WO2015054452A1 - Keratin conditioning bio-based polymers for use in personal care compositions - Google Patents

Abstract

Keratin conditioning polymers comprising at least an ethylenically unsaturated cationic monomer, a sugar containing ethylenically unsaturated monomer, optionally a monomer containing a carboxylic acid or sulfonic acid group and optionally a crosslinking agent are disclosed. The conditioning polymer is useful in personal care and home care compositions and especially useful as conditioning agents for keratinous substrates such as hair, skin and nails.

Description

Keratin Conditioning Bio-based Polymers for Use in Personal Care Compositions

Field of the Invention

The present application is directed to copolymers formed from sugar containing

(meth)acrylates and cationic monomers and their use in personal care compositions.

Background Hair is composed of keratin, a sulfur-containing fibrous protein. The isoelectric point of keratin, and more specifically of hair, is generally in the pH range of 3.2-4.0. Therefore, at the pH of a typical shampoo, hair carries a net negative charge. Consequently, cationic polymers have long been used as conditioners in shampoo formulations, or as a separate conditioning treatment to improve the wet and dry combability of the hair. The substantivity of the cationic polymers for negatively charged hair along with film formation facilitates detangling during wet hair combing and a reduction in static flyaway during dry hair combing. Cationic polymers generally also impart softness and suppleness to hair.

Although cationic polymers have long been used as conditioners in personal care compositions such as shampoos and bodywashes, the commercially available polymers are deficient in providing certain combinations of effects on keratinic substrates. For example, there is a need for new "green" materials which are capable of providing stand- alone conditioning and conditioning via enhanced deposition of silicone are highly desirable.

Summary of the Invention The present invention embodies novel conditioning polymers.

A keratin conditioning polymer formed from i.) a cationic monomer defined by formula (I) or formula (II)

(I) (I I)

in which:

R and R² are independently hydrogen or methyl, R³, R⁴ and R⁵ are independently linear or branched C C₃o alkyl radicals, X is NH, NR⁶ or oxygen, R₆ is Ci-C₆ alkyl, L is C_nH_2n, n is an integer from 1 to 5,

R⁷ and R⁸, independently of each other, represent a hydrogen atom or a linear or branched d -C₆ alkyl group,

R⁹ and R ⁰, independently of each other, represent an alkyl, hydroxyalkyi group wherein the alkyl group is a linear or branched Ci -C₆ chain, o and p are integers between 1 and 3; and

X^" represents a counterion; ii) an α, β ethylenically unsaturated sugar monomer; iii) optionally, at least one anionic monomer or potentially anionic monomer selected from the group consisting of ethylenically unsaturated carboxylic acid and ethylenically unsaturated sulfonic acid containing monomers; and (iv) optionally, a crosslinking monomer.

The invention also encompasses personal care compositions comprising the conditioning polymer described above.

The personal care compositions of particular interest are those personal care compositions which are applied to the body, including the skin and hair and which further contain a cosmetically acceptable carrier or adjuvants.

These personal care compositions comprising the conditioning polymer described above may also comprise a cosmetically acceptable carrier other than water.

The personal care compositions of particular interest are personal care compositions which are shampoos, rinse off conditioners and bodywashes. Thus the personal care composition may be a personal care cleansing composition.

Several method embodiments are envisioned.

A method for conditioning a keratinous substrate comprising treating the keratinous substrate with an effective amount of a composition comprising the polymer described above and further comprising cosmetically acceptable carrier other than water.

A method for enhancing the deposition of silicone onto skin, hair or nails which comprises topically applying to said skin, hair or nails a composition comprising a) the polymer described above; and b) at least one silicone compound. Detailed Description of the Invention

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about" . Molecular weight means weight average molecular weight (Mw) expressed as g/mole.

All percentages, parts and ratios are based upon the total weight of the compositions of the present invention, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and, therefore do not include solvents or byproducts that may be included in commercially available materials, unless otherwise specified.

Monomers are ethylenically unsaturated compounds capable of being polymerized.

A monomer unit is the unit that is formed from the ethylenically unsaturated compound after polymerization.

