polymeric stabilizers can be used in amounts up to about 2% by weight based on the total emulsion weight. If employed, polymeric stabilizers are preferably present at a level of from about 0.0001 to about 1 percent by weight, more preferably from about 0.01 to about 0.5 percent by weight.

Polymer stabilizers used in accordance with the present invention are miscible in water in any proportion or have a solubility in water at 20° C. of at least about 0.1% by weight and do not precipitate from these aqueous solutions on dilution with water at the aforementioned temperatures, then they are called water-soluble. The molecular weight of the water-soluble synthetic polymer stabilizers is generally from about 5,000 to about 2,000,000, preferably from about 25,000 to about 1,500,000 Daltons. The viscosity of the aqueous solution of the polymeric stabilizer is generally about 1 to about 10,000 mPa·s at a concentration of about 2 to about 10% by weight and a temperature of about 20°C.

A particularly preferred polymeric stabilizer is an allyl modified hydroxyethyl cellulose, such as the TYLOSE ^(R) AM-HEC grade from Clariant. The reactive allyl groups in the side chains increase the grafting ability of cellulose ethers, leading to stable emulsions. A preferred TYLOSE ^(R) stabilizer is allyl-modified hydroxyethylcellulose powder (particle size <180 [mu]m) TYLOSE ^(R) AM H40 YP2 (AMHEC).

Exemplary preferred free radical initiators include, but are not limited to, water-soluble inorganic persulfate compounds such as ammonium persulfate, potassium persulfate, and sodium persulfate; peroxides such as hydrogen peroxide, benzoyl peroxide, Acetyl peroxide, and lauryl peroxide; organic hydroperoxides, such as cumene hydroperoxide and tert-butyl hydroperoxide; organic peracids, such as peracetic acid; and oil-soluble free radical generators, such as 2, 2'-azobisisobutyronitrile, and the like, and mixtures thereof. Peroxides and peracids can optionally be activated with reducing agents such as sodium bisulfite or ascorbic acid, transition metals, hydrazine, and the like. Particularly suitable free radical polymerization initiators include water-soluble azo polymerization initiators such as 2,2'-azobis(tert-alkyl) compounds having hydrosolubilizing substituents on the alkyl group. Preferred azo polymerization catalysts include VAZO ^(R) free radical polymerization initiators available from DuPont, such as VAZO ^(R) 44 (2,2'-azobis(2-(4,5-dihydroimidazolyl)propane), VAZO ^(R) 56 (2,2'-azobis(2-methylpropaminium) dihydrochloride), and VAZO ^(R) 68 (4,4'-azobis(4-cyanovaleric acid)).

Other emulsion polymerization additives well known in the emulsion polymerization art, such as solvents, buffers, chelating agents, inorganic electrolytes, chain terminators, and pH adjusters, may be included in the polymerization system as desired.

In general, the preferred general emulsion polymerization procedure for preparing the cationic associative polymers and cationic emulsion polymers of the present invention is as follows:

The monomer emulsion is preferably prepared in a reactor equipped with a nitrogen inlet and an agitator, wherein the required amount of each monomer is mixed in an emulsified amount of nonionic surfactant, or nonionic surfactant and anionic surfactant A certain amount of water of the mixture was combined under a nitrogen atmosphere, and the mixture was stirred. The degree of agitation required to form emulsions from monomer mixtures of the above types is well known to those skilled in the art. The emulsion so formed is substantially deoxygenated by any suitable method known in the art, such as by sparging with nitrogen gas, and a free radical initiator is then added to the emulsion with continuous mixing to initiate polymerization. The temperature of the emulsion can be adjusted to a temperature of about 20 to about 60°C as needed before or after adding the initiator. After addition of the initiator, the temperature of the polymerization mixture is typically adjusted to a temperature of about 60 to 80°C and maintained at that temperature for a sufficient time to complete the polymerization, usually about 3 to about 14 hours. If desired, unreacted residual monomers can be destroyed or further polymerized by adding various redox reagents or catalysts. The resulting polymer emulsion can then be cooled and drained from the reactor and collected.

Those skilled in the art of polymers will recognize that the amount of each monomeric component can be adjusted to obtain a polymer having any desired ratio of the monomeric components. Water can also be used in varying proportions as desired. Water-miscible solvents, such as alcohols, and other polymerization additives as described above may also be included in the reaction mixture. Preferred alcohols include glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, and the like.

The product polymer emulsion can be prepared to preferably comprise from about 1% to about 60% total polymer solids, more preferably from about 10% to about 40% total polymer solids, most preferably from about 15% to about 25% total polymer solids, Based on polymer weight.

Prior to any neutralization, the as-made polymer emulsion typically has a pH of about 7.5 or higher, a Brookfield viscosity of no more than about 100 mPa·s (spindle #2, 20 rpm) at ambient room temperature, and, for example, by the following method D The measured particle size does not exceed about 300 nm.

If desired, cationic associative polymer emulsions can be prepared by adjusting the pH, if an acidic pH is desired, to a value preferably from about 1 to no more than about 7 with acidic materials, preferably organic acids, inorganic acids, and the like. further processing. Emulsions of cationic associative polymers typically swell to form smooth, viscous solutions that are flowable and sprayable, or gel at neutral to acidic pHs, and the polymers are generally substantially stable at these pH values. The cationic associative polymer emulsion can be diluted with water or a solvent, or concentrated by evaporating a portion of the water. Alternatively, the resulting cationic associative polymer emulsion can be dried substantially to a powder or crystalline form by employing equipment well known in the art, for example, spray dryers, drum dryers, freeze dryers, and the like.

The cationic associative polymer of the present invention can be prepared by emulsion polymerization and used by introducing various known additives and conventional auxiliary agents, and solvents other than water into the liquid cationic associative polymer emulsion product as required , such that the intended use form of the final composition is obtained without altering or adversely affecting the technical characteristics or performance of the cationic associative polymer. Alternatively, the cationic associative polymer may be introduced as an ingredient, preferably in liquid form, into the formulation using conventional mixing equipment.

Preferred cationic associative polymers of this invention provide a Brookfield viscosity of about 300 mPa. to about 100,000 mPa·s or more (Brookfield RVT, 20 rpm, at ambient room temperature of about 25°C).

The multipurpose cationic associative polymers of the present invention are useful as emulsifiers, stabilizers, suspending agents, film formers, conditioners, moisturizers, spreading aids, and for increasing the potency of chemically and physiologically active ingredients and cosmetic materials , vehicles for deposition or delivery, and as excipients for improving the psychosensory, and aesthetic properties of formulations in which they are included. The cationic character of the cationic associative polymers renders them useful as antistatic agents and, under certain conditions, also provide insecticidal, bacteriostatic, antiseptic, and antimicrobial activity. Cationic associative polymers are useful in a variety of products for personal care, health care, household care, institutional and industrial (collectively "I&I") care, and for medical and industrial applications. The cationic associative polymers are preferably incorporated into non-basic, ie, pH acidic to substantially neutral compositions, but are not limited thereto.

The amount of cationic associative polymers that can be used depends on the purpose of the formulation including them and can be readily determined by one skilled in the art of formulation. For example, cationic associative polymers can be used in amounts (active weight %) generally from about 0.01% to about 25%, based on the weight of the total composition, as long as the physicochemical and functional properties of the composition comprising the cationic associative polymer are achieved, But not limited to this. Thus in a given composition or application, the cationic associative polymers of the present invention may, but need not, serve more than one function, such as thickener and conditioner, film former and carrier, and the like, as follows Describe in more detail.

The polymers of the present invention can be used as rheology modifiers or emulsion stabilizers in conventional emulsion formulations by introducing the polymers into the formulation at any step during the process of forming oil-in-water or water-in-oil or multiphase emulsions agent. For example, a polymer supplied as an aqueous emulsion product may be included with the water phase components. In a preferred emulsion embodiment, the polymer is added to the formulation after the final emulsion has been formed and cooled, the pH is adjusted down with an organic or inorganic acid to optimize acid swelling to the desired viscosity, and the final composition is subsequently adjusted to desired pH. If the pH of the finished composition or formulation comprising an acid-swellable cationic associative polymer is more acidic than required for the intended use of the formulation, the pH may subsequently be further adjusted with any, preferably physiologically tolerable, inorganic or organic base .

Compositions comprising cationic associative polymers can be packaged and dispensed from containers such as jars, bottles, tubes, spray bottles, wipes, cans, roll-on containers, stick containers, and the like (but not limited to these). There is no limitation on the form of the product into which the cationic associative polymer can be introduced, as long as the purpose of using the product is achieved. For example, personal care and healthcare products comprising cationic associative polymers can be, but are not limited to, gels, sprays (liquids or foams), emulsions (creams, lotions, pastes), liquids (rinses, washes), Hair lotions), sticks, ointments, suppositories, impregnated liniments, patches, and the like are applied to the skin, hair, scalp, and nails.

The cationic associative polymers of the present invention are suitable for use in the preparation of personal care (cosmetics, toiletry products, medicated cosmetics) and topical health care products, including, but not limited to, hair care products such as shampoos (including combination shampoos such as " 2-in-1" conditioning shampoos); post-shampoo rinses; styling and styling treatments, including styling aids such as gels and sprays, grooming aids such as pomades, conditioners, perms, volume hair smoothing products, and the like; skin care products (face, body, hands, scalp, and feet), such as creams, lotions, conditioners, and cleansing products; anti-acne products; anti-aging products (exfoliating agents , keratolytics, anticellulite, anti-wrinkle, and the like); skin protectants such as sunscreens, sunblocks, sunscreens, oils, silicones, and the like; skin color products (enhancing Whitening agents, lightening agents, sunless tanning accelerators, and the like); hair coloring agents (hair dyes, hair color rinses, highlighters, bleaching agents and the like); coloring skin coloring agents (face and body cosmetics , foundation, mascara, rouge, lip products, and the like); bath and shower products (body cleansers, body washes, shower gels, liquid soaps, soap bars, synthetic detergent bars, conditioning liquid bath oils, foam baths, bath powders, and the like); nail care products (polishes, polish removers, strengtheners, extenders, hardeners, cuticle removers, softeners, and the like); and Any aqueous acidic to substantially neutral composition into which an effective amount of the cationic associative polymer may be introduced to effect a beneficial or desired physical or chemical action therein during storage and/or use.

Toiletries and health and beauty aids (commonly referred to as HBAs) comprising cationic associative polymers may include, but are not limited to, hair removal products (shaving creams and lotions, depilatory agents, post-shave skin conditioners, and the like products); deodorants and antiperspirants; oral care products (mouth, teeth and gums) such as mouthwashes, dentifrices such as toothpaste, tooth powders, tooth polishes, teeth whiteners, breath fresheners, denture sticks mixtures, and the like; facial and body hair bleaching agents; and the like. Other health and beauty aids that may contain cationic associative polymers include, but are not limited to, synthetic tanning enhancers such as dihydroxyacetone (DHA), tyrosine, tyrosine esters, and the like. Sun tanning occasions; contains active ingredients such as kojic acid, hydroquinone, arbutin, fruits, plants or plant extracts, (lemon peel extract, chamomile, green tea, paper mulberry extract, and the like), Skin depigmentation, whitening, and lightening formulations of ascorbyl acid derivatives (ascorbyl palmitate, ascorbyl stearate, magnesium ascorbyl phosphate, and the like); foot care products such as keratin Cereal and callus removers, foot soaks, foot powders (medicinal, such as antifungal athlete's foot powders, ointments, sprays, and the like, and antiperspirant powders, or non-medicinal moisture absorbent powders), liquids Foot sprays (non-medicated, such as cooling, and deodorant sprays, and medicated antifungal sprays, antiperspirant sprays, and the like), and foot and nail conditioners (lotions and creams, nail softeners, and the like).

Topical health and beauty aids that can include cationic associative polymers (e.g., as spreading aids and film formers) include, but are not limited to, skin protection sprays, creams, lotions, gels, sticks, and powder products , such as insect repellents, antipruritics, antibacterials, disinfectants, sunblocks, sunscreens, skin tightening and toning creams and lotions, wart removing compositions, and the like.

Cationic associative polymers are especially useful as suspending agents for particles, such as mica, pearlescent agents, beads, and the like, making them suitable for use in skin products containing particles, microabrasives, and abrasives, such as showers containing exfoliating scrubs Gels, masks and skin cleansers. Many cosmetically useful particulate exfoliating agents are known in the art, and the choice and amount will depend on the desired exfoliating effect of using the composition, as will be recognized by those skilled in the cosmetic art. Useful exfoliating agents include, but are not limited to, bioabrasives, inorganic abrasives, synthetic polymers, and the like, and mixtures thereof. Bioabrasives include, but are not limited to, shell, seed, and pit or stone granules or powders derived from nuts, such as from walnut (Juglans regia) shells, almonds, pecans, and the like; fruit sources, such as apricots , avocado, coconut, olive, peach, and the like; vegetable sources such as corn on the cob, oat bran, rice, bush rosehip seeds, jojoba (wax, seed powder), microcrystalline cellulose, ground loofah, Ground seaweed, and the like; animal sources, such as oyster shells, silk, microcrystalline collagen, and the like. Inorganic abrasives include, but are not limited to, tin oxide, talc, silica (hydrated, colloidal, and the like), kaolin, precipitated chalk, salt (sodium chloride, Dead Sea salt, and the like), ground pumice, and the like. Synthetic polymers include, but are not limited to, microcrystalline polyamides (nylons), microcrystalline polyesters (polycarbonates), and the like. The polymers of the invention can also be used to suspend gas bubbles in liquid media.

Cationic associative polymers are useful as thickeners and film formers in various dermatologically medicated cosmetic compositions for topical improvement of skin conditions caused by dryness, photodamage, aging, acne, and similar factors Symptoms, comprising conditioners, moisturizers, antioxidants, exfoliants, keratolytics, vitamins, and the like, generally contain active acidic ingredients and have a pH of about 0.5 to about 5. If the cationic associative polymer is incorporated into these aforementioned acidic product embodiments, the active acid ingredient can be used as an active skin treatment agent and as an acid swelling agent for the cationic associative polymer to achieve the desired viscosity.

In a medicated cosmetic aspect, cationic associative polymers can be used as thickeners for containing acidic anti-aging, anti-cellulite, and anti-acne agents, hydroxycarboxylic acids such as alpha-hydroxy acids (AHA), beta- Hydroxy acids (BHA), alpha-amino acids, alpha-keto acids (AKA), and mixtures thereof are used as active ingredients in active skin treatment lotions and creams. In these medicated cosmetics, AHAs may include, but are not limited to, lactic acid, glycolic acid, fruit acids such as malic acid, citric acid, tartaric acid, extracts of natural compounds containing AHAs such as apple extract, apricot extract , and analogues, honey extract, 2-hydroxycaprylic acid, glyceric acid (dihydroxypropionic acid), tartronic acid (hydroxypropanedioic acid), gluconic acid, mandelic acid, benzilic acid, azelaic acid, alpha - Lipoic acid, salicylic acid, AHA salts and derivatives such as arginine glycolate, ammonium glycolate, sodium glycolate, arginine lactate, ammonium lactate, sodium lactate, alpha-hydroxybutyrate, alpha -Hydroxyisobutyric acid, alpha-hydroxyisocaproic acid, alpha-hydroxyisovalerate, altropolic acid, and the like. BHAs may include, but are not limited to, 3-hydroxypropionic acid, beta-hydroxybutyric acid, beta-phenyllactic acid, beta-phenylpyruvic acid, and the like. Alpha-amino acids include, but are not limited to, alpha-aminodicarboxylic acids, such as aspartic acid, glutamic acid, and mixtures thereof, sometimes used in combination with fruit acids. AKA includes pyruvate. In some antiaging compositions, the acidic active agent may be retinoic acid, halogenated carboxylic acids such as trichloroacetic acid, acidic antioxidants such as ascorbic acid (vitamin C), mineral acids, phytic acid, lysophosphatidic acid, and the like things. Some acidic anti-acne actives, for example, may include salicylic acid, salicylic acid derivatives such as 5-octanoylsalicylic acid, retinoic acid, and derivatives thereof.

COSMETICS & TOILETRIES ^(R) , C&T Ingredient Resource Series, "AHAs & Cellulite Products How They Work" (published 1995), and "Medicated Cosmetics" (published 1998) discuss the use or formulation of active skin treatment compositions, which Both are available from Allured Publishing Company, incorporated herein by reference. Compositions comprising alpha-amino acids acidified with ascorbic acid are described in US No. 6,197,317 B1, and commercial medicated cosmetic formulations employing these acids in antiaging, skin care systems are sold under the trade name AFA by exCel Cosmeceuticals (Bloomfield Hills, MI) . For example, the term "AFA" as described in the suppliers' commercial literature was codified by the developers to describe the amino acid/vitamin C combination as an acronym for amino acid fruit acid and as "amino acid Filaggrin based antioxidant".

Other healthcare products in which cationic associative polymers may be included are medical products, such as topical and non-topical medications, and devices. In pharmaceutical formulations, cationic associative polymers can be used in products such as creams, pomades, gels, pastes, ointments, tablets, gel capsules, purgative fluids (enemas, emetics, colon, and the like), suppositories, antifungal foams, ophthalmic products (eye products such as eye drops, artificial tears, glaucoma drug delivery drops, contact lens cleaners, and the like), ear products (wax softeners, wax removers, otitis drug delivery drops, and the like), nasal products (drops, ointments, sprays, and the like), and wound care (liquid bandages, wound dressings, antibiotic creams, Ointments, and the like), but not limited to, are used as thickeners and/or lubricants.

The film-forming and acid-swellable characteristics of cationic associative polymers make the cationic associative polymers particularly useful as excipients in topical medical compositions for facilitating and increasing the transdermal delivery of active ingredients to or through the skin for To increase the potency of anti-acne formulations and topical analgesics, and to control the release of drugs such as antacids from tablets, or syrups, at low pH, such as in the stomach; to control the release of drugs from tablets, lozenges, Release of chewables, and the like in the mildly acidic environment of the mouth; or from the mildly acidic environment of the vagina from suppositories, ointments, creams, and the like; facilitates release of dandruff control agents from shampoos, oils Deposition in creams, and the like; increased deposition of colorants derived from coloring cosmetics (cosmetics, lip sticks, rouge, and the like) on the skin and hair dyes of colorants derived from hair dyes, and the like deposition.

In addition to the foregoing, the cationic character of the polymers of the present invention at acidic pH and their surprising cationic compatibility render the cationic associative polymers useful as antistatic agents in a variety of personal care, health care, I&I, and medical applications. , Insecticide, antimicrobial, and other thickeners for antiseptic compositions. For example, the polymers can be found in over-the-counter (OTC) health care and pharmaceutical products that typically employ cationic biocides, such as in oral care compositions for platelet and tartar control, and liquid excipients containing therapeutic agents , used as a thickening agent in syrups, gels, and the like. Under certain controlled pH conditions, the cationic character of the cationic associative polymer may itself provide antistatic activity or insecticidal, antimicrobial, or similar antiseptic activity.

The polymers of the present invention are useful as (but not limited to) lubricant coatings for medical devices, such as soft tissue implants, surgical gloves, catheters, cannulas, and the like, as medical instruments, wound dressings, and the like Removable protective film coatings for things, used as mucoadhesives, especially in the acidic environment of the stomach, used as formulated products for medical applications, such as disinfectant hand creams, antiviral products (for anionic viruses) , antibiotic ointments, sprays and creams, non-drops, sprayable disinfectants for hospitals, carriers and thickeners for hard surface antimicrobial finishes applied during routine maintenance, and the like.

The polymers of the present invention are useful in home care, and I&I applications, for example, as rheology modifiers, fabric conditioners, antistatic agents, especially for improving formulation efficiency or improving disinfection by "sticking to surfaces" agent, and the effectiveness of insecticidal formulations, and for synergistically enhancing fabric softening efficacy with conventional fabric softeners. Typical household and I&I products that may contain the polymers of the invention include, but are not limited to, laundry and fabric care products such as detergents, fabric softeners (liquid or sheet), ironing sprays, dry cleaning aids, anti-wrinkle Sprays, stain removers and the like; hard surface cleaners for kitchens and bathrooms and appliances used or provided therein, such as toilet bowl gels, pipe and spray head cleaners, hard water deposit removers, floor and tile cleaners , wall cleaners, floor and chrome fixture polishes, alkali-strip vinyl floor cleaners, marble and ceramic cleaners, air freshener gels, liquid cleaners for pans, and the like; disinfectant cleaners, Such as toilet bowl and bidet cleaners, disinfectant hand soaps, house deodorizers, and the like.

The polymers of the present invention can be used as rheology modifiers, dispersants, stabilizers, accelerators, or antimicrobial agents, and the like in industrial product applications, including, but not limited to, textiles (processing, finishing, printing) , and dyeing auxiliaries, protective washable surface coatings, preparation of synthetic leather by saturating nonwovens, and the like, manufacture of woven fabrics, nonwovens, natural and synthetic fibers and the like); water treatment (wastewater , cooling water, drinking water purification, and the like); chemical pill containment agents (acid-pill absorbers, and the like); leather and hide working (processing aids, finishing, coating, embossing, and the like articles); paper and paper manufacture (surface coatings, such as pigmented coatings, antistatic coatings, and the like, pulp binders, surface sizing agents, dry and wet strength enhancers, wet-laid felts, and the like manufacture of objects); printing (inks, anti-wicking inkjet printer inks, thickeners for ink formulations containing cationic dyes for printing acrylic fabrics, and the like); paints (pigments and grinding additives for crosslinking agent for epoxy latex emulsions, particle suspension aids for clays, pigments, and the like); mill effluent treatment (phenols in paper mill effluents, and flocculants for the like); metal processing ( Acid etch cleaners, low pH metal coatings, pickling agents in chill roll steel treatments, and the like); adhesives (clear adhesives, for bonding metals, plastics, wood, and the like) Adhesion promoters, nonwoven floc adhesives, tie coats, binders, and the like); wood preservation; and industrial structural products for building and roads (cement plasticizers, asphalt at low pH Emulsion stabilizer, acid etchant for cement, consistency modifier for concrete, mortar, putty, and the like). The polymers of the present invention are especially useful as thickeners for rust removers, acid truck cleaners, scale removers, and the like, and as materials containing particles such as clays, pigments (titanium dioxide, calcium carbonate, and other minerals) , Abrasives, and similar products are used as dispersion stabilizers for various aforementioned industrial applications, and for drilling muds.

Products comprising the polymers of the present invention may contain a variety of conventional additives and adjuvants known in the art, some of which may serve more than one function. Amounts may vary depending on the use or nature of the product and can be readily determined by one skilled in the art of formulation or from the literature. The term "cosmetic adjuvant" includes cosmetically and pharmaceutically acceptable product stabilizing and product finishing agents used to maintain the physical stability of the composition and its visible aesthetic appearance and marketability during the useful shelf life of the composition. attraction.

The term "fixation" as applied to polymers includes film-forming, adhesive or coating properties deposited on the surface to which the polymer is applied. As commonly understood in the hair care art, and as used herein, the terms "hair styling and hair fixing" collectively refer to hair styling agents, which are hair fixing and film forming agents and are applied topically to the hair to actively contribute to ease of styling and / or maintain the hairstyle, and maintain the reshapeability of the hairstyle. Thus, hair styling compositions include hair styling, hair fixing, and hair grooming products generally applied to the hair (wet or dry) in the form of gels, rinses, emulsions (oil-in-water, water-in-oil or multiphase), such as lotions and creams, pomades, sprays (pressurized or not), injections (spritzes), foams such as mousses, shampoos, solids such as sticks, semi-solids and the like or applied from a hair styling aid in which the hair styling composition is impregnated or coated, such that the hair styling agent is in contact with the hair for a period of time until it is removed by washing.

The term "conditioning agent", and grammatical variants thereof, when referring to compositions for use in skin care and hair care includes cosmetically and pharmaceutically useful materials which are humectants, humectants, and emollients. Some conditioning agents are considered to serve more than one function in the composition, such as emulsifiers, lubricants, and solvents.

Preferred hair care composition embodiments comprise the polymers of the present invention in an amount effective to provide the hair care composition with properties such as hair fixative properties, hair conditioning properties, viscous properties (thickening, rheology modification), or combination. Optionally, the hair care composition can include one or more auxiliary film formers, auxiliary hair fixatives, auxiliary hair conditioning agents, auxiliary rheology modifiers, or mixtures thereof.

Preferred skin care composition embodiments comprise the polymers of the present invention in amounts effective to provide the skin care composition with properties such as skin conditioning properties, viscous properties (thickening, rheology modification), or combinations thereof. Optionally, the skin care compositions can include one or more auxiliary skin conditioning agents, auxiliary rheology modifiers, or mixtures thereof.

Product formulations comprising the polymers of the present invention may contain various additives and cosmetic auxiliaries conventionally or commonly included in personal care, household care, institutional care, and industrial care products, and industrial processes, including, but not limited to , acidifying or alkalizing pH adjusters and buffering agents; auxiliary fixative and film formers, such as nonionic, anionic, cationic, or amphoteric polymers of synthetic or natural origin, and the like; auxiliary rheology modifiers, such as increasing Viscopolymers, gums, or resins thickeners or gelling agents; additives, such as emulsifiers, emulsion stabilizers, waxes, dispersants, and the like, and viscosity control agents, such as solvents, electrolytes, and the like; auxiliary Conditioning agents, such as antistatic agents, synthetic oils, vegetable or animal oils, silicone oils, monomeric or polymeric quaternized ammonium compounds and their derivatives, shine enhancers, moisturizers, emollients, humectants, Lubricants, sunscreens, and the like; oxidizing agents; reducing agents; surfactants, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants, and silicone derivatives thereof; polymeric film modifiers, Such as plasticizers, tackifiers, tackifiers, wetting agents, and the like; product stabilizers and finishing agents, such as chelating agents, opacifying agents, pearlizing agents, proteinaceous materials and their derivatives, vitamins and their derivatives preservatives, fragrances, solubilizers, colorants (temporary or permanent), such as pigments and dyes, UV absorbers, and the like; propellants (water-miscible or water-immiscible), such as fluorinated hydrocarbons, liquid Volatile hydrocarbons, compressed gases, and the like; and mixtures thereof.

The additives and adjunct ingredients, products, or materials discussed herein that may be used with the cationic associative polymers of the present invention will be referred to by the International Nomenclature commonly known as the INCI nomenclature or their common chemical names, where the INCI nomenclature is established in the International They are assigned to them in the International Cosmetic Ingredient Dictionary (published by the Cosmetic, Toiletry, and Fragrance Association, Washington DC) (hereinafter referred to as the INCI Dictionary), as may be found in any edition thereof, e.g., Part 1 of the Sixth Edition. and Volume 2 (1995) or Volumes 1-3 (1997, 2000) of the Seventh and Eighth Editions. Multiple suppliers of materials listed by INCI name, trade name, or both can be found in the INCI dictionary and in many trade publications, the latter including but not limited to 2001 McCutcheon's Directories, Volume 1: Emulsifiers & Detergents and Volume 2: Functional Materials (published by McCutcheon's Division, Manufacturing Confectioner Publishing Co., Glen Rock, NJ (2001)); and 2001 Cosmetic Bench Reference, Edition of COSMETICS & TOILETRIES ^® , 115(13) (published by Allured Publishing Corporation, Carol Stream, IL (2001)); the disclosure of each publication is hereby incorporated by reference. These components and formulations of the compositions are additionally described in detail in well-known references, such as Cosmetics Science and Technology, First Edition (Sagarin (ed.)) (published 1957), and Second Edition (Balsam , et al. (ed.)) (published 1972-74); and The Chemistry and Manufacture of Cosmetics, second edition (deNavarre (ed.)) (published 1975), and third edition (Schlossman (editor)) (published in 2000), both available from Allured Publishing Corporation; Rieger (editor), Harry's Cosmeticology, Eighth Edition, Chemical Publishing, Co., Inc., Newyork, NY (2000); and Various formulations available to those skilled in the pharmaceutical arts, such as Remington's Pharmaceutical Sciences, Fourteenth Edition, Mack Publishing Company, Easton, PA (1970); the relevant disclosure of each publication is hereby incorporated by reference herein invention.

Formulated for personal care and topical, dermatological health care, application to the skin and mucous membranes for cleansing or soothing, by the presence of a drug or pharmaceutically acceptable compound, and by the controlled conditions available for manufacture of the product. Compositions use many of the same or similar physiologically tolerable ingredients compounded and formulated into the same or similar product forms differing primarily in the purity level of the selected ingredients. Likewise, many of the ingredients in the products for home use and I&I are the same or similar to those described above, differing mainly in the amounts and grades of materials used. It is also known that the selection and allowable amounts of ingredients may also be restricted by government regulations at the national, regional, local or international level. Therefore, the discussion herein of various ingredients that can be used in personal care and health care products can be applied to household and I&I products and industrial settings.

The choice and amount of ingredients in formulated compositions comprising cationic associative polymers will vary according to the product and its function, as is well known to those skilled in the art of formulation. Formulation ingredients for personal care and topical health care products may typically include, but are not limited to, solvents, surfactants (as cleansers, emulsifiers, foam boosters, hydrotropes, solubilizers, and suspending agents), Non-surfactant suspending agents, emulsifying agents, skin conditioning agents (emollients, wetting agents, moisturizers, and the like), hair conditioning agents, hair fixatives, film formers, skin protectants, binders, Chelating agents, antimicrobial agents, antifungal agents, antidandruff agents, abrasives, adhesives, absorbents, dyes, deodorants, antiperspirants, opacifying and pearlizing agents, antioxidants, preservatives, propellants, spreading Adjuvants, sunscreens, sunless skin tanning accelerators, UV light absorbers, pH regulators, botanicals, hair colorants, oxidizing agents, reducing agents, skin bleaching agents, pigments, physiologically active agents, anti-inflammatory agents, topical Narcotics, fragrances and fragrance solubilizers, and the like, in addition to previously discussed ingredients which may not appear here. Oral care products, for example, may contain anticaries, antitartar and/or antiplatelet agents in addition to surfactants, abrasives, wetting agents, and flavorants. An in-depth listing of substances and their conventional functions and product classes appears in the INCI Dictionary in general and in Parts 4 and 5 of Volume II of the Seventh Edition in particular, which is hereby incorporated by reference.

The polymers of the invention formulated into aqueous emulsions are especially useful in water-based formulations, and formulations comprising water-miscible co-solvents, but are not limited thereto. Commonly used solvents are generally liquids such as water (deionized, distilled or purified), alcohols, polyols, and the like, and mixtures thereof. Non-aqueous or hydrophobic co-solvents are often used in essentially anhydrous products such as nail varnishes, aerosol propellant sprays, or for specific functions such as removing oil, sebum, cosmetics, or for dissolving dyes, fragrances, and Analogs, or are introduced into the oil phase of the emulsion. Non-limiting examples of non-aqueous auxiliary solvents include straight and branched chain alcohols, such as ethanol, propanol, isopropanol, hexanol, and the like; aromatic alcohols, such as benzyl alcohol, cyclohexanol, and the like substances; saturated _C12 - _C30 fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and the like. Non-limiting examples of polyols include polyhydric alcohols such as glycerin, propylene glycol, butylene glycol, hexylene glycol, _C2 - _C4 alkoxylated alcohols and _C2 - _C4 alkoxylated polyols, such as those having about Ethoxylated, propoxylated, and butoxylated ethers of alcohols, diols, and polyols of 2 to about 30 carbon atoms and 1 to about 40 alkoxy units, polypropylene glycol, polybutylene Alcohols, and the like. Non-limiting examples of non-aqueous auxiliary solvents include silicones, and silicone derivatives, such as cyclomethicone, and the like, ketones, such as acetone and methyl ethyl ketone; natural and synthetic oils and waxes, such as vegetable oils, vegetable oils, animal oils, essential oils, mineral oils, C ₇ -C ₄₀ isoparaffins, alkyl carboxylates such as ethyl acetate, amyl acetate, ethyl lactate, and the like, jojoba oil, Shark liver oil, and the like. Some of the aforementioned non-aqueous co-solvents may also be conditioners and emulsifiers.

Surfactants are generally used as detergents, emulsifiers, foam boosters, hydrotropes and suspending agents. The polymers of the invention can be used in formulations comprising all classes of surfactants, ie anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants. As used herein, the term "amphoteric surfactant" includes zwitterionic surfactants. In addition to the aforementioned references, the following literature discusses classes of surfactants: Cosmetics & Toiletries( ^{R )} C&T Ingredient Resource Serices, "The Encyclopedia of Surfactants", 2nd Edition, Rieger (Ed.), Allured Publishing Corporation (1996); Schwartz, et al., Surface Active Agents, Their Chemistry and Technology (Published 1949); and Surface Active Agents and Detergents, pp. Volume II, Published 1958, Interscience Publishers; each incorporated herein by reference.

Surprisingly, the polymers of the present invention can be used in compositions containing relatively high concentrations (about 10-40% by weight) of anionic surfactants, such as shampoos and 2-in-1 liquid conditioners for hair and body (bath) products / Detergents are used as thickeners and deposition aids. The cationic associative polymers of the present invention are compatible with cationic surfactants having antistatic activity, such as those used in hair care products and fabric care products.

Anionic surfactants include substances that have negatively charged hydrophobes or that carry a negative charge when the pH is raised to neutral or above, such as acyl amino acids, and salts thereof, e.g., acyl glutamates, acyl peptides, creatine Amino acid salts, and taurates; carboxylic acids, and their salts, for example, alkanol acids and alkanoates, ester carboxylic acids, and ether carboxylic acids; phosphoric acid esters and their salts; sulfonic acids and their salts, for example , acyl isethionates, alkylaryl sulfonates, alkyl sulfonates, and sulfosuccinates; and sulfates, such as alkyl ether sulfates and alkyl sulfates.

Non-limiting examples of anionic surfactants include monobasic salts of acyl glutamate that are slightly acidic in aqueous solution, such as sodium acyl glutamate and sodium hydrogenated tallow glutamate; salts of acyl-hydrolyzed proteins such as potassium, Palmitoyl hydrolyzed milk protein, sodium cocoyl hydrolyzed soy protein, and TEA-rosin acyl hydrolyzed collagen; acyl sarcosinates such as myristoyl sarcosinate, sodium cocoyl sarcosinate, and TEA - Lauroyl sarcosinate; salts of sodium methylacyl taurate, such as sodium lauroyl taurate and sodium methylcocoyl taurate; alkanoic acids and alkanoic acid salts, such as form water-soluble soaps Fatty acids derived from animal and vegetable glycerides and water-insoluble emulsifying soaps (including sodium stearate, aluminum stearate, and zinc undecylenate); esters of carboxylic acids such as dinonoxynol -9-citrates; acyl lactylates such as calcium stearoyl lactylate and laureth-6 citrate; polyoxyethylene chains of varying lengths derived from ethoxylated alcohols or phenolic ether carboxylic acids, such as nonoxynol-8 carboxylic acid, and sodium tridecyl poly(oxyethylene) ether-13 carboxylate; mono- and diesters of phosphoric acid and their salts, such as phospholipids, di Lauryl poly(oxyethylene) ether-4-phosphate, DEA-oleyl poly(oxyethylene) ether-10 phosphate, and triethanolamine lauryl phosphate; acyl isethionates such as cocoyl isethionate Sodium sulfonates; alkylarylbenzenesulfonates, such as alpha-olefin sulfonates (AOS) and alkali metal, alkaline earth metal, and alkanolamine salts thereof, and sodium dodecylbenzenesulfonate; alkyl Sulfonates, such as sodium C ₁₂ -C ₁₄ olefin sulfonate, sodium cocomonoglyceride sulfonate, sodium C ₁₂ -C ₁₅ pareth-15 sulfonate, and sodium lauryl sulfoacetate; sulfosuccinate, Such as mono- and diesters of sulfosuccinic acid, their salts and their alkoxylated alkyl and alkylamido derivatives, such as sodium di(C ₄ -C ₁₀ )alkyl sulfosuccinate, lauryl poly( disodium oxyethylene) ether sulfosuccinate, oleamido MEA-disodium sulfosuccinate, and C ₁₂ -C ₁₅ pareth disodium sulfosuccinate; alkyl ether sulfates such as sodium lauryl ether sulfate and Ammonium (with about 1 to about 12 moles of ethylene oxide); alkyl sulfates such as sodium, ammonium and triethanolamine salts of C ₁₂ -C ₁₈ alkyl sulfates, sodium C ₁₂ -C ₁₄ olefin sulfates, lauryl poly(oxygen Sodium vinyl) ether-6 carboxylate, sodium _C12 - _C18 pareth sulfate, and the like.

Cationic surfactants can have hydrophobes that carry a positive charge or are uncharged at pH values near neutral or lower, such as alkylamines, alkylimidazolines, ethoxylated amines, and quaternary ammonium compounds. The cationic surfactants used in cosmetics are preferably N-derivatives and the neutralizing anions can be inorganic or organic. Cationic surfactant materials useful herein are quaternary ammonium compounds corresponding to the general formula: (R ¹⁰ R ¹¹ R ¹² R ¹³ N ⁺ )E ⁻ , wherein R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are independently is selected from aliphatic groups having 1 to about 22 carbon atoms, or aromatic, alkoxy, polyoxyalkylene, alkylamido, having 1 to about 22 carbon atoms in the alkyl chain, hydroxyalkyl, aryl or alkylaryl group; and E ^- is a salt-forming anion such as selected from halogen, (eg chloride, bromide), acetate, citrate, lactate, glycolate, phosphate , nitrates, sulfates, and alkyl sulfates. In addition to carbon and hydrogen atoms, aliphatic groups may also contain ether linkages, ester linkages, and other groups such as amino groups. Longer chain aliphatic groups, eg, those having about 12 or more carbons, can be saturated or unsaturated.

The alkylamines may be salts of substituted or unsubstituted primary, secondary and tertiary aliphatic _C12 - _C22 alkylamines, and are sometimes referred to as "amidoamines". Non-limiting examples of alkylamines and salts thereof include dimethyl cocoamine, dimethyl palmitamine, dioctylamine, dimethylstearylamine, dimethyl soyamine, soyamine, myristylamine , tridecylamine, ethylstearylamine, N-tallowpropanediamine, ethoxylated stearylamine, dihydroxyethylstearylamine, arachidyl behenylamine, di Methyllaurylamine, stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropanediamine dichloride, and aminodimethicone ( End-blocked silicone polymers, such as the INCI name for aminoethylaminopropylsiloxane). Non-limiting examples of amidoamines and salts thereof include stearamidopropyl dimethylamine, stearamidopropyl dimethylamine citrate, palmitamidopropyl diethylamine, and coconut oil Amidopropyl Dimethylamine Lactate. Other cationic surfactants include distearyldimethylammonium chloride, dicetyldimethylammonium chloride, guar hydroxypropyltrimethylammonium chloride, and the like. At low pH, amine oxides can be protonated and behave similarly to N-alkylamines.

Non-limiting examples of alkyl imidazolines include alkyl hydroxyethyl imidazolines, such as stearyl hydroxyethyl imidazoline, coco hydroxyethyl imidazoline, ethyl hydroxymethyl oleyl oxazoline, and the like . Non-limiting examples of ethoxylated amines include PEG-cocopolyamine, PEG-15 tallowamine, quaternium-52, and the like.

Quaternary ammonium compounds are monomeric or polymeric materials that contain at least one nitrogen atom that is covalently bonded to four alkyl and/or aryl substituents and that remains positively charged regardless of the pH of the environment. Quaternary ammonium compounds include many substances widely used as surfactants, conditioning agents, antistatic agents, and antimicrobial agents, and include alkyl benzyl dimethyl ammonium salts, alkyl betaines, heterocyclic ammonium salts, and tetra Alkyl ammonium salts. Long chain (fatty) alkyl benzyl dimethyl ammonium salts are preferred as conditioners, antistatic agents, and fabric softeners, as discussed in more detail below. Other quaternary ammonium compounds include quaternary ammonium silicones.

Non-limiting examples of alkyl benzyl dimethyl ammonium salts include stearyl dimethyl benzyl ammonium chloride (stearalkonium), benzalkonium chloride, quaternium-63, oleyl dimethyl benzyl ammonium chloride, Lauryldimethylammonium chloride, and the like. Alkyl betaine compounds include alkylamidopropyl betaine, alkylamidopropyl hydroxysultaine, and sodium alkylamidopropyl hydroxyphosphoryl betaine. Non-limiting examples of alkyl betaine compounds include oleyl betaine, coco-betaine, cocoamidopropyl betaine, coco-hydroxysultaine, coco/oleamidopropyl betaine , Coco-Sultaine, Cocamidopropyl Hydroxysultaine, and Sodium Lauroamidopropyl Hydroxyphosphoryl Betaine. Heterocyclic ammonium salts include alkyl ethyl morpholinium ethosulfates, isostearyl ethyliminium ethosulfates, and alkylpyridinium chlorides, and are generally used as emulsifiers. Non-limiting examples of heterocyclic ammonium salts include cetylpyridinium chloride, isostearylethyliminium ethosulfate, and the like. Non-limiting examples of tetraalkylammonium salts include cocamidopropylethyldimethylammonium ethosulfate, hydroxyethylcetyldimethylammonium chloride, quaternium-18, and cocodimonium Methylammonium hydroxypropyl hydrolyzed proteins such as hair keratin, and the like.

The polymers of the present invention are surprisingly compatible with cationic surfactants and other cationic compounds suitable as antistatic agents. The term "antistatic agent" refers to ingredients that modify the electrical properties of cosmetic raw materials or human surfaces (skin, hair, etc.) and textiles by, for example, reducing their propensity to acquire an electrical charge and thus condition hair, skin and fabrics. The cationic compatibility of cationic associative polymers makes them suitable for incorporation into formulations containing antistatic agents commonly used in hair care compositions, such as shampoos, post-shampoo conditioning rinses, hair sprays, hair dressings and the like. Antistatic agents can be used in amounts up to about 30% by weight of the final composition, but are not limited thereto.