"α, β ethylenically unsaturation" is a phrase well known in the art and typically refers to (meth)acryl functionality.

Amphoteric or ampholytic may be used interchangeably, and describe a polymer that comprises anionic monomeric units and cationic monomeric units. An ampholytic polymer may be: anionic at a pH that is higher than its isoelectric point; and cationic at a pH that is lower than its isoelectric point: wherein the isoelectric point is the pH at which the net charge on a polymer is zero.

(Meth)acryl refers to both the acrylic and methacrylic derivatives.

Potential anionic monomers are monomers which upon hydrolysis form an acid such as an anhydride.

The term "polymer" as used herein shall include materials whether made by polymerization of one type of monomer or made by two (i.e., copolymers) or more types of monomers.

The term "ter-polymer" for purposes of the invention means a polymer formed from at least three different monomers. Thus the ter-polymer may contain more than three monomers.

The term "water soluble" as used herein, means that the polymer is soluble in water in the present composition. In general, the polymer may be soluble at 25 °C at a concentration of 0.1 % by weight of the water solvent, preferably at 1 %, more preferably at 5% and most preferably at 15%.

Keratinous substrates may include human or animal skin and hair or nails.

The term "skin" as used herein includes the skin on the face, neck, chest, back, arms, hands, legs and scalp.

As used herein, the term "effective amount" refers to that amount of a composition necessary to bring about a desired result, such as, for example, the amount needed to condition a keratin or hair-containing substrate.

The compositions of the present application may further comprise for example a

cosmetically acceptable vehicle. This phrase "cosmetically acceptable vehicle ", as used herein, means one or more compatible solid or liquid fillers, diluents, extenders and the like, which are cosmetically acceptable. As used herein "cosmetically acceptable" means a material (e.g., compound or composition) which is suitable for use in contact with human skin, hair or nails. The type of carrier or vehicle utilized in the present invention depends on the type of product desired. The compositions useful in the present invention may be a wide variety of product types. These include, but are not limited to, shampoos, 2-in-1

conditioners, rinse-off conditioners, lotions, creams, gels, sprays, pastes, mousses, and suspensions.

The novel keratin conditioning polymer of the application is formed from at least two monomers selected from at least i) and ii), i.) a cationic monomers encompassed by formula (I) or formula (II)

in which: R and R² are independently hydrogen or methyl,

R³, R⁴ and R⁵ are independently linear or branched C₁-C30 alkyl radicals, for example d-Cs alkyl radicals or C₁-C4 alkyl radicals,

X is NH, NR⁶ or oxygen, for example NH,

R₆ is Ci-C₆ alkyl,

n is an integer from 1 to 5, for example 2 or 3, especially 3,

R⁷ and R⁸, independently of each other, represent a hydrogen atom or a linear or branched d -C₆ alkyl group,

R⁹ and R ⁰, independently of each other, represent an Ci-C₆alkyl, hydroxyalkyi group wherein the alkyl group is a linear or branched d -C₆ chain, o and p are integers between 1 and 3, for example 1 or 2, most typically 1 ; and

X^" represents a counterion; ii) an α, β ethylenically unsaturated sugar monomer; iii) optionally, at least one anionic monomer selected from the group consisting of ethylenically unsaturated monocarboxylic and dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, ethylenically unsaturated sulfonic acid containing monomers and salts thereof; and

(iv) optionally, a crosslinking monomer.

In regard to formula (I), R₃, R₄ and R₅ are for example C₁-C14, Ci-C₈, C^Ce or d-C₄. Most typically R₃, R₄ and R₅ are C₁-C4 such as methyl, ethyl, isopropyl, propyl, butyl or a mixture thereof. The cationic monomer of formula (I) used in the inventive conditioning polymer is for example selected from the group consisting of (meth)acryloyloxyethyl-N,N,N- trimethylammonium chloride, (meth)acryloyloxyethyl-N-ethyl-N,N-dimethylammonium monoethyl sulfate, (meth)acryloyloxyethyl-N,N,N-triethylammonium monoethyl sulfate, (meth)acrylamidopropyl-N,N,N-trimethylammonium chloride, (meth)acrylamidopropyl-N- ethyl-N,N-dimethylammonium monoethyl sulfate, (meth)acrylamidopropyl-N,N-diethyl-N- methylammonium chloride, (meth)acrylamidopropyl-N,N-diethyl-N-methylammonium monomethyl sulfate and mixtures thereof,

For example (meth)acrylamidopropyl-N,N,N-trimethylammonium chloride,

(meth)acrylamidopropyl-N-ethyl-N,N-dimethylammonium monoethyl sulfate,

(meth)acryamidopropyl-N,N-diethyl-N-methylammonium chloride,

(meth)acrylamidopropyl-N,N-diethyl-N-methylammonium monomethyl sulfate and mixtures thereof and especially acrylamidopropyl-N,N,N-trimethylammonium chloride.

In regard to the cationic monomer of formula (II)

R⁷ and R⁸, represent a hydrogen atom or a linear or branched Ci -C₆ alkyl group. Thus for example R⁷ and R⁸ could be hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, isobutyl, pentyl or hexyl. More typically however, R⁷ and R⁸ is independently hydrogen or methyl. R⁹ and R ⁰, independently of each other, represent an alkyl, hydroxyalkyl group wherein the alkyl group is a linear or branched Ci -C₆ alkyl chain.

When R⁹ and R ⁰ is C^-C_e alkyl, this means for purposes of this application that the C C₆ alkyl may be branched or unbranched radical for example Ci-C₂, C₁-C4 alkyl, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl and n-hexyl.

Most typically R⁹ and R ⁰ are d-C₄ alkyl or d-C₂ alkyl and R⁷ and R⁸ are hydrogen.

Hydroxyalkyl is similarily defined as Ci-C₆ alkyl but the alkyl radical may be branched or unbranched and further substituted by 1 , 2 or 3 hydroxy radicals. For example, the hydroxyl substituted alkyl may be -CH₂OH, -CH₂CH₂OH, -CH₂(OH)CH₂CH₂OH, - CH₂CH₂CH(CH₃)CH₂OH and -CH₂CH₂(OH)CH₃.

The counterion X^" may be virtually any counterion organic or inorganic. Inorganic anions means anions such as halogens including fluoride, chloride, bromide and iodide, sulfate, sulfite, bisulfate, borate, nitrate, phosphate or phosphonate. Organic anions would include for example carbonate, bicarbonate, formate, acetate, benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate, fumarate, maleate, itaconate, glycolate, gluconate, malate, mandelate, tiglate, ascorbate, polymethacrylate, a carboxylate of nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylene-diaminetetraacetic acid or of diethylenetriaminepentaacetic acid, a diethylenetriaminepentamethylenephosphonate, an alkylsulfonate or an arylsulfonate.

Most typically the monomers represented by formula (II) are for example,

diallydialkylammonium monomers.

Those commonly available monomers of formula (II) include diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallydimethylammonlum sulfate, diallydimethylammonium phosphate, dimethyallydimethyammonium chloride,

diethylallyldimethylammonium chloride, diallyldi(beta-hydroxyethyl)ammonium chloride and diallyldiethylammonium chloride. o and p are integers between 1 and 3, most typically o and p are 1 ; The cationic monomer of formula (I) or formula (II) or a mixture of formula (I) and (II) will for example make up at least about 30 to about 96, about 40 to about 95, about 45 to about 92 weight percent of the formed conditioning polymer.

A minimum of about 40 or 50 weight % component i) is most typical. α, β ethylenically Unsaturated Sugar Monomer

Component ii) is an α, β ethylenically unsaturated sugar monomer. This would include any α, β ethylenically unsaturated sugar.

For example, sugar containing α, β ethylenically unsaturated sugar monomers are described in U.S. Patent Nos. 5,854,030 and 7,767,425 herein entirely incorporated by reference.