Antistatic agents include, but are not limited to, quaternary ammonium compounds, protein derivatives, synthetic quaternary ammonium polymers, amines, protonated amine oxides, betaines, and the like, which in addition to any surfactant properties imparted by these materials, It can also be used as an antistatic agent in certain formulations and under controlled pH conditions. In addition to the antistatic agents discussed above, non-limiting examples of quaternary ammonium compounds that can be used as antistatic agents are acetamidopropyltrimethylammonium chloride, behenylamidopropyldimethylamine, 20 Dialkanoamidopropyl ethyl dimethyl ammonium ethosulfate, behenyl trimethyl ammonium chloride, cetyl polyoxyethylene ether morpholine  ethyl sulfate, cetyl trimethyl ammonium chloride Methyl Ammonium Chloride, Cocamidopropyl Ethyl Dimonium Ethyl Sulfate, Dicetyl Dimonium Chloride, Dimethicone Hydroxypropyl Trimonium Chloride , Hydroxyethylbehenylamidopropyldimethylammonium chloride, quaternium-26, quaternium-27, quaternium-53, quaternium-63, quaternium-70, quaternium-72, quaternium-76 hydrolyzed collagen, PPG-9 Diethylmethylammonium Chloride, PPG-25 Diethylmethylammonium Chloride, PPG-40 Diethylmethylammonium Chloride, Stearyl Dimethylbenzyl Ammonium Chloride, Stearyl Amidopropyl ethyl dimethyl ammonium ethosulfate, stearyl dimethyl ammonium hydroxypropyl hydrolyzed wheat protein, stearyl dimethyl ammonium hydroxypropyl hydrolyzed collagen, wheat germ amidopropyl dimethyl benzyl ammonium chloride, wheat germ amidopropyl ethyl dimethyl ammonium ethosulfate, and the like.

Synthesis of quaternary ammonium polymers, including film-forming and conditioning polymers. Non-limiting examples of synthetic quaternary ammonium polymers include polymers and copolymers of dimethyldiallylammonium chloride, such as polyquaternium-4, polyquaternium-6, polyquaternium-7, polyquaternium-22, polyquaternium-10, polyquaternium -11, polyquaternium-15, polyquaternium-16, polyquaternium-24, polyquaternium-28, polyquaternium-32, polyquaternium-33, polyquaternium-35, polyquaternium-37, polyquaternium-39, polyquaternium-44, PEG-2-cocoa ammonium chloride, quaternium-52, and the like.

The term "hair styling composition" includes compositions comprising at least one polymer according to the invention as a hair styling agent which are applied to the hair (wet or dry) before, during or after shaping the hair into the desired shape (curly or straight). products, but not limited to product form.

The polymers of the present invention are surprisingly useful as the sole film-forming, rheology-modifying, conditioning fixatives in hair styling and hair styling compositions. The polymers of the present invention may also be used in combination with commercially available auxiliary hair fixative polymers, such as nonionic, cationic, and amphoteric hair styling polymers, cationic conditioning polymers, and combinations thereof. It has surprisingly been found that by suitable combination of the polymers of the present invention with auxiliary conventional hair fixative and/or hair conditioning polymers, viscosity and hair styling performance properties are unexpectedly increased. Conventional Polymers Hair fixative and hair styling polymers are well known in the art and include gums and resins of natural origin and neutral or anionic polymers of synthetic origin. Listings of commercially available hair fixative and conditioning fixative polymers are readily found in INCI dictionaries, supplier web sites, and commercial literature. See, e.g., The Encyclopedia of Polymers published in Cosmetics & Toiletries( ^{R )} , 117(12), December 2002 (Allured Publishing Corporation, Carol Stream, IL), and the relevant disclosure is incorporated herein by reference and into the present invention.

Suitable commercially available nonionic polymers (i.e., neutral) for use as hair styling or fixing polymers include, but are not limited to, polyvinylpyrrolidone (PVP), polyvinylpyrrolidone/vinyl acetate copolymer ( PVP/VA), and the like. Commercially available cationic immobilizing polymers include, but are not limited to, polymers with INCI designations, polyquaterniums such as polyquaternium-4, diallyldimethylammonium chloride/hydroxyethylcellulose copolymers (such as CELQUAT ^(R) H- 100, National Starch); polyquaternium-11, quaternized vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer (such as GAFQUAT ^(R) 734, 755, 755N, ISP); polyquaternium-16, quaternized vinyl Polypyrrolidone/vinylimidazolium chloride copolymer (such as LUVIQUAT ^® FC-370, BASF); polyquaternium-28, vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloride copolymer (such as GAFQUAT ^® HS-100, ISP); polyquaternium-46, quaternized vinylcaprolactam/vinylpyrrolidone/methylvinylimidazolium  methosulfate copolymer; polyquaternium-55, quaternized vinylpyrrolidone/dimethyl Aminopropylmethacrylamide/lauryldimethylpropylmethacrylamidoammonium chloride copolymers (such as STYLEZETMW, ISP), and similar; and amino-substituted polymers that are cationic at acidic pH substances, such as vinyl caprolactam/PVP/dimethylaminoethyl methacrylate copolymer (such as GAFFIX ^® VC-713, ISP); PVP/dimethylaminoethyl methacrylate copolymer (such as copolymer 845, ISP), PVP/DMAPA acrylate copolymer (eg STYLEZE ^™ CC-10, ISP), pyrrolidone carboxylate salt of chitosan with INCI designation, chitosan PCA (eg ^KYTAMER® PC, Amerchol) , and analogs.

Suitable amphoteric immobilizing polymers include, but are not limited to, octylacrylamide/acrylates/butylaminoethyl methacrylate copolymers (such as AMPHOMER ^(R) polymers, National Starch), acrylates/lauryl acrylate/acrylic acid Stearyl esters/ethylamine oxide methacrylate copolymers (such as DIAFORMER ^(R) polymers, Clariant Corp.), and the like.

Suitable commercial conditioning polymers include polymeric quats such as, but not limited to, polyquaternium-7 (a polymeric quat of acrylamide and dimethyldiallylammonium chloride monomers), such as MACKERNIUM ^™ -007 , McIntyre Group, Ltd.; polyquaternium-10 (polymer quaternary ammonium salt of hydroxyethylcellulose reacted with trimethylammonium substituted epoxide), such as UCARE ^(R) polymers JR, LK, LR, SR series, Amerchol and CELQUAT ^(R) SC series, National Starch; polyquaternium-39 (polymer quaternary ammonium salt of acrylic acid, diallyldimethylammonium chloride and acrylamide), such as MERQUAT ^(R ) and MERQUAT ^(R) Plus polymers, Ondeo Nalco; Quaternized derivatives of natural gums, eg, guar hydroxypropyltrimethylammonium chloride (eg JAGUAR ^(R) and JAGUAR ^(R) Excel polymers, Rhodia, Inc.), and the like.

A number of quaternary ammonium compounds are used in fabric conditioning and fabric care, they are commonly referred to as fabric softeners, and are typically used in amounts up to about 20% by weight of the total formulation, but are not limited thereto. Fabric softeners useful in combination with the cationic associative polymers of the present invention typically include long chain alkylated quaternary ammonium compounds such as dialkyldimethyl quaternary ammonium compounds, imidazoline quaternary compounds, amidoamine quaternary compounds, dihydroxypropyl quaternary compounds, Dialkyl ester quaternization derivatives of ammonium compounds; dialkyl ester quaternization derivatives of methyl triethanol ammonium compounds, ester amidoamine compounds, and diester quaternization derivatives of dimethyldiethanol ammonium chloride , for example as described in Whalley's review article "Fabric Conditioners", HAPPI, pp. 55-58 (February 1995), incorporated herein by reference.

In addition to the previously discussed antistatic agents, non-limiting examples of dialkyldimethyl quaternary ammonium compounds include N,N-Dioleyl-N,N-Dimethylammonium Chloride, N,N-Ditallowyl -N,N-Dimethylammonium ethosulfate, N,N-di(hydrogenated-tallowyl)-N,N-dimethylammonium chloride, and the like. Non-limiting examples of imidazoline quaternary compounds include 1-N-methyl-3-N-tallowamidoethyl imidazolinium chloride, 3-methyl-1-tallowamidoethyl-2- tallow imidazolinium methosulfate (available under the tradename VARISOFT ^(R) 475 from Witco Chemical Company), and the like. Non-limiting examples of amidoamine quaternary compounds include N-alkyl-N-methyl-N,N-bis(2-tallowamidoethyl)ammonium salts, where the alkyl group can be methyl, ethyl, radical, hydroxyethyl, and the like. Non-limiting examples of dialkyl ester quaternized derivatives of dihydroxypropyl ammonium compounds include 1,2-ditallowoyloxy-3-N,N,N-trimethylpropaneammonium chloride, 1, 2-Di-canolanoyloxy-3-N,N,N-trimethylpropaneammonium chloride, and the like.

Additionally, other classes of long chain (e.g., natural oil and fatty acid derived) alkylated quaternary ammonium compounds are suitable fabric softeners, including, but not limited to, N,N-di(alkyloxyethyl)-N , N-dimethylammonium salts such as N,N-bis(tallowyloxyethyl)-N,N-dimethylammonium chloride, N,N-bis(canola oxyethyl) )-N,N-Dimethylammonium chloride, and the like; N,N-bis(alkyloxyethyl)-N-methyl-N-(2-hydroxyethyl)ammonium salts such as N, N-bis(tallowyloxyethyl)-N-methyl-N-(2-hydroxyethyl)ammonium chloride, N,N-bis(canoladoxyethyl)-N- Methyl-N-(2-hydroxyethyl)ammonium chloride, and similar; N,N-di(2-alkyloxy-2-oxoethyl)-N,N-dimethylammonium salts , such as N,N-bis(2-tallowyloxy-2-oxoethyl)-N,N-dimethylammonium chloride, N,N-bis(2-lowerucinoyloxy -2-oxoethyl)-N,N-dimethylammonium chloride, and the like; N,N-di(2-alkyloxyethylcarbonyloxyethyl)-N,N-di Methylammonium salts, such as N,N-bis(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium chloride, N,N-bis(2-canola Anoyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium chloride, and the like; N-(2-alkanoyloxy-2-ethyl)-N-(2-alk oxy-2-oxoethyl)-N,N-dimethylammonium salts, such as N-(2-tallowyloxy-2-ethyl)-N-(2-tallowyloxy -2-oxoethyl)-N,N-dimethylammonium chloride, N-(2-canolaloyloxy-2-ethyl)-N-(2-canolaloyloxy N,N,N-tris(alkyloxyethyl)-N-methylammonium salts such as N , N,N-tris(tallowyloxyethyl)-N-methylammonium chloride, N,N,N-tris(canolaoxyethyl)-N-methylammonium chloride , and the like; N-(2-alkyloxy-2-oxoethyl)-N-alkyl-N,N-dimethylammonium salts, such as N-(2-tallowyloxy- 2-oxoethyl)-N-tallow-N,N-dimethylammonium chloride, N-(2-canolacetyloxy-2-oxoethyl)-N-canola sauerkraut-N,N-dimethylammonium chloride, and the like.

Preferably, the long chain alkyl group is derived from tallow, canola, or palm oil, but other alkyl groups derived from, for example, soybean oil and coconut oil are also suitable, such as lauryl, oleyl, Castor oil, stearyl, palmityl, and similar fatty alkyl groups. The quaternary ammonium compound can have any anionic group as a counterion, for example, chloride, bromide, methylsulfate (ie, methylsulfate), acetate, formate, sulfate, nitrate, and the like.

Examples of preferred quaternary ammonium fabric softening compounds include N-methyl-N,N-bis(tallowamidoethyl)-N-(2-hydroxyethyl)ammonium methylsulfate and N-methyl-N, N-bis(hydrogenated-tallowamidoethyl)-N-(2-hydroxyethyl)ammonium methylsulfate, where these materials are available from Witco Chemical Company under the tradenames VARISOFT ^(R) 222 and VARISOFT ^(R) 110, respectively; methyl Dialkyl ester quaternized derivatives of triethanolammonium salts such as the DEHYQUART ^(R) AU series bis(acyloxyethyl)hydroxyethylmethylammonium methylsulfate ester quaternary ammonium compounds such as DEHYQUART ^(R) AU35 from Cognis, AU46, AU56, and the like; and N,N-bis(tallowyloxyethyl)-N,N-dimethylammonium chloride, wherein the tallow chains are at least partially unsaturated. Other preferred fabric softeners include the well-known dialkyldimethylammonium salts such as N,N-ditallow-N,N-dimethylammonium methylsulfate, N,N-di(hydrogenated-tallow base)-N,N-dimethylammonium chloride, N,N-distearyl-N,N-dimethylammonium chloride, N,N-di(docosyl)-N,N -Dimethylammonium chloride, N,N-Di(hydrogenated tallow)-N,N-Dimethylammonium chloride (trade name ADOGEN ^(R) 442), N,N-Ditallow-N,N- Dimethylammonium chloride (trade name ADOGEN ^® 470, PRAEPAGEN ^® 3445), N,N-distearyl-N,N-dimethylammonium chloride (trade name AROSURF ^® TA-100), all obtained from Witco Chemical Company; N,N-bis(behenyl)-N,N-dimethylammonium chloride sold under the trade name KEMAMINE( ^R ) Q-2802C by the Humko Chemical Division of Witco Chemical Corporation; and under the trade name VARISOFT ^<(R) SDC is sold by Witco Chemical Company and N,N-Dimethyl-N-stearyl-N-benzyl ammonium chloride is sold as AMMONYX ^(R) 490 by Onyx Chemical Company.

Any of the foregoing fabric softeners, and mixtures thereof, may be used in combination with the cationic associative polymers of the present invention, especially in laundry and fabric care products. For ester-containing fabric softeners, the pH of the composition can affect the stability of the fabric softener, especially under prolonged storage conditions. The pH as defined herein is measured in the neat composition at about 20°C. Preferably, the pH of the composition is below about 6. For optimum hydrolytic stability of these compositions, the pH is preferably from about 2 to about 5, more preferably from about 2.5 to about 3.5.

In addition to the aforementioned protein derivatives, non-limiting examples of protein derivatives include cocodimethylammonium hydroxypropyl hydrolyzed casein, cocodimethylammonium hydroxypropyl hydrolyzed collagen, cocodimethylammonium hydroxypropyl hydrolyzed Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Silk, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Cocodimonium Hydroxypropyl Hydrolyzed Silk Amino Acids, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Keratin , Hydroxypropyltrimonium Hydrolyzed Silk, Hydroxypropyltrimonium Hydrolyzed Rice Bran, Hydroxypropyltrimonium Hydrolyzed Soybean Protein, Hydroxypropyltrimonium Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Trimethylammonium hydrolyzed wheat protein, soy ethyl dimethyl ammonium ethosulfate, soy ethyl morpholinium ethosulfate, and the like.

Nonionic surfactants are generally uncharged amphiphiles and are usually alkoxylated to varying degrees. Classes of nonionic surfactants include alcohols, alkanolamides, amine oxides, esters, and ethers. Nonionic alcohols are generally hydroxy derivatives of long chain C ₈ -C ₁₈ alkanes, such as cetearyl alcohol, hydrogenated tallow alcohol, lanolin alcohol, alkanolamides, and the like. Alkanolamides contain at least one alkoxy group or a polyoxyethylene group and include alkanol-derived amides such as acylamide DEA, N-alkylpyrrolidone, palmitamide MEA, arachidamide MIPA, and the like and Ethoxylated amides such as PEG-50 tallowamide. Amine oxides include alkyl amine oxides, such as lauryl amine oxide; and amidopropyl morpholine oxides, such as cocamidopropyl amine oxide; and the like. Esters include ethoxylated carboxylic acids such as PEG-8 dilaurate, PEG-8 laurate, and the like; ethoxylated glycerides such as PEG-4 castor oil, PEG-120 glycerol stearate Esters, triolein PEG-6 ester, and analogs; glycol esters and their derivatives, such as diol stearate SE, propylene glycol ricinoleate, and analogs; monoglycerides, such as glyceryl myristate esters, glyceryl palmitate lactate, and the like; polyglyceryl esters, such as polyglyceryl-6-distearate, polyglyceryl-4-oleyl ether, and the like, polyols Esters and ethers, such as methyl glucosyl poly(oxyethylene) ether-20-sesquistearate, sucrose distearate; and the like; sorbitan/sorbitan esters, such as polysorbate- 60. SORBITANE SESIISOSTEARATE, AND THE LIKE; AND TRYESTERS OF PHOSPHIC ACID, SUCH AS TRIDECES POLY(OXYETHYLENE)ETHER-3-PHOSPHATE, TRIOLEYL POLY(POLYOXYETHYLENE)ETHER -8-Phosphate, and the like. Ethers include ethoxylated alcohols such as ceteareth-10, nonoxynol-9, and similar; ethoxylated lanolins such as PEG-20 lanolin, PPG - 12-PEG-65 lanolin oil, and similar; ethoxylated polysiloxanes, such as dimethicone copolyol, and similar; propoxylated POE ethers, such as meroxapol 314, po Roxamer 122, PPG-5-Ceteth-20, and the like; and alkyl polyglycosides, such as lauryl dextrose, and the like.

Nonionic surfactants can be used as emulsifiers, suspending agents, solubilizers, foam boosters, and in some cases as hydrotropes. Non-limiting examples of generally preferred nonionic surfactants include linear or branched chain alcohol ethoxylates, C ₈ -C ₁₂ alkylphenol alkoxylates, such as octylphenol ethoxylate, polyoxyethylene Ethyl polyoxypropylene block copolymers, and the like; C ₈ -C ₂₂ fatty acid esters of polyoxyethylene glycol mono- and di-glycerides; sorbitan esters and ethoxylated sorbitan esters; C ₈ -C ₂₂ fatty acid diol esters; block copolymers of ethylene oxide and propylene oxide; and the like. Non-limiting examples of surfactant foam boosters or hydrotropes include alkanolamides, such as acetamide MEA, monoethanolamide, diethanolamide, cocamide DEA, isopropanolamide, and the like; amine oxides, Such as hydrogenated tallow amine oxide; short chain alkylaryl sulfonates, such as sodium toluene sulfonate; sulfosuccinates, such as disodium stearyl sulfosuccinate; and the like.

Amphoteric and zwitterionic surfactants are those compounds that have the ability to behave as acids or bases by carrying a positive charge in strongly acidic media, a negative charge in strongly basic media, and forming zwitterionic species at intermediate pH. The main classes of amphoteric surfactants are acyl/dialkylethylenediamines and their derivatives such as disodium cocoamphocarboxymethylhydroxypropyl sulfate, disodium cocoamphodipropionate, cocoamphoacetic acid Sodium, sodium lauryl amphopropionate PG-acetate, sodium tallow amphopropionate, sodium undecenyl amphopropionate, and similar; and N-alkyl amino acids such as aminopropyl lauryl glutamine, soy Glycine dihydroxyethyl ester, lauryl alanine, and the like.

Some suitable zwitterionic surfactants for use in the compositions of the present invention include those broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, wherein the aliphatic groups can be linear or Branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and the other substituent contains anionic hydrosolubilizing groups, such as carboxyl, sulfonate, sulfate, phosphate, phosphonate, and the like things. Types of zwitterionic surfactants include alkylsulfamates, alkylbetaines and alkylamidobetaines such as stearamidopropyldimethylamine, diethylaminoethylstearamide, di Methylstearylamine, Dimethylsoyamine, Soyamine, Myristylamine, Tridecylamine, Ethylstearylamine, N-tallowpropanediamine, Ethoxylated (5 Molar Ethylene Oxide ) stearylamine, dihydroxyethylstearylamine, arachidylbehenylamine, and the like. Some suitable betaine surfactants include, but are not limited to, alkyl betaines, alkylamidopropyl betaines, alkyl sultaines, alkyl glycine esters, alkyl carboxyglycinate esters, alkyl amphopropionates , alkylamidopropyl hydroxysultaines, acyl taurates, and acyl glutamates, wherein the alkyl and acyl groups have 8 to 18 carbon atoms. Non-limiting examples of preferred amphoteric surfactants include cocamidopropyl betaine, sodium cocoamphoacetate, cocoamidopropyl hydroxysultaine, and sodium cocoamphopropionate, which are particularly suitable Gentle cleanser for skin and hair.

A pH adjuster can be added to the above acid-swellable, or water-swellable cationic associative polymers or to formulations comprising cationic associative polymers. Thus, the pH adjuster can be used in any amount necessary to obtain the desired pH in the final composition. Non-limiting examples of alkaline pH adjusters include alkali metal hydroxides; such as sodium hydroxide, and potassium hydroxide; ammonium hydroxide; organic bases such as triethanolamine, diisopropylamine, dodecylamine, Diisopropanolamine, aminomethylpropanol, cocoamine, oleylamine, morpholine, tripentylamine, triethylamine, trimethylamine (2-amino-2-hydroxymethyl)-1, 3-propanediol), and tetrakis(hydroxypropyl)ethylenediamine; and alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, and the like, and mixtures thereof. Acidic pH adjusters can be organic acids, including amino acids, and inorganic mineral acids. Non-limiting examples of acidic pH adjusters include acetic acid, citric acid, fumaric acid, glutamic acid, glycolic acid, hydrochloric acid, lactic acid, nitric acid, phosphoric acid, sodium bisulfate, sulfuric acid, tartaric acid, and the like, and the like mixture.

The polymers of the present invention are useful as thickeners, film formers, or as dye or pigment suspending agents for facilitating the deposition of colorants on hair and skin. Colorants for hair can be temporary, semi-permanent, or permanent hair dyes or color restorers that gradually color the hair. Temporary and semi-permanent hair dyes are usually in the form of rinses, gels, sprays, shampoos, sticks, and the like, and hair color restorers are usually in the form of hair dressings or lotions. Permanent hair dyes, and longer-lasting semi-permanent hair dyes are generally two-component products, one of which contains an oxidative dye intermediate and a dye coupler, and the other contains a stabilizing oxidizing agent, usually hydrogen peroxide ( at about pH 3-4) and mixed together immediately before use. It is known that these two-component hair coloring products are formulated with a surfactant component, usually a combination of nonionic or anionic surfactants, for thickening when preparing the dye mixture. In addition to the foregoing, a general discussion of hair coloring chemistry and composition is found in Brown et al., SCC Manograph (Monograph), "Permanent Hair Dyes", Society of Cosmetic Chemists (1996), incorporated herein by reference . The polymers of the present invention can be incorporated into either or both of these two-component hair coloring systems as thickeners for the acid stabilized oxidative part or in the non-oxidative part to be thickened when mixed with the acidic part .