For instance U.S. 7,767,425 teaches the synthesis of sugar acrylates which comprises the reaction of a sugar compound with an (meth)acrylic acid compound or an alkyl ester thereof in a liquid medium comprising an organic solvent in the presence of an acrylate-transferring enzyme. The sugar compounds are open-chain and cyclic monosaccharides, oligosaccharides and polysaccharides, and also oxidized, reduced, alkylated, esterified, aminated sugars from natural and synthetic sources. In particular, the sugar compounds are selected from the group consisting of monosaccharides and oligosaccharides and the esterifiable derivatives thereof in an optically pure form or as a stereoisomer mixture. Esterifiable monosaccharides are selected from the group consisting of aldoses and ketoses, in particular aldopentoses and aldohexoses and ketopentoses and ketohexoses and the esterifiable derivatives thereof, in particular Ci-C₃₀-alkyl glycosides. Preferred oligosaccharides are selected from the group consisting of disaccharides and trisaccharides and the esterifiable derivatives thereof. Further possible sugars are Ci-C₃₀-alkyl glycosides containing one or more functional groups in the alkyl chain, and glycosides which bear polyalkylene glycol radicals, for example polyethylene glycol or polypropylene glycol radicals. Non-restricting examples of suitable functional groups are 0-, S- or N-containing groups, such as HO, HS, amino, carboxyl or carbonyl and ether and thioether bridges. For example, d-Cao-alkyl glycosides, for example d-Ce-alkyl glycosides, in particular methyl glycopyranosides, methyl-. alpha. -D-glucopyranoside, are of interest.

U.S. 5,854, 030 also teaches acrylated sugars. The following structure is representative of the acrylated sugars taught in U.S. 5,854,030:

wherein the S is selected from the group consisting of sucrose acrylated at the 1 '-position, raffinose at the 1 "-position, fructose at the 1 -position, trehalose at the 6-position, a- and β- phenyl- or alkylglucosides at the 6-position, a- and β-haloglucosides at the 6-position, a - and -phenyl or alkylgalactosides at the 6-position, a- and β-halogalactosides at the 6- position, a- β-phenyl- or alkymannosides at the 6-position, a - and β-halomannosides at the 6-position, and mixtures thereof; R is selected from the group consisting of hydrogen, straight chain alkanes having from about 1-3 carbon atoms, and mixtures thereof.

Accordingly, the α, β ethylenically unsaturated sugar monomer may be defined as any sugar esterified with (meth)acrylic acid or (meth)acrylic ester monomer. Of special interest are the sugar esters of (meth)acrylic glycocide wherein the sugar of the ester is a C Cao-alkyl glycosides, for example CrC₆-alkyl glycosides, in particular methyl glycopyranosides or methyl-. alpha. -D-glucopyranoside ester.

Also, of high interest are (meth)acrylate of sorbitol. This would also include di(meth)acrylates of sorbitol. For example, two sugar monomers of special interest are:

wherein R is hydrogen or methyl.

The content of the α, β ethylenically unsaturated sugar making up the conditioning polymer varies widely. For instance, the weight % of α, β ethylenically unsaturated sugar varies from about 5 to about 50 weight %, about 7 to about 40, and about 8 to about 30 or about 8 to 20 weight % based on the total weight of the conditioning polymer.

The Anionic Component iii)

The anionic component or potentially anionic component (ie. anhydride) iii) is optional and as explained above is defined as an anionic monomer selected from the group consisting of ethylenically unsaturated monocarboxylic and dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, ethylenically unsaturated sulfonic acid containing monomers and salts thereof.

The anionic monomers of component iii) will typically contain carboxylic acids or sulfonic acid groups. For example, acrylic acid (AA), methacrylic acid (MAA), 2-acrylamido-2- methylpropane sulfonic acid (AMPSA), 2-methacrylamido-2-methylpropane sulfonic acid (MAMPSA), crotonic acid, 2-methyl crotonic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and mixtures thereof are considered. For example, the conditioning polymer is formed from anionic monomers of component iii) which are monoethylenically unsaturated C₃-C₆ monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 2-ethylpropenoic acid or ethylenically unsaturated C₄-C₆ dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid or the anhydrides thereof, for example maleic anhydride, or salts thereof.

The salts of the anionic monomer are typically organic or inorganic salts. For example inorganic salts would include monovalent or divalent metal ion such as sodium, potassium, lithium or ammonium. Organic salts would include for example organic ammonium ion.