In addition to the ingredients discussed above, other ingredients commonly used in anti-acne products, facial and body hair bleaches, and antimicrobial products include oxidizing agents such as hydrogen peroxide, benzoyl peroxide, and water-soluble inorganic persulfate compounds such as persulfate Ammonium Sulfate, Potassium Persulfate, and Sodium Persulfate.

The polymers of the present invention are especially useful as water-insoluble (hydrophobic) oily materials such as natural and synthetic oils, fats, and waxes, including, for example, vegetable oils, animal oils and fats, paraffinic oils and waxes, silicone oils and waxes; and Analogous emulsification aids. Many oily materials are used as solvents, carriers, emollients, or conditioning agents, for example, in hair and skin care products.

The polymers of the present invention are surprisingly useful stabilizers for silicone fluids commonly used in shampoo products, such as so-called "two-in-one" combination cleansing/conditioning shampoos. Silicone fluids are generally described as alkyl silicone polymers. The most common class of silicone polymers are linear polydimethylsiloxanes with the general formula _CH3- (Si( _CH3 ) ₂ -O) _W -Si( _CH3 ) ₃ , where w represents integer. Silicones can also be branched materials, where one or more alkyl groups in the polymer are replaced with oxygen to create branch points. Silicone liquids are generally water-insoluble and oily having a viscosity of several mPa·s to hundreds of thousands of mPa·s.

One class of silicones that are particularly useful in hair care products are the so-called rigid silicones (also known as silicone gums), such as described in U.S. Patent No. 4,902,499, incorporated herein by reference, which typically have a have a viscosity of about 600,000 mPa·s (at about 20°C) and have a weight average molecular weight of at least about 500,000 Daltons as determined by intrinsic viscosity measurements. The polymers of the present invention are surprisingly effective for stabilizing 2-in-1 shampoo formulations containing rigid silicone conditioners.

Another class of silicone materials which are especially useful in combination with the polymers of the present invention are the volatile silicones which are commonly used as lubricants in hair care products, such as shampoos. Volatile silicones include cyclic and linear polydimethylsiloxanes, and the like. Cyclic volatile silicones generally contain from about 3 to about 7 silicon atoms interrupted by oxygen atoms in a cyclic ring structure. Each silicon atom is additionally substituted by two alkyl groups, usually methyl groups. Linear volatile silicones are silicone fluids as described above having a viscosity of not more than about 25 mPa·s. Volatile silicones are described in Todd and Byers, "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, Vol. 91(1), pp. 27-32 (1976 ), and Kasprzak, "Volatile Silicones", Soap/Cosmetics/Chemical Specialties (Soap/Cosmetics/Chemical Specialities), pp. 40-43 (December 1986), each incorporated herein by reference and into the present invention.

Other silicone oils include dimethicone copolyols, which are linear or branched copolymers of dimethylsiloxane (dimethicone) and alkylene oxide. Dimethicone polyols can be random or block copolymers. A generally useful class of dimethicone polyols are those having polydimethylsiloxane blocks and polyoxyalkylene blocks, such as polyethylene oxide, polypropylene oxide, or both. segment copolymers. Silicone fluids including volatile silicones, silicone gums, and silicone copolymers are available from a variety of commercial sources such as Dow Corning, General Electric Company, and Noveon, Inc.

Other oily materials that may be used in combination with the polymers of the present invention include, for example, acetylated lanolin alcohols; lanolin alcohol concentrates; esters of lanolin fatty acids such as isopropyl esters of lanolin fatty acids; polyol fatty acids; ethoxylated Alcohols, such as ethoxylates and castor oil; sterols; sterol esters; sterol ethoxylates; and similar materials. Many of these esters and ethoxylates are also useful as nonionic surfactants.

Many ingredients are known in the art as conditioners for hair or skin, and humectants, and in addition to those discussed above, non-limiting examples include PCA (DL-pyrrolidone carboxylic acid) and its salts, such as lysine Acid PCA, aluminum PCA, copper PCA, chitosan PCA, and analogs, allantoin; urea; hyaluronic acid and its salts; ceramides; sorbic acid and its salts; sugars and starches and their derivatives; milk Amide MEA; and the like.

The following examples further illustrate the preparation and use of preferred embodiments but are not intended to be limiting.

Materials and Procedures

These materials are generally available from chemical suppliers known to those skilled in the chemical arts or from designated suppliers.

1. Material abbreviation and product name EA ethyl acrylate DMAEMA 2-(N,N-Dimethylamino)ethyl methacrylate DEAEMA 2-(N,N-Diethylamino)ethyl methacrylate TBAEMA 2-(tert-butylamino)ethyl methacrylate DMAPMAm 2-(N,N-Dimethylamino)propylmethacrylamide DMANPA 2-(N,N-Dimethylamino)neopentyl Acrylate TMCHMA 3,3,5-Trimethylcyclohexyl methacrylate MMA Methyl methacrylate BEM25 Beheneth-25 Methacrylate CCEM25 Approximately 1:1 mixture of choleth-25 methacrylate and ceteth-25 methacrylate LEM23 Laureth-23 Methacrylate TEM25 Tristyrylphenol ethoxylated (25) methacrylate CSEM25 Cetyl octadecyl polyoxyethylene ether-25 methacrylate HEMA 2-Hydroxyethyl methacrylate EOBDMA Ethoxylated (30) bisphenol A dimethacrylate TEGDMA Triethylene glycol dimethacrylate R307 Random ethoxylated/propoxylated 1,4-butanediol with the empirical formula CH ₂ =CH—O(CH ₂ ) ₄ O(C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₃₀ H Alcohol vinyl ether (EMULSOGEN ^(R) R307, Clariant Corporation) RAL307 Random ethoxylated/ _{propoxylated allyl ether with empirical formula CH2=CHCH2O(C3H6O ) 4 ( C2H4O ) 30H} (EMULSOGEN ^(R) RAL307 _, Clariant company) R208 Random ethoxylation/propoxylation of 1,4-butanediol with the empirical formula CH ₂ =CH—O(CH ₂ ) ₄ O(C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₂₀ H Alcohol vinyl ether (EMULSOGEN ^(R) R208, Clariant Corporation) C897 Ethoxylated octylphenol, INCI designation octoxynol-40, is reported to have an HLB of 18 (IGEPAL ^(R) CA-897, Rhodia, Inc.) P-38 Ethoxylated (27) cetyl stearyl alcohol, INCI designation Cetyl Stedecyl Ether-27, reported to have an HLB of 19 (PLURAFAC ^(R) A-38, BASF Corp.) P-39 Ethoxylated (55) cetyl stearyl alcohol, INCI designation Cetyl Stedecyl Ether-55, is reported to have an HLB of 24 (PLURAFAC( ^R) A-39, BASF Corp. ) E407 Secondary C ₁₁ ethoxylate with 40 ethylene oxide units per alcohol unit (EMULSOGEN ^(R) EPN 407, Clariant company) F127 A block copolymer of ethylene oxide and propylene oxide reported to have an HLB of 22 and the formula: HO(C ₂ H ₄ O) ₉₈ (C ₃ H ₆ ) ₆₇ (C ₂ H ₄ O) ₉₈ H, (PLURONIC ^(R) F127 , BASF Corp.) L-35 A block copolymer of ethylene oxide and propylene oxide reported to have an HLB of 19 and the formula: HO(C ₂ H ₄ O) ₁₁ (C ₃ H ₆ ) ₁₆ (C ₂ H ₄ O) ₁₁ H, (PLURONIC ^® L35 , BASF Corp.) X1005 Ethoxylated (100) isotridecyl alcohol (GENAPOL ^(R) X1005, Clariant Corp.) A5060 Ethoxylated (50) linear fatty alcohol (DISPONIL ^(R) A5060; Cognis) AMHEC Allyl-modified hydroxyethylcellulose powder (<180 μm) (TYLOSE ^(R) AM H40 YP2; Clariant Corp.)

2. Method.

A. Viscosity. The recorded viscosity of each polymer-containing composition was measured in millipascals using a Brookfield Rotating Spindle Viscometer, (Brookfield, Model RVT) at 20 rotations per minute (rpm) at ambient room temperature from about 20 to about 25°C. Seconds (mPa·s) meter (called Brookfield viscosity).

"Thin or low viscosity generally refers to a pourable, excess moisture product having a viscosity up to about 1,000 mPa·s; "medium viscosity" refers to a product having a viscosity above 1,000 to about 3,000 mPa·s; "high "Viscosity" means a product having a viscosity greater than 3,000 to about 10,000 mPa·s; and "gel" means a product having a viscosity greater than 10,000 mPa·s, unless otherwise indicated.

B. Transparency. If noted, the transparency of polymer-containing compositions is measured by a Brinkmann PC 920 colorimeter at least about 24 hours after the composition is made, as %T (transmittance). Transparency measurements were performed relative to deionized water (transparency rating 100%). Compositions having a transparency of about 60% or more are substantially transparent; compositions having a transparency of about 45-59% are judged substantially translucent.

C. Turbidity. If recorded, the turbidity of a polymer-containing composition is measured in Nephelometric Turbidity Units (NTU) using a Nephelometric Turbidity Meter using distilled water (NTU = 0) as a standard. Compositions with an NTU value of about 90 or higher were judged to be cloudy.

D. Particle size. The particle size of the polymer emulsion was measured in nanometers (nm) using a NICOMP ³⁷⁰ auto-dilution submicron particle size analyzer (Particle Sizing System, Santa Barbara, CA) according to the manufacturer's recommended operating procedures, and the data was recorded as 50 Value in % volume.

E. Stability. The stability of a polymer product emulsion or formulated composition is assessed by one or more of the following procedures.

1. Freeze/thaw cycle. A sample of about 20 grams of test product was subjected to at least one freeze/thaw (F/T) cycle by freezing the sample at a temperature of about -12°C for about 16 hours and subsequently thawing it at a temperature of about 26°C for about 8 hours. The samples were then visually inspected for phase separation. If an emulsion exhibits creaming, or an increase in viscosity that adversely affects flow, it fails the F/T test. Products that remained essentially unchanged through five F/T cycles were judged to be very stable.

2. Storage. Samples of the test product were stored at one or more of the following temperatures: a) at ambient room temperature from about 20 to about 25°C for at least one week and up to about six months; b) at elevated temperatures in an oven Store for up to about 5 weeks (accelerated aging storage) at a selected temperature of about 5 to about 45°C (unless otherwise indicated).

Stability was determined by periodic visual observation of stored samples for visible settling or a significant increase in measurable Brookfield viscosity measured at selected intervals given in the Examples below. Under ambient temperature storage, the samples were visually inspected daily for one week, then every two weeks for a total storage period of about two months or then monthly for a total storage period of up to about six months. At any storage temperature, a composition is judged to be stable a) if no settling is observed, or if some settling occurs which does not exceed about 2% of the total sample volume, and b) if no increase in viscosity occurs, or if some settling occurs increase, which does not exceed approximately 1,000 mPa·s.

E. High Humidity Curl Retention (HHCR). The hair styling effectiveness of polymers employs a well-known technique commonly referred to as High Humidity Curl Retention (HHCR), based on its role in absorption from the applied composition and from high humidity (approximately 90% relative humidity (RH)) of the surrounding atmosphere. Measured by the ability of the water to hold curls in place afterward. Descriptions of the HHCR method are readily found in the cosmetic literature. See, e.g., Ch.30, Harry's Cosmetology, Eighth Edition, M.J.Rieger, Ph.D. (Ed.), 666-667, Chemical Publishing Co., Inc., New York, NY (2000), and Diaz et al., J. Soc. Cosmet. Chem., 34, 205-212 (July 1983), the relevant disclosure of each of which is hereby incorporated by reference.

Commercially blended tresses of Caucasian untreated (virgin) human hair were made from natural brown or black European human hair supplied by International Hair Importers and Products Inc., New York. Each tress (approximately 3 gram weight) was approximately 7 inches (approximately 18 cm) long and was glued to the scalp (root) ends. Prior to use, each tress was pre-cleaned by washing with a dilute aqueous solution of sodium lauryl sulfate (10% SLS), followed by rinsing well with deionized water at ambient room temperature and blotting dry with paper towels. The initial elongated length (L _e ) of the hair was determined. About 0.8 grams of the polymer-containing composition to be evaluated is applied to the tresses and distributed evenly from the scalp to the ends. The treated tresses were then wound onto a curling iron having an outer diameter of about 3 cm and dried overnight on the curling iron at ambient room temperature from about 21 to about 23°C. After drying, the curling irons are carefully removed, leaving the hair shaped into individual curls, the initial length (L _i ) of the curls is measured, and the curled tresses are hung vertically at a temperature set at an ambient temperature of about 26 to about In a humidity chamber at 27°C and ambient high humidity about 90% RH.

% Curl Retention (HHCR) is determined by measuring the curl length when the curl is relaxed after exposure to humidity for a selected interval ( _Lt ). The following equations were used to calculate % Curl Retention, relative to initial curl length (L _i ) and length of fully extended hair before curling (L _e ).

% curl retention = (L _e -L _t )/(L _e -L _i )×100

Changes in coil length (sagging, helix formation) were measured and monitored periodically over a period of about 4 to about 24 hours, with a final reading after about 24 hours. A general benchmark for good high humidity resistance is about 70% or more curl retention (HHCR) at about 90% RH for a minimum of about 0.75 hours. A hair styling effectiveness (ie, HHCR) of about 70% was judged very good for at least 1.25 hours to about 3 hours, and a HHCR of greater than about 70% after at least about 3 hours or longer was judged excellent. An HHCR of no more than 50% was judged weak.

Example 1. Polymer

The cationic acid-swellable associative polymer identified as Polymer A in Table 2 was prepared according to the general procedure described above or, for example, as detailed below.

The monomer emulsion contains about 350 wt. prepared in a reactor containing about 7 parts by weight of C897 nonionic surfactant and about 0.3 parts by weight of sodium lauryl sulfate (30%) anionic surfactant. The resulting mixture was stirred (about 200 rpm) at a temperature of about 30 to about 40°C under nitrogen atmosphere until an emulsion was obtained. A solution of about 0.15 parts by weight sodium persulfate in about 3 parts by weight water was then added to the monomer emulsion under mixing to initiate polymerization. The temperature of the reaction mixture was maintained at a temperature of about 60 to about 62°C for about 2.5 hours after the addition of the initiator. Additional amounts of initiator (about 0.02 parts by weight sodium persulfate in about 3.5 parts by weight water for each additional amount of initiator added) were added at about 0.5 hour and about 1.5 hours after reaction initiation.

The resulting polymer emulsion was cooled to a temperature of about 44 to about 46°C over about 45 minutes and the oxidizing solution was added to the reaction mixture in two portions and then at 1 hour intervals. Each oxidation (redox) solution contained about 0.15 parts by weight t-butyl hydroperoxide (70%), about 0.015 parts by weight sodium lauryl sulfate (30%), and about 0.15 parts by weight metabisulfite in about 9 parts by weight water sodium.

The polymer emulsion was then cooled to ambient room temperature and drained from the reactor, bottled, and stored at ambient room temperature under an inert atmosphere. The resulting polymer emulsion, Polymer A, had a total polymer solids of about 21% by weight, a pH of about 8.3, and a viscosity of about 32 mPa·s. The concentration of residual ethyl acrylate monomer is less than about 1.2 ppm and the concentration of residual DMAEMA is less than about 9 ppm.

Contrast polymer CP-1, CP-2, CP-3, CP-4 and CP-5 with the monomer component shown in Table 1 and surfactant respectively, and have the monomer component shown in Table 2 and 2A respectively The cationic associative polymers of the present invention (Polymers B-Y and AA-AT) of the bulk component and surfactant were prepared following the general procedure used above for the preparation of Polymer A. The amount of each monomer type and surfactant was adjusted as necessary to achieve the monomer weight % and surfactant weight % values listed in Tables 1, 2, and 2A. All % monomer values in the table are weight % based on total monomer mixture weight; whereas all % surfactant values are based on total emulsion weight (i.e., the combined weight of all monomers, additives, surfactants, and water ). All emulsions were prepared at an active polymer concentration of at least about 15% by weight and up to about 20% by weight based on the total emulsion weight. Polymer emulsions CP-1 and CP-2 in Table 1 and emulsions B, C, D, E and F in Table 2 also contained about 2.5% by weight, based on the total emulsion weight, of propylene glycol as an emulsification aid.

In Tables 1, 2, and 2A, ASV = amino-substituted vinyl; HNV = hydrophobic nonionic vinyl, AV = associative vinyl; and in Tables 2 and 2A, Mon. = monomer; and SVS =Semihydrophobic vinyl surfactant.

Table 1. Comparative Acidic Polymer Emulsions Polymer number ASV monomer (%) HNV monomer (%) AV monomer (%) Other monomers (%) Non-ionic surfactant (%) CP-1 DMAEMA(37) EA(57.7) BEM25(5) EOBDMA(0.3) C897(7) CP-2 DMAEMA(37) EA(60) BEM25(3) --- C897(7) CP-3 DMAEMA(35) EA(61.9) BEM25(3) TEGDMA(0.1) P-38(6.9) CP-4 DMAEMA(35) EA(61.9) BEM25(3) TEGDMA(0.1) P-39(6.9) CP-5 DMAEMA(35) EA(61.9) BEM25(3) TEGDMA(0.1) F127(1.4); L-35(5.6)

Table 2. Cationic associative polymer emulsions Polymer number ASV monomer (%) HNV monomer (%) AV monomer (%) SVS monomer (%) Other monomers (%) Surfactant(%) A DMAEMA(37) EA(55.85) BEM25(3) R208(2) TEGDMA(0.15); HEMA(2) C897(7) B DMAEMA(37) EA(55.85) BEM25(3) R307(2) TEGDMA(0.15); HEMA(2) C897(7) C DMAEMA(37) EA(52.85) BEM25(3) R307(5) TEGDMA(0.15); HEMA(2) C897(7) D. DMAEMA(31) EA(61.85) BEM25(3) R307(2) TEGDMA(0.15); HEMA(2) C897(7) E. DMAEMA(34) EA(58.85) BEM25(3) R307(2) TEGDMA(0.15); HEMA(2) C897(7) f DMAEMA(40) EA(52.85) BEM25(3) R307(2) TEGDMA(0.15); HEMA(2) C897(7) G DMAEMA(34) EA(56.85) BEM25(3) R307(6) TEGDMA(0.15) C897(5.5) h DMAEMA(34) EA(55.85) BEM25(3) R307(7) TEGDMA(0.15) C897(5) I DMAEMA(37) EA(55.85) BEM25(3) R307(2) TEGDMA(0.15); HEMA(2) P-38(7) J DMAEMA(31) EA(60.85) BEM25(3) R208(3) TEGDMA(0.15); HEMA(2) P-38(6.5) K DMAEMA(35) EA(55.9) BEM25(3) R208(4) TEGDMA(0.1); HEMA(2) P-38(6.5) L DMAEMA(40) EA(52.85) BEM25(3) R307(2) TEGDMA(0.15); HEMA(2) P-38(6.5) m DMAEMA(35) EA(57.85) BEM25(3) R307(2) TEGDMA(0.15); HEMA(2) P-38(5.6); P-39(1.4) N DMAEMA(31) EA(59.85) BEM25(3) R307(4) TEGDMA(0.15); HEMA(2) P-39(6.5) o DMAEMA(35) EA(57.85) BEM25(3) R208(2) TEGDMA(0.15); HEMA(2) P-39(7) P DMAEMA(40) EA(51.9) BEM25(3) R307(3) TEGDMA(0.1); HEMA(2) P-39(7) Q DMAEMA(35) EA(56.9) BEM25(3) R307(3) TEGDMA(0.1); HEMA(2) F127(1.4); L-35(5.6) R DMAEMA(37) EA(55.85) BEM25(3) R307(2) TEGDMA(0.15); HEMA(2) P127(7) S DMAEMA(37) EA(55.85) BEM25(3) R307(2) TEGDMA(0.15); HEMA(2) F127(6) T DMAEMA(37) EA(55.85) BEM25(3) R307(2) TEGDMA.(0.15); HEMA(2) F127(5) u DMAEMA(34) EA(58.85) BEM25(3) R307(4) TEGDMA(0.15) C897(6.5) V DMAEMA(34) EA(57.85) BEM25(3) R307(5) TEGDMA(0.15) C897(6.5) W DMAEMA(35) EA(55.9) BEM25(3) R307(4) TEGDMA(0.1)HEMA(2) P-38(7) x DMAEMA(35) EA(55.9) BEM25(3) RAL307(4) TEGDMA(0.1)HEMA(2) E407(7) Y DMAEMA(35) EA(55.9) BEM25(3) RAL307(4) TEGDMA(0.1)HEMA(2) E407(5.5)

Table 2A. Cationic associative polymer emulsions Polymer number ASV monomer (%) HNV monomer (%) AV monomer (%) SVS monomer (%) Other monomers (%) Surfactant(%) AAA DMAEMA(30)TBAEMA(5) EA(55.9) BEM25(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7) AB DMAEMA(25)TBAEMA(10) EA(55.9) BEM25(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7) AC DMAEMA(30)DMAPMAm(5) EA(55.9) BEM25(3) RAL307(4) TEGDMA(0.1); HEMA(2) E-407(5.5) AD DMAEMA(35) EA(50.9)TMCHMA(5) BEM25(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7) AE DMAEMA(35) EA(53.9)TMCHMA(2) BEM25(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7) AF DMAEMA(35) EA(55.9) CSEM25(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7) AG DMAEMA(35) EA(56.4) CSEM25(1)BEM25(1.5) R307(4) TEGDMA(0.1); HEMA(2) P-38(7) AH DMAEMA(35) EA(55.9) BEM25(3) RAL307(4) TEGDMA(0.1); HEMA(2) P-38(7) AI DEAEMA(35) EA(55.9) BEM25(3) RAL307(4) TEGDMA(0.1); HEMA(2) E-407(5.5) AJ DMAEMA(35) EA(55.9) CSEM25(3) R307(4) TEGDMA(0.1); HEMA(2) A5060(7) AK DMAEMA(35) EA(55.9) CSEM25(3) R307(4) TEGDMA(0.1); HEMA(2) X1005(7) AL DMAEMA(35) EA(55.9) CSEM25(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7)AMHEC(0.05) AM DMAEMA(35) EA(55.9) CSEM25(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7)AMHEC(0.1) AN DMAEMA(35) EA(55.9) CCEM25(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7) AO DMAEMA(35) EA(55.9) LEM23(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7) AP DMAEMA(35) EA(57.4) TEM25(1.5) R307(4) TEGDMA(0.1); HEMA(2) P-38(7) AQ DMAEMA(35) EA(52.9)TMCHMA(3) CSEM25(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7) AR DMAEMA(35) EA(52.9)MMA(3) CSEM25(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7) AS DMAEMA(30)DMANPA(5) EA(55.9) CSEM25(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7) AT DMANPA(35) EA(55.9) CSEM25(3) R307(4) TEGDMA(0.1); HEMA(2) P-38(7)

After polymer preparation, the product emulsion was analyzed to determine pH, % total solids based on polymer content, Brookfield viscosity (spindle #2, 20 rpm, ambient room temperature) and particle size (nm). The unneutralized product polymer emulsion generally has a pH of about pH 7.5 to about 9; total solids of about 15 to about 25% by weight; a Brookfield viscosity of about 10 to about 100 mPa·s, and an average particle size of about 80 nm to about 260 nm.