The anionic monomer of component iii) are especially compounds of formula (VI) or anhydrides:

(VI) where R₁₂ and R₁₃ are independently hydrogen or CrC₆alkyl, Ri₄ is hydrogen, Ci-C₆alkyl or a COOM group and

M is hydrogen, a monovalent or divalent metal ion, ammonium or an organic ammonium ion.

An important embodiment is the conditioning polymer, wherein the anionic monomer of component iii) is a compound of formula (VI) or the anhydrides thereof:

(VI) R₁₂ and R₁₃ are hydrogen ,

R-I4 is hydrogen, methyl or a COOM group,

M is hydrogen, a monovalent or divalent metal ion, ammonium or an organic ammonium ion.

The anionic monomer or component iii) will for example make up 0 to about 35, about 1 to about 30, about 4 or about 10 to about 15 weight percent of the total weight of the formed conditioning polymer.

Most often component iii) will vary from about 0 to about 20 or 30 wt. %. For example, the component iii) will most often be a minimum of about 1 ,2, 3 or 4 wt. % and a maximum of about 25 wt.%, for example about 5 to about 20 wt. %, wherein the wt. % is based on the total weight of the conditioning polymer.

The molar ratio of component i) and iii) may vary from 12: 1 to 1.1 : 1 , for example 5:1 to 1.5:1. Thus the conditioning polymer will typically carry a cationic charge regardless of the pH of the medium in which the conditioning polymer is dispersed or dissolved.

The conditioning polymer may comprise additional monomers other than those defined by the monomer groups i), ii) and optionally iii) and optional crosslinker iv).

For example the conditioning polymer may optionally include monomers not defined by either components i), ii), iii) or crosslinker of iv)

For example the conditioning polymer may optionally also contain monomers such as for example the conditioning polymer may optionally also contain monoethylenically

unsaturated imidazoles and their alkyl derivatives and quaternized products, esters and basic esters of a, β-unsaturated C₃-C₆ acids, basic amides of a, β-unsaturated C₃-C₆ acids, substituted and unsubstituted amides of a, β-unsaturated C₃-C₆ acids, diallyamine and derivative of diallyamines (other than formula (II)), vinylpyridine and their quaternized derivatives, vinyl ethers and Ci-C₆ hydroxy substituted alkyl (meth)acrylates. Thus the conditioning polymer may optionally contain further cationic monomers or nonionic monomers. The most typical nonionic monomers are esters of a, β-unsaturated C₃-C₆ acids and amides of a, β-unsaturated C₃-C₆ acids, C-i-C₆ hydroxy substituted alkyl (meth)acrylates and vinyl ethers of alcohols containing from 1 to 10 carbon atoms, aliphatic hydrocarbons having from 2 to 8 carbon atoms and 1 or 2 double bonds, or mixtures of these monomers.

Monoethylenically unsaturated imidazoles and their alkyl derivatives and quaternized products would include such monomers as N-vinylimidazole, N-vinyl-2methylimidazole, N- vinyl 4-methylimidazole, N-vinyl-5-methylimidazol, N-vinyl-2-ethylimidazole, N- vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline. Esters and basic esters of ethylenically unsaturated carboxylic acids, in particular esters of a, β-unsaturated C₃-C₆ acids and amides of a, β-unsaturated C₃-C₆ acids may be part of the conditioning polymer.

Esters of a, β-unsaturated C₃-C₆ acids would include such monomers as C-i-C₈ esters of α,β- ethylenically unsaturated C₃-C₆ mono carboxylic acids such as, methyl (meth)acrylate, ethyl (meth)acrylate, methyl ethacrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n- propyl ethacrylate, ethyl ethacrylate, isopropyl ethacrylate, n butyl (meth)acrylate, n-butyl ethacrylate, tert-butyl (meth)acrylate, tert-butyl ethacrylate, isobutyl (meth)acrylate, isobutyl ethacrylate, sec-butyl (meth)acrylate, butyl ethacrylate, 2-pentyl (meth)acrylate, 3-pentyl (meth)acrylate, isopentyl (meth)acrylate and neopentyl (meth)acry-"late and mixtures thereof.