Product emulsions of the cationic associative polymers shown in Table 2 remained stable based on studies up to five F/T cycles, and storage at ambient room temperature for at least about 5 months. The viscosity of the foregoing cationic associative polymer emulsions stored at a temperature of about 45°C for about 5 weeks remained stable with any viscosity increase not greater than about 100 mPa·s noted.

In contrast, the product emulsions of the comparative cationic polymers (i.e., lacking any SVS monomer) shown in Table 1 had either poor emulsion stability, i.e., less than 2 months at room temperature (CP-1, CP-2 and CP -5) or the product coagulates so that the viscosity is judged not to be measurable (CP-3 and CP-4).

Example 2. Cationic Salt Compatibility

This example illustrates the combination of all cationic associative polymers of Example 1 (except polymers H, X, and Y of Table 2) with the cationic quaternary ammonium salt, cetyltrimethylammonium chloride (INCI name XVI Alkanetrimethylammonium chloride, referred to herein briefly as CTAC), is based on Brookfield viscosity and turbidity (NTU). Aqueous compositions were prepared comprising cationic associative polymers as described below at an active polymer weight concentration of about 2% and a CTAC amount of about 0.5, 1 and 1.5 weight percent (active weight basis). If determined, the viscosity and turbidity values are shown in Tables 3, 3A, 3B and 3C below.

table 3 polymer %CTAC Viscosity mPa·s Turbidity NTU 2% 0.5 1 1.5 A 25,000 --- A x 26,500 --- A x 16,750 --- A x 10,250 4 B 25,600 --- B x 26,800 --- B x 14,420 --- B x 7,680 --- C 16,700 --- C x 27,150 --- C x 15,650 --- C x 8,100 --- D. 7,600 --- D. x 8,160 20 D. x 4,300 10 D. x 2,040 10 E. 16,580 - E. x 16,460 26 E. x 9,280 25 E. x 4,290 twenty two f 22,230 --- f x 25,200 14 f x 12,840 12 f x 6,820 12 G 15,500 --- G x 17,250 --- G x 9,100 --- G x 4,900 -

Table 3A polymer %CTAC Viscosity mPa·s Turbidity NTU 2% 0.5 1 1.5 I 31,350 18 I x 24,950 29 I x 17,400 13 I x 10,200 12 J 12,500 14 J x 9,800 6 J x 6,100 5 J x 2,900 6 K 25,750 7 K x 21,000 6 K x 13,500 4 K x 7,100 4 L 21,250 17 L x 22,750 13 L x 12,800 10 L x 6,500 10 m 25,500 29 m x 21,500 10 m x 10,750 10 m x 5,000 9 N 12,900 17 N x 11,100 6 N x 4,800 7 N x 1,950 5 o 21,250 14 o x 21,000 11 o x 11,000 8 o x 4,800 8

Table 3B polymer %CTAC Viscosity mPa·s Turbidity NTU 2% 0.5 1 1.5 P 30,250 36 P x 27,250 14 P x 18,250 13 P x 10,100 12 Q 12,100 47 Q x 9,000 13 Q x 5,900 7 Q x 2,850 7 R 8,680 18 R x 13,220 10 R x 11,400 7 R x 7,800 7 S 17,400 18 S x 23,100 12 S x 15,850 10 S x 9,020 9 T 17,860 19 T x 20,900 13 T x 16,050 12 T x 9,240 11 u 18,850 --- u x 17,500 --- u x 9,800 --- u x 5,500 8 V 18,250 --- V x 17,000 --- V x 8,000 --- V x 5,100 4

Table 3C polymer %CTAC Viscosity mPa·s Turbidity NTU 2% 0.5 1 1.5 W 28,750 --- W x 24,500 --- W x 13,350 --- W x 7,300 ---

All aqueous cationic associative polymer compositions are smooth textured and flowable. In contrast, aqueous compositions prepared using CP-1 shown in Example 1 of Table 1 at a weight concentration of 2% active polymer had a Brookfield viscosity of about 50,400 mPa s (without CTAC), about 57,400 mPa s (with 0.6% CTAC) , about 28,050 mPa·s (with 1.2% CTAC) and about 28,300 mPa·s (with 1.5% CTAC) and has a solidified grainy texture. Likewise, compositions comprising CP-2 were either solidified or granular.

Based on evaluations for Polymers I, J, K, L, M, N, O, P, Q, R, S, and T, the Brookfield viscosity of compositions containing 1.5% CTAC remained essentially unchanged.

Example 2A

This example illustrates the applicability of cationic associative polymers to provide substantially clear aqueous compositions of varying viscosities through appropriate selection of monomers and surfactants.

As shown in Table 3, Example 2, at 2% active polymer weight (in water), the cationic associative polymers (polymers A-C, E-Q and S-W) yielded gels with Brookfield viscosities from about 12,100 mPa·s to about 31,350 mPa·s and Polymers D and R provide high Brookfield viscosities of about 7,600 mPa·s and 8,680 mPa·s, respectively.

At 2% active polymer weight (in water), polymers H, X, and Y shown in Example 1 of Table 2 provide high Brookfield viscosities of about 6,400 mPa s, and about 31,800 mPa s, and 18,900 mPa, respectively · s gel.

Likewise, at 2% active polymer weight (in water), the polymers AA-AH, AJ-AN, and AP-AR listed in Example 1 of Table 2A provide polymers with Brookfield viscosities of about 10,300 mPa·s to about 30,700 A substantially transparent gel of mPa·s. Polymers AI and AO listed in Table 2A, Example 1, at 2% active polymer weight (in water) provided a medium Brookfield viscosity of about 2,530 mPa·s to about 8,800 mPa·s, respectively. Polymer emulsions containing polymer stabilizers (eg, AMHEC), polymers AL and AM listed in Table 2A gave slippery gels with good slip properties.

The NTU value of the aqueous cationic associative polymer (polymer AD-AG) is about 12 to about 31. The transparency of the aqueous cationic associative polymer (polymer Y, AA-AC, and AH-AR) is about 70% (Polymer AH), to about 93% T (Polymer Y).

Substantially clear gels with higher viscosities are obtained by increasing the amount of cationic associative polymer. For example, in the case of Polymer AQ at 3% active polymer weight, or Polymer AR, the viscosity increased to about 44,400 mPa·s, and 61,500 mPa·s, respectively, and the transparency was essentially unchanged (%T is about 85 to about 88%). The viscosity of polymer AR at 3% active polymer weight was reduced to about 42,500 mPa·s by including about 10% ethanol without loss of clarity (%T was about 89).

Example 3

This example illustrates the compatibility of the cationic associative polymer (Polymer A of Example 1) with various cationic quaternary ammonium salts shown in Table 4 at various active weight % concentrations in aqueous solution. Compatibility is based on Brookfield viscosity and transparency (%T) determinations such as described in Methods A and B, respectively. All compositions shown in Table 4 were easily spreadable or flowable and had an aesthetically pleasing, smooth texture without lumps or graininess.

Table 4 Cation salt INCI/trade name % cationic salt % Polymer A Viscosity mPa·s Transparency %T none - 2 25,000 79 Oleyl Dimethyl Benzyl Ammonium Chloride (Note 1) 1 2 11,000 97 VARISOFT ^® Clear (Note 2) 1 2 7,300 88 Polyquaternium-4 (Note 3) 1 2 15,300 87 JAGUAR ^(R) C-145 (Note 4) 1 1.5 22,600 - Distearyldimethylammonium chloride (Note 5) 2.5 0.75 8,100 - Distearyl Dimethyl Ammonium Chloride 2.5 1.5 41,200 - Dicetyldimethylammonium chloride (Note 6) 2.5 1.5 32,000 -

Note 1. INCI designation of oleyl dimethyl benzyl ammonium chloride

Note 2. Trade names for mixtures with INCI designations, Palmimidopropyltrimethylammonium Chloride; and PPG-3 Myristyl Ether and Trimethylpentanol Hydroxyethyl Ether, sold by Degussa Care Specialties.

Note 3. INCI designation for copolymers of hydroxyethylcellulose and diallyldimethylammonium chloride, such as CELQUAT ^(R) H-100, sold by National Starch.

Note 4.INCI Named Compound Guar Hydroxypropyltrimethylammonium Chloride - Poulenc trade name.

Note 5. INCI nomenclature for distearyldimethylammonium chloride.

Note 6. INCI nomenclature for dicetyldimethylammonium chloride.

Example 4. Acidic Skin Care Lotion

This example illustrates the use of about 0.5 to about 0.6 active weight percent of cationic associative polymer A of Example 1 in an acidic skin care emulsion formulated as shown in Table 5 containing about 5% alpha-hydroxy acid (lactic acid) .

table 5 Element INCI/trade name wt% 1. Water, deionized, to 100% qs 2. Mineral oil, USP 15 3. Glyceryl stearate, acid stable, self-emulsifying (Note 7) 3.5 4. Cetyl Alcohol 2.5 5. Dow Corning 1401 fluid (note 8) 1 6. Metal ion chelating agent 0.05 7. Propylene Glycol 4 8. Polymer A, Example 1 (active %) 0.5-0.6 9. Lactic Acid (85%) 6 10. Spices qs 11. _NH4OH (30%), to about pH 3-3.5 qs

q.s. = Quantity sufficient to meet the requirements

Note 7. Preferred INCI compounds, Glyceryl Stearate (and) PEG-100 Stearate, such as ARLACEL ^(R) 165, sold by Uniqema.

Note 8. The INCI designation of the mixture Cyclomethicone (and) Dimethiconol is the DowCorning Corp. trade name.

The formulation is prepared at a temperature of about 55 to about 65°C, wherein an oil phase comprising ingredients 2, 3, 4 and 5 and an aqueous phase comprising ingredients 1, 6, 7, 8 and 9 are prepared separately at elevated temperature, And then add the oil phase to the water phase and mix until a homogeneous emulsion is formed. The emulsion was then cooled to about 30°C, perfumed with ingredient 10 and the final pH adjusted with ingredient 11.

The emulsion had a pH of about 2 before adjusting the pH with ingredient 11. The finished emulsion had a pH of about 3.3 and a Brookfield viscosity of about 11,420 mPa·s (24-hour viscosity). The lotion is a very smooth, glossy lotion.

The viscosity of the lotion can be increased to a viscous cream as desired by increasing the amount of associative polymer. The compositions are judged suitable for use as acidic skin care products of the type employing alpha-hydroxy acids (AHA), beta-hydroxy acids (BHA), and the like.

Example 5. Fabric softener

This example illustrates the use of the cationic associative polymer of Example 1, Polymer A (Example 5A) and Cationic Salt Compatibility of Polymer I (Examples 5B, 5C).

Table 6 Element wt% The polymers given in Table 6A 0.25-0.35 (activity) Water, deionized, to 100% qs Glycolic acid (50%), to about pH 3 qs DEHYQUART ^(R) AU35 (35%) (Note 9) 5

Note 9. Esterquat, trade name for methyl triethanolammonium methyl sulfate dialkyl ester, sold by Cognis Corp.

The composition was prepared by neutralizing the polymer in water with glycolic acid to give a gel having a pH of about 4, then adding the esterquat component to the gel and mixing until uniform. The pH of this homogeneous mixture was then adjusted to about pH 3 with glycolic acid.

The viscosity of the composition was measured initially and after 24 hours and stability was determined by measuring the viscosity after storage at a temperature of about 5°C for about 12 weeks and after storage at a temperature of about 50°C for about 4 weeks. The results are shown in Table 6A.

Table 6A Example 5A Example 5B Example 5C Example 1 Polymer A I I Active weight % 0.25 0.25 0.35 Exterior smooth smooth smooth Brookfield viscosity, mPa s immediately 338 245 395 24 hours 435 365 760 12 weeks @ 5℃ --- 390 690 4 weeks @50℃ --- 1,320 4,550

For comparison, the composition was prepared again except that the cationic associative polymer was replaced by about 0.2% and about 0.4% of an acid-swellable, acid-swellable polymer reported to have a non-ionic/cationic charge, sold under the trade name STRUCTURE ^(R) Plus by National Starch & Chemical. , a commercial rheology modifier. The INCI designation for this material is Acrylates/Aminoacrylate/C _10-30 Alkyl PEG-20 Itaconate Copolymer and is supplied as a liquid emulsion with about 21% solids and a pH of about 8 to about 9 according to the manufacturer . The formulations had immediate Brookfield viscosities of about 140 mPa·s and about 250 mPa·s at active weight % concentrations of about 0.2% and 0.4% STRUCTURE( ^R) Plus, respectively, and they had grainy texture and non-uniform flow properties, respectively .

Example 6. Hair Conditioning Hair Styling Composition

This example illustrates the cationic associative polymer A of Example 1 as a thickener in two acidic hydrogels containing hair fixative, polyvinylpyrrolidone (PVP), suitable for conditioning, fixing and styling hair (Example 6A, use in Example 6B). Table 7 gives the compositions along with Brookfield viscosities and % clarity.

Table 7 Element Example 6A Example 6B INCI/trade name Active weight % Active weight % Water, deionized, to 100% qs qs Polymer A, Example 1 2 2 pvp 3 3 CTAC 1 Polyquaternium-11 (Note 10) --- 0.5 preservative qs qs Glycolic acid (50%) to about pH 4.5 to about pH 4.3 Exterior smooth buttery gel smooth buttery gel Viscosity, mPa·s 7,500 11,800 % transparency 84 91

Note 10. INCI designation for neutralized quaternized vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer sold under the tradename GAFQUAT ^(R) 755N by International Specialty Products.

Each composition was made by blending all ingredients (except glycolic acid in water) and then lowering the pH with glycolic acid. Both products were smoothly spreadable and free of any non-aesthetic "sticky" properties and provided good hair styling efficacy (70% HHCR, about 1 hour).

Example 7. Insecticide Compatibility

This example illustrates the compatibility of Polymer A of Example 1 with the cationic insecticide salts in the four formulations given in Table 8 (Examples 7A, 7B, 7C and 7D), as well as the Brookfield viscosity.

Table 8 wt% activity Ingredients (INCI/trade name) Example 7A Example 7B Example 7C Example 7D Water, deionized, to 100% qs qs qs qs Polymer A, Example 1 0.75 0.75 0.75 0.75 Didecyldimethylammonium chloride (Note 11) 0.1 0.3 --- --- Benzalkonium Chloride (Note 12) --- --- 0.1 0.3 Glycolic acid (50%) to pH 4-4.5 qs qs qs qs Brookfield viscosity.mPa·s immediately 306 94 284 93 24 hours --- 174 --- 137

Note 11. INCI designation for didecyldimethylammonium chloride, sold under the trade name BARDAC ^(R) 2250 by Lonza, Inc.

Note 12. INCI designation for alkyl dimethyl benzyl ammonium chloride mixture (C ₁₄ , 50%; C ₁₂ , 40%; C ₁₆ 10%) sold by Lonza, Inc. under the trade name BARQUAT ^(R) MB 50

All compositions are homogeneous and have smooth flow characteristics.

Example 8. Hair conditioner

This example illustrates the use of Polymer I (Example 8A, 8B) and Polymer Q (Example 8C) in the hair conditioner formulations shown in Table 9 and at active amounts, and storage based on storage viscosity. stability.

Table 9 wt% activity Ingredients (INCI/trade name) Example 8A Example 8B Example 8C 1a. Polymer I, Example 1 1 1 --- 1b. Polymer Q, Example 1 --- --- 1.5 2. Water, deionized, to 100% qs qs qs 3. Dicetyl Dimethyl Ammonium Chloride 3.3 3.3 3.3 4. Propylene Glycol 0.5 0.5 0.5 5. Stearamidopropyl Dimethylamine 0.5 0.5 0.5 6. Spices qs qs qs 7. Cyclomethicone (Note 13) 2 --- 2 8. Panthenol 0.1 0.1 0.1 9. Glycolic acid (50%) to pH 4.5 qs qs qs 10. Preservatives qs qs qs Brookfield viscosity, mPa s and (pH) immediately 5,000 --- 6,200 24 hours 5,600 (4.4) 10,000(4.4) 7,100(4.4) 12 weeks storage @45℃ 2,450 (4.2) 9,400 (4.7) 3,375 (4.3) 12 weeks storage @ room temperature 5,100(4.1) 9,700 (4.3) 7,000(4.3)

Note 13. Cyclic dimethyl polysiloxane compounds with an average of 3-6 siloxane units, such as the INCI designation of siloxane SF1173 (General Electric).

The composition is prepared by blending ingredients 2, 3, 4 and 5 together at a temperature of about 62 to about 63°C until homogeneous, cooling the blend to a temperature of about 46 to about 47°C, and then blending in ingredients 1a or 1b, as given, component 7, if present, blend components 8, 6 and 10 until homogeneous. The pH of the product was then adjusted to about pH 4.5 with ingredient 9.

All compositions are smooth-textured and flowable.

Example 9. Hair conditioner

This example illustrates the use of Polymer I of Example 1 at two concentrations (Examples 9A, 9B) in formulations shown in Table 10 suitable for use as hair conditioners.

Table 10 Ingredients (INCI/trade name) wt% activity Phase A Water, deionized, to 100% qs Polymer I in the amount shown in Table 10A 1-1.5 Phase B Stearyl Dimethyl Benzyl Ammonium Chloride 3 Polyquaternium-28 (Note 14) 1 panthenol 1 UV stabilizer qs sodium lactate 0.5 Dow Corning 1401 Liquid (Note 15) 30 Phase C Lactic acid, to the pH shown in Table 10A qs

NOTE 14. INCI nomenclature for quaternary ammonium salts composed of vinylpyrrolidone and dimethylaminopropylmethacrylamide monomers.

Note 15. Dow Corning trade name for the INCI blend Cyclomethicone (and) Dimethiconol.

The composition is made by premixing the components of Phase A and heating the mixture to a temperature of about 55 to about 60°C. Phase B ingredients were added in the order listed, the batch was stirred until homogeneous, the batch was then cooled to a temperature of about 30°C, and the pH was adjusted to about 4.5 with Phase C. The final product has a creamy white appearance, very good flow properties and a silky feel to the touch. The storage stability of the compositions based on Brookfield viscosity is shown in Table 10A.

Table 10A Example 9A Example 9B Polymer I, active wt% 1.5 1 pH start 4.6 4.4 24 hours 4.4 4.6 Brookfield viscosity, mPa s start 10,580 6,300 24 hours 13,540 8,040 8 weeks @ 5℃ 17,140 8,160 8 weeks @45℃ 8,380 2,960

Example 10. Gels

This example illustrates the use of Polymer I of Example 1 in three low pH hydrogels (Examples 10A, 10B, and 10C) at the amounts of active polymer weight % shown in Table 11.

Table 11 Active weight % Element Example 10A Example 10B Example 10C Polymer I, Example 1 2 2.5 3 Deionized, water, to 100% qs qs qs Citric acid (50%) 25 25 25 pH 1.8 1.8 1.5 Brookfield viscosity, mPa s 11,600 21,000 37,000

These gels are judged suitable for use as general purpose rust and stain removing acid cleaners, such as acid toilet bowl cleaners, truck cleaners, tanker cleaners, floor cleaners and the like.

Hydrogels can also be made using inorganic mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid instead of citric acid, resulting in economical low pH gels suitable for rust removal or industrial applications.