Basic esters and would include such monomers as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl(meth)acrylate, diethylaminoethyl (meth)acrylate,

diethylaminopropyl(meth)acrylate, dimethylaminobutyl(meth)acrylate,

diethylaminobutyl(meth)acrylate and the protonated forms thereof.

The basic amides of the a, β-unsaturated C₃-C₆ acids would include

dimethylaminoethyl(meth)acrylamide,diethylaminoethyl(meth)acrylamide,

dimethylaminopropyl(meth)acrylamide and diethylaminoprpropyl(meth)acrylamide and the protonated forms thereof. Substituted and unsubstituted amides of a, β-unsaturated C₃-C₆ acids would include such monomers as (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl

(meth)acrylamide, N-acetyl (meth)acrylamide, N-butyl (meth)acrylamide, N,N-dibutyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-ethyl (meth)acrylamide and N,N-diethyl (meth)acrylamide.

Diallyamine and derivative of diallyamines are also considered. For example diallylamine, diallylmethylamine and diallylethylamine.

Vinylpyridine and their quaternized derivatives are also possible cationic monomers in addition to component i). Accordingly, vinylpyridine, 2-vinylpyridine, N-methy-4-vinylpyridine and N-methyl-2-vinylpyridine are considered.

C -C_e hydroxy substituted alkyl (meth)acrylates would include such monomers as hydroxy(meth)acrylates which are the esters of (meth)acrylic acid with d-C₄-alkanediols. For examples hydroxyl(meth)acrylates might be selected from the group consisting of hydroxymethyl (meth)acrylate, hyroxyethyl (meth)acrylate, hydroxymethyl ethacrylate, hydroxy-n-propyl (meth)acrylate, hydroxyl-isopropyl (meth)acrylate, hydroxy-n-butyl

(meth)acrylate, hydroxyl-tert-butyl (meth)acrylate, hydroxyl-isobutyl (meth)acrylate, hydroxyl- sec-butyl (meth)acrylate and mixtures thereof.

Examples of vinyl ethers include vinyl methyl ether, vinyl ethyl ether or vinyl isobutyl ether. Preferred vinylethers are those of alcohols containing from 1 to 20 carbon atoms..

Thus examples of vinyl ethers would include allyl vinylether, butoxyethyl vinylether, tert-butyl vinylether, ethyl vinylether, 2-hydroxyethyl vinylether, isoamyl vinyllether, isobutyl vinylether, isopropyl vinylether, methyl vinylether, dodecyl or lauryl vinylether, propyl vinylether, hexadecyl vinylether, 4-hydroxybutyl vinylether, isoamyl vinylether, isobutyl vinylether, isooctyl vinylether, isopropyl vinylether, methyl vinylether and octadecyl vinylether.

Preferred vinylethers are those of alcohols containing from 1 to 18 carbon atoms..

The conditioning polymer may be formed substantially from monomer units i), ii) or i), ii) and iii) above. The Crosslinking Agent of Component iv)

"Cross-linked" as used herein refers to at least two chains of the conditioning polymer attached by bridges, referred to herein as "cross-linking agentsor monomers" comprising an element, a group, bond or a compound which joins certain carbon atoms of the chains by primary chemical bonds.

"Polyfunctional" cross-linking agents may comprise monomers having: at least two double bonds; at least a double bond and a reactive group; or at least two reactive groups.

Suitable cross-linking agents include, but are not limited to, polyfunctional epoxy

compounds, dihaloalkyi compounds, diisocyanate compounds and compounds containing at least two activated olefinic double bonds.