Example 11. Clear Shower Gel

This example illustrates the use of Polymer I of Example 1 in a clear gel composition at about 1% by weight active polymer. The gel compositions were prepared using the formulations shown in Table 12 at varying pH levels (gels A, B, and C).

Table 12 Ingredients (INCI/trade name) weight% 1. Water, deionized, to 100% qs 2. Polymer I, Example 1 (active %) 1 3. Sodium Laureth-3 Sulfate (28%) 40 4. Glycolic acid (50%), to about pH 4 2.5 5. Cocamidopropyl Betaine (35%) 14.3 6. Preservatives qs 7. Sodium hydroxide, to about pH 5-5.6, for gels B and C as shown below qs

Gel A

Gel A was prepared as follows. Ingredients 1 and 2 were premixed, ingredient 3 was added to the premix with gentle mixing and the mixture was then neutralized to about pH 4 with ingredient 4. Ingredients 6 and 7 were then added to the neutralized polymer gel with stirring mixing until the gel was uniform and clear. Gel A had a pH of about 4.2, a Brookfield viscosity of about 4,280 mPa·s, and was judged stable based on five freeze/thaw cycles.

Gel B

Gel B was made by adjusting the pH of previously prepared clear gel A to about pH 5.2 with ingredient 7. Viscosity, turbidity and stability of samples of Gel B were determined. Gel B had a Brookfield viscosity of about 3,380 mPa·s, and was judged stable based on five freeze/thaw cycles.

Gel C

Gel C was made by further adjusting the pH of the remaining previously prepared Gel B to about pH 5.6 with ingredient 7. Gel C had a Brookfield viscosity of about 3,380 mPa·s, and was judged to be stable based on five freeze/thaw cycles.

The turbidity values of gels A, B and C are each about 41 NTU. All gels were judged to be suitable for use as clear shower gels.

Example 12. Shampoo

This example illustrates the use of Polymer I of Example 1 in a shampoo composition having the formulation shown in Table 13 at about 1% by weight active polymer.

Table 13 Ingredients (INCI/trade name) weight% 1. Water, deionized, to 100% qs 2. Sodium Laureth-3 Sulfate (28%) 40 3. Cocamidopropyl Betaine (35%) 5 4. Cocamide DEA 3 5. Polymer I, Example 1 (active %) 1 6. Citric acid (50%), to about pH 4-4.6 qs 7. Spices qs

The shampoo was made by blending the ingredients in the order listed, then adjusting the pH with ingredient 6 as needed, and mixing until homogeneous. The pH of the finished shampoo is about 4.6. The shampoo had a Brookfield viscosity of about 5,580 mPa·s, a turbidity value of about 53 NTU and was judged stable based on five freeze/thaw cycles. The shampoo was judged to be suitable as a general-purpose shampoo.

For comparison, a shampoo without polymer I component 5 was similarly prepared. The comparative shampoo had a pH of about 4.5, was non-viscous (Brookfield viscosity about 115 mPa·s), and clear (turbidity value about 3 NTU).

Example 13. Anti-Dandruff Shampoo

This example illustrates that the cationic associative polymer I of Example 1 contains zinc bis(2-pyrithione) as the active dandruff control ingredient at about 1% by weight active polymer, and has the following formulation shown in Table 14 Use in an anti-dandruff shampoo composition.

Table 14 Ingredients (INCI/trade name) weight% 1. Water, deionized, to 100% qs 2. Polymer I, Example 1 (active %) 1 3. Glycolic acid (50%), to about pH 4-4.5 qs 4. PLANTAREN ^(R) PS-100 (50%) (Note 16) 25 5. Cocamide DEA 3 6. Cocamidopropyl Betaine (35%) 5 7. Zinc bis(2-pyridine oxide) (48%) (Note 17) 2 8. Preservatives qs 9. Spices qs

Note 16. Trade designation for nonionic/anionic surfactant blends of alkyl polyglycosides with alkyl distribution _C8 - _C16 and ammonium laureth sulfate, sold by Cognis, Corp.

Note 17. INCI designation for the compound sold by Arch Chemicals, Inc. as a 48% dispersion under the trade name Zinc OMADINE ⁽ R).

The shampoo was made by blending the ingredients in the order listed, then adjusting the pH with ingredient 3 as needed, and mixing until homogeneous.

The pH of the finished shampoo is about 4.5. The shampoo has a Brookfield viscosity of about 9,500 mPa·s and has a smooth, creamy texture and lotion-like appearance. The shampoo remains physically stable after storage at ambient room temperature for at least about five months and is judged stable based on five freeze/thaw cycles.

For comparison, a shampoo was similarly prepared without Polymer I Ingredient 2. The comparative shampoo had a pH of about 4.5, and was non-viscous (Brookfield viscosity about 115 mPa·s), and unstable (physically separated within two weeks of storage at ambient room temperature).

Example 14. Conditioning Shampoo

This example illustrates the use of the polymer W of Example 1 at about 1.5% by weight active polymer in a conditioning shampoo composition having the formulation shown in Table 15.

Table 15 Ingredients (INCI/trade name) weight% Phase A 1. Water, deionized, to 100% qs 2. Polymer W, Example 1 (active %) 1.5 3. Sodium Laureth-3 Sulfate (28%) 30 4. Glycolic acid (50%), to about pH 4.5 qs Phase B 5. Cocamidopropyl Hydroxysultaine (50%) 10 6. Disodium Laureth Sulfosuccinate (40%) (Note 18) 10 Phase C 7. Water, deionized, to 100% 3 8. Mica and titanium dioxide (Note 19) 0.2 Phase D 9. Polydimethylsiloxane (60,000cSt) 3 10. Preservatives qs 11. Spices qs 12. Citric acid (50%), to about pH 4.5 qs

Note 18. INCI nomenclature for the disodium salt of the ethoxylated lauryl alcohol half ester of sulfosuccinic acid having an average number of 1 to 4 ethylene oxide units.

Note 19. A mixture sold under the tradename TIMIRON ^(R) MP-115 Starluster by Rona/Merck KGaA, reported to have 69-75% mica and 25-31% titanium dioxide.

Shampoos are prepared as follows. Phase A was made by blending ingredients 1 and 2, adding ingredient 3 with gentle mixing and then acidifying the mixture with ingredient 4 to about pH 4.5. Add the ingredients of Phase B to Phase A in the order given with mixing. Phase C was made separately by premixing ingredients 7 and 8, and then adding phase C to the mixture of phases A and B. The remaining ingredients 9, 10 and 11 of phase D were added to the batch in the order given and the pH was adjusted to about 4.5 with ingredient 12.

The pH of the finished shampoo is about 4.6. The shampoo had a satin finish appearance which was judged to be more pearlescent than the comparative shampoo made without polymer W. The shampoo flows smoothly and the silicone component remains emulsified during storage aging for at least one week at ambient room temperature. The shampoo had a Brookfield viscosity of about 7,120 mPa·s, and was judged to be stable based on five freeze/thaw cycles. This shampoo is judged suitable for use as a conditioning shampoo of the type commonly referred to as a "2-in-1" conditioning shampoo.

For comparison, a shampoo similarly prepared without the polymer W component has a pH of about 4.6, is non-viscous (Brookfield viscosity below 100 mPa·s), and unstable (physically separates within 24 hours at ambient room temperature). ). Similarly, shampoos formulated with an equivalent of Polyquaternium-32 (INCI designation for SALCARE ^(R) SC-92, Ciba Specialty Chemicals) instead of polymer W were unstable and exhibited phase separation. (SALCARE ^(R) SC-92 is a trade name for a cationic copolymer liquid dispersion mixture reportedly containing acetamide, N,N,N-trimethyl-2-[(2-methyl-1-oxo-2 -propenyl)oxy]-, chloride ion, polymer with 2-acrylamide).

Example 15. Cationic Cream Conditioner

This example illustrates the use of Polymer W in the cationic cream conditioner formulations shown in Table 16 at about 1.6% by weight active polymer.

Table 16 Element wt% basis 1. Water, deionized, to 100% qs 2. Glycerin 3.8 3. Propylene glycol 2 4. Stearyl Dimethyl Benzyl Ammonium Chloride (25%) 2.3 5. Preservatives qs 6. Mineral oil (light) 5 7. Polymer W, Example 1 (active weight %) 1.6 8. Citric acid (50%) to pH 3.2-3.8 qs

The cream formulation is made by mixing ingredients 1, 2 and 3 without aeration. Add ingredient 4 to the mixture and blend well, then add ingredients 5 and 6. Ingredient 7 was then added to the previous mixture and mixed well, then the pH range was adjusted. The resulting formulation has a white creamy appearance and a smooth consistency. The formulations were judged to be stable based on freeze/thaw cycles. The initial Brookfield viscosity was about 14,400 mPa·s, and remained substantially unchanged at ambient room temperature and when stored at a temperature of about 45°C for at least four weeks.

Example 16. Cationic Conditioning Agents

This example illustrates the use of polymer W in the cationic conditioner formulations shown in Table 17 at about 2% by weight active polymer.

Table 17 Element wt% basis 1. Water, deionized, to 100% qs 2. Glycerin 3.8 3. Propylene glycol 2 4. CTAC 2 5. Preservatives qs 6. Polymer W, Example 1 (active weight %) 2 7. Citric acid (50%) to pH 3.5 qs Brookfield viscosity, mPa s 3,770 Transparency (%T) 83

A clear conditioner formulation was made by mixing ingredients 1, 2 and 3 without aeration. Add ingredient 4 to the mixture and blend well, then add ingredient 5. Ingredient 6 was then added to the previous mixture and mixed well, then ingredient 7 was used to adjust the pH. The resulting formulation was substantially clear and had a smooth consistency.

For comparison, a second conditioner was prepared similarly except that the commercial cationic polymer Structure ^(R) Plus described in Example 5 was used in place of Polymer W at the same 2% active polymer weight. The composition had a Brookfield viscosity of about 450 mPa·s, a clarity (%T) of 77, and an undesired lumpy, grainy consistency.

For further comparison, a third conditioner was prepared similarly, except that the conventional nonionic water-soluble thickener hydroxyethylcellulose (NATROSOL ^(R ) 250HHR, CS Cosmetic High Purity Grade, Aqualon/Hercules, Wilmington, DE) was present at 1% active weight The following is used to replace polymer W. The resulting composition had a Brookfield viscosity of about 3,900 mPa·s, a clarity (%T) of about 97, and a non-aesthetic "sticky" consistency.

Polymer W was judged to be directly dyeable to hair based on a variation of the well-known "Rubine dye test" for cation adsorption in the absence of CTAC, using white yak hair and determined from conditioning with glacial acetic acid to Adsorption of a solution of about 0.5% pyrazole dye (Clariant) at about pH 3.5. (See, for example, Crawford, et al., "Replacement of Rubine dyes for detection of cationic surfactants on keratin," J.Soc.Cosm.Chem., V31, pp. 273-278 (1980 September/October 2009), the relevant disclosure of which is incorporated by reference.

Example 17. Hair care styling and conditioning compositions

This example demonstrates that the cationic associative polymer (Polymer AF of Example 1 of Table 2A) is useful in aqueous hair care conditioning compositions for styling, styling, and/or conditioning hair at about 3% by weight active polymer. use in . In one study, polymer AF alone (Example 17A) was used as the sole conditioning, rheology modifying, film forming hair fixative polymer. In another study, polymers AF were mixed with about 3% by weight of active polymer of commercial nonionic assisted hair fixative polymers (Examples 17B-17D); about 3% by weight of active polymer of commercial cationic assisted hair fixative polymers ( Examples 17E-17L); about 1% or about 3% by weight of active polymer; commercial amphoteric auxiliary hair fixative polymers (Examples 17M and 17N, respectively); or about 1% or about 3% by weight of active polymer of commercial auxiliary Cationic conditioning polymers (Examples 17O-17T) were used in combination in the aqueous formulations and in the amounts indicated in Table 18.

Table 18 Ingredients (INCI/trade name) wt% 1. Polymer AF, Example 1 (active wt %) 3 2. Water, deionized, to 100% qs 3. Commercial polymers (wt% active), given in Table 18A Examples 17B-17L, 17N-17S 3 Example 17M, Example 17T 1 4. Preservatives qs 5. Glycolic acid (50%) to pH 4-6 qs

Each composition was prepared by dispersing in water the commercial auxiliary polymer ingredient 3 given in Table 18A and mixing to obtain an aqueous polymer solution, polymers AF were then blended into the aqueous polymer solution, and the pH was adjusted with ingredient 5 to about 5, then add ingredient No. 4 and adjust the pH with ingredient 5 to a range of about 4 to about 6 as needed. The appearance of the composition was noted and after 24 hours the Brookfield viscosity was measured, as well as haze, clarity, and hair styling efficacy, if measured, as discussed below. HHCR Hair Styling Efficacy is calculated from the average of the 9 tress/compositions studied, unless otherwise indicated. If tested, the viscosity, turbidity and clarity results are shown in Table 18A.

Table 18A Example number Commercial polymer (INCI/trade name) Viscosity mPa·s Turbidity NTU Transparency %T 17A Polymer-free AF, Example 1 66,000 16.9 --- 17B PVP (Note 20) 68,400 31.3 --- 17C PVP (Note 21) 70,100 11.6 --- 17D PVP/VA (Note 22) 75,000 38.2 65 17E Polyquaternium-11 (Note 10, Table 7) 16,700 44.5 60.1 17F Polyquaternium-11 (Note 23) 13,700 51.6 --- 17G Polyquaternium-28 (Note 24) 27,350 59.3 51.5 17H Polyquaternium-4 (Note 25) 66,200 36.4 65.9 17I Polyquaternium-16 (Note 26) 3,800 116 twenty three 17J Polyquaternium-46 (Note 27) 14,900 76.5 --- 17K Polyquaternium-55 (Note 28) 22,600 37.1 69 17L Gaffix VC-713 (Note 29) 27,950 24.2 --- 17M Amphomer( ^R ) (Note 30) 71,400 opaque --- 17N Diaformer Z-731 (Note 31) 12,200 38.1 --- 17O Polyquaternium-10 (Note 32) 34,000 94 23.5 17P Polyquaternium-39 (Note 33) 4,670 opaque --- 17Q Polyquaternium-7 (Note 34) 7,400 96.3 twenty one 17R Jaguar ^(R) Excel (Note 35) 150,000 49.3 --- 17S Chitosan PCA (Note 36) 19,500 192 2 17T Polyquaternium-10 (Note 37) 82,400 53.9 ---

Notes to Table 18A

Note 20. PVP K90, BASF (weight average molecular weight is reported to be about 1,300,000 Daltons).

Note 21. PVP K30, BASF (weight average molecular weight is reported to be about 60,000 Daltons).

Note 22. PVP 73W, BASF.

Note 23. Gafquat ^(R) 734N, ISP, supplied as a 50% solution in ethanol.

Note 24. Gafquat ^(R) HS-100, ISP.

Note 25. Celquat ^(R) H-100, National Starch.

Note 26. Luviquat ^(R) FC-370, BASF.

Note 27. Luviquat ^(R) Hold, BASF.

Note 28. Styleze ^(R) W20, ISP.

Note 29. Trade name for Cationic Immobilizing Polymer with INCI designation Vinylcaprolactam/PVP/Dimethylaminoethyl Methacrylate Copolymer, sold by ISP.

Note 30. Trade name for an amphoteric polymer with the INCI designation octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, sold by National Starch.

Note 31. Tradename for amphoteric polymer with the INCI designation Acrylates/Lauryl Acrylate/Stearyl Acrylate/Ethylamine Oxide Methacrylate Copolymer, sold by Clariant as a 40% solution in ethanol .

Note 32. UCARE ^(R) Polymer JR-400, Amerchol.

Note 33. Merquat ^(R) 3330, Ondeo Nalco.

Note 34. Mackernium ^™ 007, McIntyre Group, Ltd.

Note 35. Trade name for quaternized guar derivatives with INCI designation, Guar hydroxypropyltrimethylammonium chloride, sold by Rhodia.

Note 36. Kytamer ^(R) PC, Amerchol.

Note 37. Celquat ^(R) SC-230M, National Starh & Chemical.

Example 17A. The aqueous composition comprising polymer AF as the only conditioning, immobilizing polymer has a pH of about 4.1, is a clear gel, and surprisingly provides excellent hair styling efficacy (HHCR70% is about 4 hours, and at about HHCR at 8 hours is about 57%).

Examples 17B-17D. Aqueous compositions comprising Polymer AF and commercial nonionic polymers PVP (Example 17B, 17C) or PVP/VA (Example 17D) have a pH of about 4.3 to about 5.5, and are substantially transparent gel. The hair styling efficacy of the composition of Example 17B was judged to be very good (HHCR 70% of at least about 3 hours, and HHCR of about 52% at about 8 hours). Compositions comprising Polymer AF and PVP or a combination of PVP/VA (Example 17C and Example 17D) provided good to weak hair styling efficacy (HHCR 70% below 1 hour, and at about 8 hours HHCR is about 27 to about 31%), making these compositions more suitable for temporarily modifying or shaping hair rather than for hair maintenance. Example 17D was judged to be relatively stiff and suitable for obtaining novel hairstyles.

Examples 17E-17L. Compositions comprising polymers AF and a commercial cation-immobilizing polymer have a pH of about 4.1 to about 4.4. The compositions of Examples 17E, 17F, 17H, 17K, and 17L were substantially transparent. The composition of Example 17E provides excellent hair styling efficacy (HHCR 70% or more of at least about 8 hours), and the composition of Example 17K provides excellent hair efficacy for up to about 24 hours (HHCR 91% of at least about 8 hours, and 88% (at about 24 hours)), and the textures of these compositions were judged to be aesthetically smooth. The composition of Example 17I provided very good hair styling efficacy (HHCR 70% over 1 hour but less than about 2 hours) and the texture of the composition was judged to be relatively firm. The composition of Example 17H was translucent and smooth in texture and provided excellent hair styling efficacy (HHCR of about 96% or more up to about 24 hours). The composition of Example 17J had a high viscosity, was visibly cloudy (slightly cloudy), and provided excellent hair styling efficacy (HHCR 70% at least about 7 hours, and HHCR about 64% at about 8 hours).

Examples 17M-17N. Gel compositions comprising polymers AF and amphoteric polymers have a pH of about 4.2 and about 4.4. The composition of Example 17M had a viscosity of about 71,400 mPa.s, was opaque and provided good to weak hair styling efficacy (HHCR 70% at less than 1 hour, and 37% at about 8 hours). The composition of Example 17N had a viscosity of about 12,200 mPa·s and was a smooth, substantially clear gel (turbidity about 38 NTU).

Examples 17O-17T. The compositions of Examples 17O-17T comprising Polymer AF and a cationic conditioning polymer have a pH of about 4.2 to about 4.3. The composition of Example 17O is a cloudy, viscous gel that provides excellent hair styling efficacy (HHCR over 90% up to about 24 hours), making it suitable for custom or novelty hair styles and where high hold is desired. The composition of Example 17P has a high viscosity, is opaque, and provides excellent hair styling efficacy (HHCR over 90% up to about 24 hours). The composition of Example 17Q has a high viscosity, is smooth, and provides very good hair styling efficacy (HHCR 70% or more for at least 2 hours, and HHCR about 51% (at about 8 hours)). The composition of Example 17R was a viscous, substantially clear gel. The composition of Example 17S was a cloudy, dark gel judged suitable for use where product clarity was not a concern. The composition of Example 17T was a substantially clear gel. Hydroalcoholic composition.

In a second study, the formulations of Examples 17A-17T were made into hydroalcohol compositions by repeating the above procedure, except that in step 1, the commercial polymer was dispersed in a mixture of ethanol SD-40 and water, The final hydroalcoholic hair care composition thus contains about 10% ethanol by weight. Alcohol lowered the viscosity of all compositions except Examples 17O and 17S, as discussed below.

Example 17A. The hydroalcoholic composition comprising Polymer AF (Example 17A) was also a substantially clear gel (turbidity about 21.4 NTU) with slightly lower viscosity (about 34,100 mPa·s) and provided Excellent hair styling power (HHCR 70% increased to about 5 hours).

Examples 17B-17D. Alcohol reduced the viscosity of the compositions of Examples 17B, 17C, and 17D to a range of about 38,550 mPa·s (Example 17C), to about 47,000 mPa·s (Example 17D), and increased Clarity (turbidity is about 26.3 NTU (Example 17C) to about 28 NTU (Example 17B), and the clarity of Example 17D increases to about 71.1%T). The hair styling efficacy of Example 17B increased to an excellent level (HHCR 70% at about 5 hours).

Examples 17E-17L. Alcohol reduces the viscosity of the compositions of Examples 17E, 17F, 17H, 17K, and 17L but is still a gel (viscosity is about 10,300 mPa·s (Example 17F) to about 51,200 mPa·s (Example 17H), and remain substantially transparent (turbidity is about 26.5 NTU (Example 17L) to about 36 NTU (Example 17E), and the transparency of the compositions of Examples 17E, 17H, and 17K increased to about 65.5, 76.6 and 71% T). The excellent hair styling efficacy of the composition of Example 17E was not altered by the presence of alcohol (HHCR 70% was about 8 hours). The inclusion of alcohol in the composition of Example 17G yielded A substantially transparent gel having a viscosity of about 21,400 mPa·s, a turbidity of about 40 NTU, and a transparency of about 62% T. The inclusion of alcohol in the composition of Example 17I resulted in a medium viscosity of about 2,880 mPa·s, and improved transparency (turbidity down to about 68NTU, and transparency increased to about 35% T).Including alcohol in the composition of Example 17J gives a product with a viscosity of about 13,950mPa·s, and improved transparency (turbidity down to about 66.2 NTU) gel.

Examples 17M-17N. Alcohols reduce the viscosity of the gel composition of Example 17M to about 35,000 mPa·s. The alcohol lowers the viscosity of the composition of Example 17N to a high viscosity of about 7,460 mPa·s and increases clarity (turbidity drops to about 26.4 NTU).

Examples 17O-17T. The hydroalcoholic composition of Example 17O had slightly increased viscosity and improved clarity (viscosity was about 38,100 mPa·s, turbidity was about 67 NTU, and clarity was about 30%T). The hydroalcoholic composition of Example 17P had a slightly increased viscosity of about 7,000 mPa·s, was opaque, and maintained its excellent hair styling efficacy (HHCR at 24 hours). The alcohol in the composition of Example 17Q reduced viscosity and improved clarity (viscosity was about 5,100 mPa·s, turbidity was about 52.3 NTU, and clarity was about 57%T). The alcohol in the composition of Example 17R lowered viscosity and slightly improved clarity (viscosity was about 120,000 mPa·s, turbidity was about 40.4 NTU). The alcohol in the composition of Example 17S increased viscosity and turbidity (viscosity was about 32,000 mPa·s, turbidity was about 235 NTU, and clarity was about 1.7%T). In the hydroalcoholic composition of Example 17T, the alcohol slightly lowered the viscosity to about 72,400 mPa·s and further improved clarity (turbidity to about 40.9 NTU).

Example 18. Hair conditioner composition

This example illustrates the use of a cationic associative polymer (Polymer Y of Example 1 of Table 2) as the sole conditioning agent in a hair conditioner composition at about 2% by weight active polymer in the amounts shown in Table 19. (Example 18A), combined with added dimethicone copolyol (Examples 18B, 18C), and combined with added dimethicone copolyol and quaternary ammonium compound ( Examples 18D, 18E) combined use.

Table 19 weight% Ingredients (INCI/trade name) Example 18A Example 18B Example 18C Example 18D Example 18E 1. Deionized, water, to 100% qs qs qs qs qs 2. Propylene glycol 2 2 2 - - 3. Varisoft Clear (active weight %) (Note 2, Table 4) - - - 0.6 0.3 4. Polyquaternium-39 (Note 32, Table 18A) - - - 2.5 - 5. PEG-7 Glyceryl Cocoate (Note 38) 3 3 3 2 2 6. Glycerin 3 3 3 2 2 7. Polymer Y, Example 1 (active weight %) 2 2 2 2 2 8. D-Panthenol 2 2 2 1 1 9. PEG-12 polydimethylsiloxane (Note 39) - 1 3 1 1 10. Preservatives qs qs qs qs qs 11. Chelating agent qs qs qs qs qs 12. Glycolic acid (50%), to pH qs qs qs qs qs 13. Spices qs qs qs qs qs Brookfield viscosity (mPa·s) - - 9,500 4,060 3,360

Note 38 Cetiol HE, Cognis

Note 39 Dow Corning 193, Dow Corning

The composition was prepared by lightly blending polymer Y and water, partially neutralizing the polymer solution with ingredient 12 to a pH of about 5, then blending the remaining ingredients in the order listed and adjusting the pH to about 4.

The composition of Example 18C was determined to be substantially clear (turbidity 16.5 NTU) prior to the addition of fragrance. The composition of Example 18D was substantially clear (turbidity about 5.45 NTU (freshly prepared) and about 13.9 NTU (after 24 hours)). The composition of Example 18E was substantially clear when freshly prepared (turbidity 24.4 NTU) and became opaque after 24 hours (turbidity 109.2 NTU).

Example 19. Cationic Regulator Compositions

This example illustrates the compatibility of various concentrations of the cationic associative polymer, polymer W of Example 1, with various cationic quaternary ammonium compounds in the formulations shown in Table 20 and at the amounts indicated.

Table 20 Ingredients (INCI/trade name) weight% Example 19A Example 19B Example 19C Example 19D Example 19E Example 19F Part A 1. Deionized water to 100% qs qs qs qs qs qs 2. Polymer W, Example 1 1 1 0.6 0.3 0.3 0.3 3. Propylene glycol 2.5 2.5 2.5 2.5 2.5 2.5 4. CTAC (Note 40) 1 - 1 1 - - 5. Quaternium-18 (Note 5, Table 4) - 1 - - - - 6. BTAC (Note 41) - - - - 1 - 7. Quaternium-31 (Note 6, Table 4) - - - - - 1 Part B 8. Cetyl Alcohol 2.2 2.2 1.1 1.1 1.1 1.1 9. Stearyl Alcohol 1.25 1.25 0.63 0.63 0.63 0.63 10. Hydrogenated vegetable oil (Note 42) 1.2 1.2 0.6 0.6 0.6 0.69 11. Caprylic/capric triglycerides (Note 43) 3.4 3.4 1.68 1.68 1.68 1.68 Part C 12. Preservatives qs qs qs qs qs qs Part D 13. Citric acid (10%) to pH 4-4.4 qs qs qs qs qs qs Brookfield viscosity (mPa·s) 25,000-35,000 19,000-21,000 7,400 4,000 7,700 850

Notes to Table 20

Note 40. CTAC refers to cetyltrimethylammonium chloride as described in Example 2.

Note 41. BTAC refers to a quaternary ammonium compound with the INCI name behenyltrimethylammonium chloride, designated N,N,N-trimethyl-1-behenylammonium chloride.

Note 42. INCI designation for products sold by Stepan Company under the trade name WECOBEE ^(R) S.

Note 43. INCI designation for a product sold by Stepan Company under the trade name NEOBEE ^(R) M-5.

Compositions were produced as follows. Part A was made by gradually dispersing Polymer W (ingredient 2) into water with moderate mixing agitation and mixing until a clear solution was obtained. The remaining ingredients of Part A are then added and the mixture is heated to a temperature of about 65 to about 70°C. In a separate container, Part B is made by blending the ingredients of Part B and heating the mixture to a temperature of about 65 to about 70°C, mixing until a homogeneous mixture free of solids is obtained. Part B was then added to Part A with moderate mixing and agitated until uniform (approximately 15 minutes). The resulting mixture is then cooled to a temperature of about 35 to about 40°C. Then add Part C and adjust the pH to about 4 to about 4.4 by adding Part D as needed.

All compositions had a pH of about 4 (Example 19F) and about 4.2 (Example 19B), and each composition had a glossy white, creamy appearance. The viscosities of the compositions ranged from thin (Example 19F), to high (Examples 19C, 19D and 19E) to gels (Examples 19A, 19B).

Example 20. Sanitizer composition

This example illustrates the alcohol-free, antimicrobial, sanitizer formulations shown in Table 21 for cationic associative polymers, Polymer W (Example 20A) and Polymer Y (Examples 20B, 20C, 20D, and 20E). Use in formulations and in the indicated active amounts

Table 21 wt% activity Ingredients (INCI/trade name) Example 20A Example 20B Example 20C Example 20D Example 20E 1. Water, deionized, to 100% qs qs qs qs qs 2a. Polymer W, Example 1 - - - - 2 2b. Polymer Y, Example 1 1 1.5 1.75 2 - 3. Benzethonium chloride (Note 44) 0.3 0.3 0.3 0.3 0.3 4. Glycolic acid (50%) to pH qs qs qs qs qs 5. PEG-33 (and) PEG-8 Dimethicone (and) PEG-14 (Note 45) - 1 - 2 - pH 4.6 4.4 4.5 4.6 4.4 Brookfield viscosity before adding dimethicone copolyol, mPa·S, immediately 1,400 4,500 10,200 14,650 8,560 Turbidity (NTU) 7.2 8.6 8.8 8.8 4.4 Brookfield viscosity after addition of dimethicone copolyol, mPa s - 6,500 - 9,880 -

Notes to Table 20

Note 44. INCI designation for diisobutylphenoxyethoxyethyl dimethylbenzyl ammonium chloride monohydrate, sold by Lonza, Inc. under the trade name LONZAGARD ^(R) .

Note 45. INCI designation for products marketed by Noveon, Inc.

The composition was prepared by blending ingredient 3 with ingredient 1 at ambient room temperature until uniform (about 15 minutes), then adding ingredient 2, and blending until uniform, adjusting the pH with ingredient 4 to a range of about 4.4 to about 4.7 and then Measure pH, viscosity and turbidity values. Ingredient 5 was then added to the formulations of Examples 20B and 20D given in Table 21 and the viscosity was measured again. The polymer emulsion of Polymer W of Example 1 had a total polymer solids of about 20.9% by weight and the polymer emulsion of Polymer Y of Example 1 had a total polymer solids of about 20.7% by weight.

The compositions are judged to be suitable as sanitizing compositions, and especially as hand sanitizers.

Example 21. Instrumental hair combing

The wet combing performance of the hair conditioner compositions of Examples 18A, 18B, and 18C was instrumentally evaluated by using a well-known Texture Analyzer (Texture Technology Corp.) instrument equipped with a hard rubber comb, and at a temperature of about 23°C and Carding is carried out at an ambient humidity of about 50% RH. A tress of bleached European, natural brown, human hair was moistened with deionized water, approximately 2 grams of conditioner was evenly applied by hand and distributed through the tress with the thumb or forefinger for approximately 1 minute, and the tress was then treated with Rinse in lukewarm tap water for about 30 seconds. The rinsed wet tresses were then secured with the A/TG stretching clamp of the Texture Analyzer instrument and the hair was pulled through the fine toothed portion of the comb by raising the stretching clamp at a rate of about 3 mm/s up to the full length of the tress Has been completely sorted out. The working force (grams) required to raise the tresses was recorded as a function of distance. The brushing procedure was repeated four times on the same tress for a total of five brushing pulls. For baseline measurements, five combing measurements were taken for each tress prior to application of the test composition and repeated after application of the test composition, and the % total working force was averaged.

Polymer Y (Example 18A) was judged to provide wet combing conditioning, and comb ease was further improved by the presence of dimethicone copolyol (Examples 18B, 18C). The wet combing data show that conditioning is substantially equivalent to the compositions of Examples 18B and 18C, and both compositions provide easier wet combing than the composition of Example 18A.

Example 22. Acidic Surfactant Skin Cleanser

This example illustrates the compatibility of Polymer AF of Example 1 with anionic surfactants in an acidic surfactant skin cleanser formulation comprising an amphoteric hydroxy complex of an alpha-hydroxy acid (lactic acid) and L-arginine sex.

Table 22 Element INCI/trade name wt% 1. Water, deionized, to 100% qs 2. Glycol Distearate (and) Glycerin (and) Laureth-4 (and) Cocamidopropyl Betaine (Note 46) 1 3. Coco Glucoside (and) Glyceryl Oleate (Note 47) 2 4. Cocamidopropylamine Oxide (Note 48) 1 5. Sodium Laureth Sulfate (and) Cocamidopropyl Betaine (and) Polyglucoside (Note 49) 23.5 6. Lactic Acid (and) L-Arginine Blend (Note 50) 10 7. Sodium hydroxide (50%) to pH qs 8. Preservatives qs 9. Polymer AF, Example 1 (active weight %) 1

Note 46. INCI designation for the product sold by Cognis under the trade name Euperlan ^(R) PK-3000.

Note 47. INCI designation for the product sold by Cognis under the trade name Lamesoft ^(R) PO-65 (65%).

Note 48. INCI designation for the product sold by Cognis under the trade name Standamox ^(R) CAW.

Note 49. INCI designation for the product sold by Cognis under the trade name Texapon ^(R) 611 (42.8%).

Note 50. INCI designation for the product sold by Cognis under the trade name AHCare ^(R) L-65.

The composition is made by dispersing ingredients 2 to 6 in water in the order shown, mixing well between each addition. The pH of the mixture was adjusted with ingredient 7 to a range of about 3.8 to about 3.9. Ingredient 8 was then added, followed by Polymer AF (ingredient 9), and then the pH was adjusted with Ingredient 7 to a range of about 4.1 to about 4.2 as needed.

The finished composition has a pH of about 4.1 and a Brookfield viscosity of about 5,640 mPa·s. The composition is judged to be particularly suitable for use as a body cleanser, commonly known as a body wash. Example 23. Mousse formulations

Table 23 Ingredient INCI/trade name wt% (when supplied) 1. Water, deionized, to 100% qs 2. Polymer AF, Example 1 (active polymer weight) 0.5 3. Polyquaternium 11 (20% solids) 20 4. SD alcohol 6 5. Cocamidopropyl Betaine (35%) 0.5 6. PEG 40 hydrogenated castor oil 0.3 7. Citric acid (50%) to pH qs 8. Preservatives qs 9. Spices qs

Polymer AF was dispersed in deionized water. Ingredients 3, 4, and 5 were then added in the order listed, mixing after each addition until uniform. Add ingredient 8 and mix until batch is uniform. Ingredients 6 and 9 were premixed and added to the previous batch. The pH was adjusted to about 5 with citric acid. This formulation was judged suitable for use in mousse products.

Example 24. Shampoo for color treatment and color maintenance

This example illustrates two shampoos (24A and 24B) suitable for color treatment and color maintenance.

Table 24 wt% (when supplied) Ingredients (INCI/trade name) 24A 24B 1. Water, deionized, to 100% qs qs 2. Polymer AF, Example 1 (active polymer wt %) 1 1 3. Sodium lauryl polyoxyethylene ether sulfate (Note 51) 20 20 4. Lamesoft ^(R) PO-65 (Note 47, Table 22) 3 3 5. Cocamidopropyl Betaine 5.5 5.5 6. Ammonium lauryl polyoxyethylene ether sulfate (Note 52) 15 15 7. Euperlan ^(R) PK-3000 (Note 46, Table 22) 3 3 8. Tocopherol 0.1. 0.1. 9. Preservatives qs qs 10. Sodium coco-based hydrolyzed wheat (Note 53) 0.5 0.5 11. CI Brown 17 (Note 54a) 0.13 - 12. CI Blue 99 (Note 54b) 0.13 - 13. CI Red 76 (Note 54c) 0.2 - 14. Spices qs qs 15. Citric acid (50%) to pH qs qs

Note 51. INCI designation for the product sold by Cognis under the trade name Standapol ^(R) ES-2.

Note 52. INCI designation for the product sold by Cognis under the trade name Stanvapol ^(R) EA-2.

Note 53. INCI designation for the product sold by Cognis under the trade name Gluadin ^(R) WK.

Note 54. INCI designations for (a) Arianor ^(R) Sienna Brown, (b) Arianor ^(R) Steel Blue, (c) Arianor ^(R) Madder Red (both sold by Warner Jenkinson Europe, Ltd.)

Shampoo 24A was prepared by dispersing Polymer AF in deionized water with gentle mixing, adding ingredients 3 and 6 with mixing, partially neutralizing the mixture with citric acid to a pH of about 5, and then adding the remainder in the order listed. Made with ingredients 4, 5, 7, 8, 9 and 10. A blend of ingredients 11, 12, 13 and fragrance are added to the mixture and the pH is adjusted with ingredient 15 to a range of about 4.7 to about 5.0.

Shampoo 24A was judged suitable for coloring hair during use, and for maintaining hair color through continued use as a treatment shampoo.

Shampoo 24B was prepared following the procedure of Shampoo 24A except that the colorant dye was absent. Shampoo 24B is judged suitable for washing hair that has been colored or chemically treated without removing the color from the hair.

As can be seen from the preceding examples, the polymers of the present invention are useful in a wide variety of aqueous compositions and are compatible with cationic quaternary ammonium salts, cationic surfactants and anionic surfactants. The foregoing discussion and recorded studies serve to illustrate the invention and not to limit it. Other variations within the spirit and scope of the invention are possible and readily apparent to those skilled in the art.

Claims (72)

1. A polymer which is the polymerization reaction product of a mixture of monomers comprising: a) at least one amino-substituted vinyl monomer; b) at least one hydrophobic nonionic vinyl monomer; c) at least one associative vinyl monomer selected from at least one compound of formula (III): Wherein, R ² is independently H, methyl, -C(O)OH, or -C(O)OR ³ ; R ³ is C ₁ -C ₃₀ alkyl; A is -CH ₂ C(O)O -, -C(O)O-, -O-, -CH ₂ O-, -NHC(O)NH-, -C(O)NH-, -Ar-(CE ₂ ) _z -NHC(O)O -, -Ar-(CE ₂ ) _z -NHC(O)NH-, or -CH ₂ CH ₂ NHC(O)-; Ar is a divalent aryl group; E is H or methyl; z is 0 or 1; k is an integer from 0 to 30, and m is 0 or 1, provided that if k is 0, then m is 0, and if k is 1 to 30, then m is 1; (R ⁴ -O) _n is polyoxy Alkylene, which is a homopolymer, a random copolymer, or a block copolymer having C ₂ -C ₄ oxyalkylene units, wherein R ⁴ is C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , or a mixture thereof, and n is an integer from 5 to 250; Y is -R ⁴ O-, -R ⁴ NH-, -C(O)-, -C(O)NH-, -R ⁴ NHC(O )NH-, or -C(O)NHC(O)-; and R ⁵ is selected from C ₈ -C ₄₀ straight chain alkyl, C ₈ -C ₄₀ branched alkyl, C ₈ -C ₄₀ carbocycloalkane C ₂ -C ₄₀ alkyl-substituted phenyl, aryl-substituted C ₂ -C ₄₀ alkyl, and C ₈ -C ₈₀ complex ester substituted or unsubstituted alkyl; wherein R ⁵ alk The radical group optionally contains one or more substituents selected from hydroxyl groups, alkoxy groups, and halogen groups; and d) at least one semi-hydrophobic vinyl surfactant monomer having either of the following structural formulas (IV) or (V):

Wherein, in structural formulas (IV) and (V), R ⁶ are independently H, C ₁ -C ₃₀ alkyl, -C(O)OH, or -C(O)OR ⁷ ; R ⁷ is C ₁ -C ₃₀ alkyl; A is -CH ₂ C(O)O-, -C(O)O-, -O-, -CH ₂ O-, -NHC(O)NH-, -C(O) NH-, -Ar-(CE ₂ ) _z -NHC(O)O-, -Ar-(CE ₂ ) _z -NHC(O)NH-, or -CH ₂ CH ₂ NHC(O)-; Ar is two E is H or methyl; z is 0 or 1; p is an integer from 0 to 30, and r is 0 or 1, provided that if p is 0, r is 0, and if p is 1 to 30, then r is 1; (R ⁸ -O) _v is polyoxyalkylene, which is a homopolymer, random copolymer or block copolymer with C ₂ -C ₄ oxyalkylene units, wherein R ⁸ is C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , or a mixture thereof, and v is an integer from 5 to 250; R ⁹ is H or C ₁ -C ₄ alkyl; and D is C ₈ - C ₃₀ unsaturated alkyl, or carboxy-substituted C ₈ -C ₃₀ unsaturated alkyl. 2. The polymer of claim 1, wherein the amino-substituted vinyl monomer is selected from the group consisting of mono(C ₁ -C ₄ )alkylamino(C ₁ -C ₈ )alkyl (meth)acrylates, (methyl ) di(C ₁ -C ₄ )alkylamino(C ₁ -C ₈ )alkyl acrylates, mono(C ₁ -C ₄ )alkylamino(C ₁ -C ₈ )alkyl(meth)acrylamides , di(C ₁ -C ₄ )alkylamino(C ₁ -C ₈ )alkyl(meth)acrylamide, nitrogen-containing heterocyclic (meth)acrylamide, nitrogen-containing heterocyclic (meth)acrylate, and its mixture. 3. The polymer of claim 1, wherein the hydrophobic nonionic vinyl monomer is a compound of any of the following formulas (I) or (II): (I) _CH2 =C(X)Z, (II) _CH2 =CH-OC(O)R; Wherein, in formulas (I) and (II), respectively, X is H or methyl; and Z is -C(O)OR ¹ , -C(O)NH ² , -C(O)NHR ¹ , -C (O)N(R ¹ ) ₂ , -C ₆ H ₄ R ¹ , -C ₆ H ₄ OR ¹ , -C ₆ H ₄ Cl, -CN, -NHC(O)CH ₃ , -NHC(O)H , N-(2-pyrrolidonyl), N-caprolactam, -C(O)NHC(CH ₃ ) ₃ , -C(O)NHCH ₂ CH ₂ -N-ethyleneurea, -SiR ₃ , -C (O)O(CH ₂ ) _x SiR ₃ , -C(O)NH(CH ₂ ) _x SiR ₃ , or -(CH ₂ ) _x SiR ₃ ; x is an integer from 1 to 6; R is independently C ₁ -C ₃₀ alkyl; R ¹ are independently C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkyl substituted by hydroxy or C ₁ -C ₃₀ alkyl substituted by halogen. 4. The polymer of claim 1, wherein the hydrophobic nonionic vinyl monomer is a _C1 - _C30 alkyl acrylate, a _C1 - _C30 alkyl methacrylate, or a mixture thereof. 5. The polymer of claim 1, wherein the semihydrophobic vinyl surfactant monomer comprises polymerizable unsaturated end groups and polyoxyalkylene groups covalently bonded thereto. 6. The polymer of claim 5, wherein the polyoxyalkylene group is a homopolymer, a random copolymer, or a block copolymer comprising 5 to 250 C2- _{C4 oxyalkylene} units. 7. A polymer which is the polymerization reaction product of a monomer mixture comprising, based on the weight of the total monomer mixture: (a) 10 to 70% by weight of at least one amino-substituted vinyl monomer or salt thereof; (b) 20 to 80% by weight of at least one hydrophobic nonionic vinyl monomer; (c) 0.01 to 25% by weight of at least one associative vinyl monomer; (d) 0.01 to 25% by weight of at least one semihydrophobic vinyl surfactant monomer; (e) up to 10% by weight of hydroxy-substituted nonionic vinyl monomers; (f) up to 5% by weight of crosslinking monomers; (g) up to 10% by weight chain transfer agent; and (h) Up to 2% by weight polymer stabilizer. 8. The polymer of claim 7, wherein the amino-substituted vinyl monomer is selected from the group consisting of: Mono(C ₁ -C ₄ )alkylamino(C ₁ -C ₈ )alkyl (meth)acrylate, Di(C ₁ -C ₄ )alkylamino(C ₁ -C ₈ )(meth)acrylate Alkyl esters, mono(C ₁ -C ₄ )alkylamino(C ₁ -C ₈ )alkyl(meth)acrylamides, di(C ₁ -C ₄ )alkylamino(C ₁ -C ₈ )alkanes (meth)acrylamide, nitrogen-containing heterocyclic (meth)acrylamide, nitrogen-containing heterocyclic (meth)acrylate, and mixtures thereof. 9. The polymer of claim 7, wherein the hydrophobic nonionic vinyl monomer is a compound of any of the following formulas (I) or (II): (I) _CH2 =C(X)Z, (II) _CH2 =CH-OC(O)R; Wherein, in formulas (I) and (II), respectively, X is H or methyl; and Z is -C(O)OR ¹ , -C(O)NH ₂ , -C(O)NHR ¹ , -C (O)N(R ¹ ) ₂ , -C ₆ H ₄ R ¹ , -C ₆ H ₄ OR ¹ , -C ₆ H ₄ Cl, -CN, -NHC(O)CH ₃ , -NHC(O)H , N-(2-pyrrolidonyl), N-caprolactam, -C(O)NHC(CH ₃ ) ₃ , -C(O)NHCH ₂ CH ₂ -N-ethyleneurea, -SiR ₃ , -C (O)O(CH ₂ ) _x SiR ₃ , -C(O)NH(CH ₂ ) _x SiR ₃ , or -(CH ₂ ) _x SiR ₃ ; x is an integer from 1 to 6; R is independently C ₁ -C ₃₀ alkyl; R ¹ are independently C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkyl substituted by hydroxy or C ₁ -C ₃₀ alkyl substituted by halogen. 10. The polymer of claim 7, wherein the hydrophobic nonionic vinyl monomer is a _C1 - _C30 alkyl acrylate, a _C1 - _C30 alkyl methacrylate, or a mixture thereof. 11. The polymer of claim 7, wherein the associative vinyl monomer is a compound of formula (III): Wherein, R ² is independently H, methyl, -C(O)OH, or -C(O)OR ³ ; R ³ is C ₁ -C ₃₀ alkyl; A is -CH ₂ C(O)O -, -C(O)O-, -O-, -CH ₂ O-, -NHC(O)NH-, -C(O)NH-, -Ar-(CE ₂ ) _z -NHC(O)O -, -Ar-(CE ₂ ) _z -NHC(O)NH-, or -CH ₂ CH ₂ NHC(O)-; Ar is a divalent aryl group; E is H or methyl; z is 0 or 1; k is an integer from 0 to 30, and m is 0 or 1, provided that if k is 0, then m is 0, and if k is 1 to 30, then m is 1; (R ⁴ -O) _n is polyoxy Alkylene, which is a homopolymer, a random copolymer, or a block copolymer having C ₂ -C ₄ oxyalkylene units, wherein R ⁴ is C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , or a mixture thereof, and n is an integer from 5 to 250; Y is -R ⁴ O-, -R ⁴ NH-, -C(O)-, -C(O)NH-, -R ⁴ NHC(O )NH-, or -C(O)NHC(O)-; and R ⁵ is selected from C ₈ -C ₄₀ straight chain alkyl, C ₈ -C ₄₀ branched alkyl, C ₈ -C ₄₀ carbocycloalkane C ₂ -C ₄₀ alkyl-substituted phenyl, aryl substituted C ₂ -C ₄₀ alkyl, and C ₈ -C ₈₀ complex ester substituted or unsubstituted alkyl; wherein R ⁵ alkyl The group optionally contains one or more substituents selected from hydroxyl groups, alkoxy groups, and halogen groups. 12. The polymer of claim 7, wherein the semihydrophobic vinyl surfactant monomer is a compound of any of the following structural formulas (IV) or (V):

Wherein, in structural formula (IV) and (V) respectively; R ⁶ is independently H, C ₁ -C ₃₀ alkyl, -C(O)OH, or -C(O)OR ⁷ ; R ⁷ is C ₁ -C ₃₀ alkyl; A is -CH ₂ C(O)O-, -C(O)O-, -O-, -CH ₂ O-, -NHC(O)NH-, -C(O) NH-, -Ar-(CE ₂ ) _z -NHC(O)O-, -Ar-(CE ₂ ) _z -NHC(O)NH-, or -CH ₂ CH ₂ NHC(O)-; Ar is di E is H or methyl; z is 0 or 1; p is an integer from 0 to 30, and r is 0 or 1, provided that if p is 0, r is 0, and if p is 1 to 30 30, then r is 1; (R ⁸ -O) _v is polyoxyalkylene, which is a homopolymer with C ₂ -C ₄ oxyalkylene units, a random copolymer, or a block copolymer, wherein R ⁸ is C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , or a mixture thereof, and v is an integer from 5 to 250; R ⁹ is H or C ₁ -C ₄ alkyl; and D is C ₈ -C ₃₀ unsaturated alkyl, or C ₈ -C ₃₀ unsaturated alkyl substituted by carboxy. 13. The polymer of claim 7, wherein the amino-substituted vinyl monomer is selected from the group consisting of: 3-(N,N-dimethylamino)propyl (meth)acrylate, N'-(3-N,N-dimethylamino)propyl (meth)acrylamide, 2-methacrylic acid (N,N-dimethylamino)ethyl ester, 2-(N,N-diethylamino)ethyl methacrylate, 2-(tert-butylamino)ethyl methacrylate, 2-(N, N-dimethylamino)propyl methacrylamide, and 2-(N,N-dimethylamino)neopentyl acrylate; (b) 50 to 65% by weight of at least one hydrophobic nonionic vinyl monomer selected from C ₁ -C ₃₀ alkyl esters of acrylic acid, C ₁ -C ₃₀ alkyl esters of methacrylate, and mixtures thereof; (c) 0.1 to 10% by weight of at least one associative vinyl monomer selected from polyethoxylated cetyl methacrylate, polyethoxylated cetearyl methacrylate, polyethylene glycol Oxylated stearyl (meth)acrylate, polyethoxylated arachidyl (meth)acrylate, polyethoxylated behenyl methacrylate, polyethoxylated methacrylate Lauryl Ester, Polyethoxylated Waxyl (Meth)acrylate, Polyethoxylated Montanyl (Meth)acrylate, Polyethoxylated Melalyl (Meth)acrylate, Polyethoxylated Tricodecyl (meth)acrylate, Tristyrylphenol polyethoxylated methacrylate, Hydrogenated castor oil polyethoxylated methacrylate, Canola polyethoxylate (meth)acrylates, and cholesteryl polyethoxylated methacrylates; (d) 0.1 to 10% by weight of at least one semihydrophobic vinyl surfactant monomer having one of the following formulas: CH ₂ ＝CH—O(CH ₂ ) _a O(C ₃ H ₆ O) _b (C ₂ H ₄ O) _c H or _CH2 = _CHCH2O ( _{C3H6O )d ( C2H4O} ) _{eH ;} wherein a is 2, 3, or 4; b is an integer of 1 to 10; c is an integer of 5 to 50; d is an integer of 1 to 10; and e is an integer of 5 to 50; (e) up to 10% by weight of hydroxy-substituted nonionic vinyl monomers; (f) up to 5% by weight of crosslinking monomers; (g) up to 10% by weight chain transfer agent; and (h) Up to 2% by weight polymer stabilizer. 14. The polymer of claim 7, wherein the associative vinyl monomer is selected from the group consisting of polyethoxylated cetyl methacrylate, polyethoxylated cetearyl methacrylate, polyethoxylated Stearyl (meth)acrylate, Arachidyl (meth)acrylate polyethoxylate, Behenyl methacrylate polyethoxylate, Lauryl methacrylate polyethoxylate Esters, Polyethoxylated Waxyl (Meth)acrylate, Polyethoxylated Montanyl (Meth)acrylate, Polyethoxylated Melalyl (Meth)acrylate, Polyethoxylated Dodecyl (meth)acrylate, Tristyrylphenol polyethoxylated methacrylate, Hydrogenated castor oil polyethoxylated methacrylate, Canola polyethoxylated ( meth)acrylates, and cholesteryl polyethoxylated methacrylates, and mixtures thereof. 15. The polymer of claim 7, wherein the semihydrophobic vinyl surfactant monomer comprises polymerizable unsaturated end groups and polyoxyalkylene groups covalently bonded thereto. 16. The polymer of claim 15, wherein the polyoxyalkylene group is a homopolymer, a random copolymer, or a block copolymer comprising 5 to 250 C2 _{- C4} oxyalkylene units. 17. The polymer of claim 7, wherein the monomer mixture comprises a semihydrophobic vinyl surfactant monomer having one of the following formulas: CH ₂ ＝CH—O(CH ₂ ) _a O(C ₃ H ₆ O) _b (C ₂ H ₄ O) _c H or _CH2 = _CHCH2O ( _{C3H6O )d ( C2H4O} ) _{eH ;} wherein a is 2, 3, or 4; b is an integer from 1 to 10; c is an integer from 5 to 50; d is an integer from 1 to 10; and e is an integer from 5 to 50. 18. The polymer of claim 7, wherein the monomer mixture comprises 0.01 to 10 weight percent of at least one hydroxyl-substituted nonionic vinyl monomer, based on the total monomer mixture weight. 19. The polymer of claim 18, wherein the hydroxy-substituted nonionic vinyl monomer is selected from the group consisting of hydroxy-substituted (C ₁ -C ₄ ) alkyl acrylates, hydroxy-substituted (C ₁ -C ₄ ) alkyl methacrylates , hydroxy-substituted (C ₁ -C ₄ ) alkyl acrylamides, hydroxy-substituted (C ₁ -C ₄ ) alkyl methacrylamides, and mixtures thereof. 20. The polymer of claim 18, wherein the hydroxy-substituted nonionic vinyl monomer is 2-hydroxyethyl methacrylate. 21. The polymer of claim 7, wherein the monomer mixture comprises 0.01 to 3 weight percent of at least one crosslinking monomer, based on the total monomer mixture weight. 22. The polymer of claim 21, wherein the crosslinking monomer is an acrylate ester of a polyol having at least two acrylate groups, a methacrylate ester of a polyol having at least two methacrylate groups or its combination. 23. The polymer of claim 7, wherein the monomer mixture comprises at least 0.1 weight percent chain transfer agent, based on total monomer mixture weight. 24. The polymer of claim 23, wherein the chain transfer agent is selected from the group consisting of thio compounds, disulfide compounds, phosphites, hypophosphites, haloalkyl compounds, and combinations thereof. 25. A polymer which is the polymerization reaction product of a monomer mixture comprising, based on the weight of the total monomer mixture: (a) 20 to 50% by weight of at least one amino-substituted vinyl monomer selected from 3-(N,N-dimethylamino)propyl (meth)acrylate, N′-(3-N , N-dimethylamino)propyl (meth)acrylamide, 2-(N,N-dimethylamino)ethyl methacrylate, 2-(N,N-diethylamino)methacrylate ethyl ester, 2-(tert-butylamino)ethyl methacrylate, 2-(N,N-dimethylamino)propylmethacrylamide, and 2-(N,N-dimethylamino)acrylate neopentyl ester; (b) 50 to 65% by weight of at least one hydrophobic nonionic vinyl monomer selected from C ₁ -C ₃₀ alkyl esters of acrylic acid, C ₁ -C ₃₀ alkyl esters of methacrylate, and mixtures thereof; (c) 0.1 to 10% by weight of at least one associative vinyl monomer selected from polyethoxylated cetyl methacrylate, polyethoxylated cetearyl methacrylate, polyethylene glycol Oxylated stearyl (meth)acrylate, polyethoxylated arachidyl (meth)acrylate, polyethoxylated behenyl methacrylate, polyethoxylated methacrylate Lauryl Ester, Polyethoxylated Waxyl (Meth)acrylate, Polyethoxylated Montanyl (Meth)acrylate, Polyethoxylated Melalyl (Meth)acrylate, Polyethoxylated Tricodecyl (meth)acrylate, Tristyrylphenol polyethoxylated methacrylate, Hydrogenated castor oil polyethoxylated methacrylate, Canola polyethoxylate (meth)acrylates, and cholesteryl polyethoxylated methacrylates; (d) 0.1 to 10% by weight of at least one semihydrophobic vinyl surfactant monomer having one of the following formulas: CH ₂ ＝CH—O(CH ₂ ) _a O(C ₃ H ₆ O) _b (C ₂ H ₄ O) _c H or _CH2 = _CHCH2O ( _{C3H6O )d ( C2H4O} ) _{eH ;} wherein a is 2, 3, or 4; b is an integer of 1 to 10; c is an integer of 5 to 50; d is an integer of 1 to 10; and e is an integer of 5 to 50; (e) up to 10% by weight of hydroxyl-substituted nonionic vinyl monomers; (f) up to 5% by weight of crosslinking monomers; (g) up to 10% by weight chain transfer agent; and (h) Up to 2% by weight polymer stabilizer. 26. The polymer of claim 25, wherein the monomer mixture comprises 1 to 5 weight percent of at least one hydroxyl-substituted nonionic vinyl monomer, based on the total monomer mixture weight. 27. The polymer of claim 26, wherein the hydroxy-substituted nonionic vinyl monomer is selected from the group consisting of hydroxy-substituted (C ₁ -C ₄ ) alkyl acrylates, hydroxy-substituted (C ₁ -C ₄ ) alkyl methacrylates, Hydroxy-substituted (C ₁ -C ₄ ) alkyl acrylamides, and hydroxy-substituted (C ₁ -C ₄ ) alkyl methacrylamides, and mixtures thereof. 28. The polymer of claim 26, wherein the hydroxy-substituted nonionic vinyl monomer is 2-hydroxyethyl methacrylate. 29. The polymer of claim 25, wherein the monomer mixture comprises 0.01 to 3 weight percent crosslinkable monomer, based on the total monomer mixture weight. 30. The polymer of claim 29, wherein the crosslinking monomer is an acrylate ester of a polyol having at least two acrylate groups, a methacrylate ester of a polyol having at least two methacrylate groups or its mixture. 31. The polymer of claim 25, wherein the monomer mixture comprises at least 0.1 weight percent chain transfer agent, based on total monomer mixture weight. 32. The polymer of claim 31, wherein the chain transfer agent is selected from the group consisting of thio compounds, disulfide compounds, phosphites, hypophosphites, haloalkyl compounds, and mixtures thereof. 33. A process for the preparation of the polymer of claim 1 , comprising mixing the monomer mixture in an aqueous medium at a pH of not lower than 7, in the presence of a free radical initiator and a surfactant, and The emulsion polymerization is carried out at a reaction temperature of 20 to 80°C. 34. The method of claim 33, wherein the emulsion polymerization is carried out in the presence of an emulsifying amount of at least one anionic surfactant, nonionic surfactant, amphoteric surfactant, or mixtures thereof. 35. A polymer emulsion produced by the emulsion polymerization method of claim 33. 36. A composition comprising the polymer of claim 1 and water. 37. The composition of claim 36, further comprising at least one of the following: pH adjusters, buffers, auxiliary immobilization polymers, auxiliary film formers, auxiliary rheology modifiers, auxiliary hair conditioners, auxiliary Skin conditioners, chemical curling or straightening agents, colorants, surfactants, polymer film modifiers, product stabilizers and finishes, propellants, co-solvents, or mixtures thereof. 38. The composition of claim 36, further comprising at least one quaternary ammonium compound. 39. The composition of claim 36, further comprising at least one hydroxycarboxylic acid. 40. The composition of claim 36, further comprising at least one immobilization aiding polymer. 41. A formulated composition comprising the polymer of claim 1, wherein the formulated composition is selected from the group consisting of compositions for personal care, healthcare, household care, institutional care, industrial care, and industrial processes. 42. The formulated composition of claim 41, wherein the composition for personal care is a cleanser for skin or hair. 43. The formulated composition of claim 41, wherein the composition for personal care or health care comprises at least one of the following: a pH adjuster, a buffer, an auxiliary hair fixative, an auxiliary film former, an auxiliary rheological Modifiers, auxiliary hair conditioning agents, auxiliary skin conditioning agents, chemical curling or straightening agents, colorants, surfactants, polymer film modifiers, product stabilizing and finishing agents, propellants, auxiliary solvents, or its mixture. 44. The formulated composition of claim 41, wherein the composition for household care or institutional and industrial care is a cleaner. 45. The formulated composition of claim 41, wherein the composition for household care or institutional and industrial care comprises at least one of the following: pH adjusters, buffers, auxiliary film formers, auxiliary rheology modifiers , colorants, surfactants, metal ion chelating agents, dispersants, propellants, auxiliary solvents, or mixtures thereof. 46. The formulated composition of claim 41, wherein the composition for use in an industrial process is a textile treatment. 47. The formulated composition of claim 41, wherein the composition for household care, institutional and industrial care, or industrial process is a paint or surface coating. 48. The composition of claim 41 in the form of a liquid, gel, foam, spray, emulsion, semi-solid, or solid. 49. A composition comprising the polymer of claim 25 and water. 50. The composition of claim 49, further comprising at least one of the following: pH adjusters, buffers, auxiliary hair fixatives, auxiliary film formers, auxiliary rheology modifiers, auxiliary hair conditioners, auxiliary Skin conditioners, chemical curling or straightening agents, colorants, surfactants, polymer film modifiers, product stabilizers and finishes, propellants, co-solvents, or mixtures thereof. 51. The composition of claim 49, further comprising at least one quaternary ammonium compound. 52. The composition of claim 49, further comprising at least one hydroxycarboxylic acid. 53. The composition of claim 49, further comprising at least one immobilization aiding polymer. 54. A formulated composition comprising the polymer of any one of claims 1-32, wherein the formulated composition is selected from the group consisting of personal care, health care, household care, institutional care, industrial care, or industrial processes things. 55. The formulated composition of claim 54, wherein the composition for personal care is a cleanser for skin or hair. 56. The formulated composition of claim 54, wherein the composition for personal care or health care comprises at least one of the following: a pH adjuster, a buffer, an auxiliary hair fixative, an auxiliary film former, an auxiliary rheological Modifiers, auxiliary hair conditioning agents, auxiliary skin conditioning agents, chemical curling or straightening agents, colorants, surfactants, polymer film modifiers, product stabilizing and finishing agents, propellants, auxiliary solvents, or its mixture. 57. The formulated composition of claim 54, wherein the composition for household care or institutional and industrial care is a cleaner. 58. The formulated composition of claim 54, wherein the composition for household care or institutional and industrial care comprises at least one of the following: pH adjusters, buffers, auxiliary film formers, auxiliary rheology modifiers , colorants, surfactants, metal ion chelating agents, dispersants, propellants, auxiliary solvents, or mixtures thereof. 59. The formulated composition of claim 54, wherein the composition for use in an industrial process is a textile treatment. 60. The formulated composition of claim 54, wherein the composition for household care, institutional and industrial care, or industrial process is a paint or surface coating. 61. The composition of claim 54 in the form of a liquid, gel, foam, spray, emulsion, semi-solid, or solid. 62. An aqueous polymer emulsion comprising the polymer of claim 1 and at least one surfactant. 63. The aqueous polymer emulsion of claim 54, wherein the surfactant comprises 1 to 10% by weight of the emulsion, based on the total emulsion weight. 64. The aqueous polymer emulsion of claim 54, wherein the polymer constitutes at least 15% by weight of the emulsion, based on the total emulsion weight. 65. The aqueous polymer emulsion of claim 54, wherein the surfactant comprises at least one nonionic surfactant, anionic surfactant, or a mixture thereof. 66. A hair care composition comprising an effective amount of the polymer of claim 1 to provide a hair care composition with a property selected from the group consisting of hair fixative performance, hair conditioning performance, tackiness performance, deposition aiding performance, and combinations thereof. 67. The hair care composition of claim 66, further comprising at least one auxiliary film former, hair fixative, auxiliary hair conditioning agent, auxiliary rheology modifier, or mixtures thereof. 68. The hair care composition of claim 67, wherein the auxiliary hair conditioning agent is selected from silicone fluids. 69. The hair care composition of claim 68, wherein the silicone fluid is a silicone gum, a volatile silicone or a silicone copolymer. 70. The hair care composition of claim 68, further comprising a surfactant. 71. A skin care composition comprising an effective amount of the polymer of claim 1 to provide a skin care composition with a property selected from the group consisting of skin conditioning properties, tackiness properties, deposition promoting properties, and combinations thereof. 72. The skin care composition of claim 71 comprising at least one auxiliary skin conditioning agent, auxiliary rheology modifier or mixtures thereof.