Exempliary cross-linking agents of the at least diolefinic variety are methylenebisacrylamide; methylenebismethacrylamide; 1 ,3-diallylurea , triallylurea, tetraallylurea, N,N- diallylacrylamide, tetraallylammonium chloride, tetraallylammonium sulfate,

tetraallylammonium methylsulfate, esters of unsaturated monocarboxylic and polycarboxylic acids with polyols, diacrylates and triacrylates, dimethacrylates and trimethacrylates, butanediol and ethylene glycol diacrylate and methacrylate, diethylene glycol diacrylate, poly(ethylene glycol) diacrylate, poly(propylene glycol) diacrylate and the like,

trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA). Allyl compounds may also be considered such as allyl (meth)acrylate, triallyl cyanurate, diallyl maleate, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine; allyl esters of phosphoric acid; and/or vinylphosphonic acid derivatives. MBA is the most typical cross-linking agent.

Examples of polyfunctional epoxy compounds include epihalohydrins such as

epichlorohydrin, ethylene glycol diglycidyl either (EGDE); diglycidyl ether; 1 ,2,3,4- diepoxybutane; 1 ,2,5,6-diepoxyhexane; poly(propylene glycol) diglycidyl ether (PPGDE);

1 ,4-butanediol diglycidyl ether, 3-bis(glycidyloxy)methyl-1 ,2-propanediol, bisphenol A diglycidyl ether (BADGE), poly(phenylglycidyl ether-co-formaldehyde), glycerol propoxylate triglycidyl ether, N,N-diglycidyl-4-glycidyloxyaniline, triglycidyl isocyanurate and the like. Examples of dihaloalkyl compounds include 1 ,2-dichloroethane, 1 ,2-dibromoethane, 1 ,3- dichloropropane, 1 ,4-dichlobutane, 1 ,6-dichlorohexane, 1 ,10-dichlorodecane and the like. Preferred dihaloalkyl cross-linkers are 1 ,2-dibromoethane and 1 ,2-dichloroethane. Diisocyanate compounds can be used as the cross-linking agent for base polymers containing primary or secondary amino groups. Examples of diisocyanate compounds are isophorone diisocyanate (IPDI), 1 , 4-diisocyanobutane, hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI) and the like. The polyfunctional cross-linking units may be added during the formation of the conditioning polymer at amounts that range from 20 to 10,000 ppm of the total monomer content. For example, 20 to 1000 ppm, 50 to 800 ppm or 75 to 600 ppm are envisioned.

Most typical crosslinkers are methylenebisacrylamide (MBA); methylenebismethacrylamide.

The weight fraction of crosslinking comonomers, based on the total mass of the copolymers, is not more than 5 %, 3% or 2% by weight, more typically from 0.00002 to 2% by weight, and most preferably from 0.00002 to 1 % by weight.

The Formed Conditioning Polymer

The average molecular weight (Mw) of the conditioning polymer ranges for example from about 10,000 to about 18,000,000, about 25,000 to about 5,000,000, typically about 35,000 to about 1 ,800,000. Alternatively, the Mw may vary from about 15,000 to about 1 ,000,000 or about 10,000 or about 20,000 to about 800,000. For example, about 100,000 to about 1 ,000,000 or about 120,000 to about 800,000 are envisioned.

The conditioning polymer may be either water soluble, water-swellable or water dispersible but the polymer should be dispersible or soluble in the formulation. Thus there are a number of particular embodiments of interest in regard to the conditioning polymer:

The conditioning polymer may be formed from monomers, i.) cationic monomers encompassed by formula (I) or (II)

in which: R and R² are independently hydrogen or methyl, R³, R⁴ and R⁵ are d-C₄ alkyl radicals, X is NH,

n is 3, R⁷ and R⁸ are hydrogen or methyl,

R⁹ and R ⁰ are methyl or ethyl, especially methyl, o and p are 1 , and

X- is an anion derived from an organic or inorganic acid, ii) an α, β ethylenically unsaturated sugar monomer such as the reaction of a sugar compound with an (meth)acrylic acid compound or an alkyl ester thereof to form a sugar ester of (meth)acrylate; iii) optionally, at least one anionic monomer potentially anionic monomer selected from the group consisting of ethylenically unsaturated monocarboxylic and dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, ethylenically unsaturated sulfonic acid containing monomers and salts thereof;

and

(iv) optionally, a crosslinking monomer.

Alternatively, the conditioning polymer may be formed from

i.) a cationic monomers encompassed by formula (I) or (II)

(I) (ll) in which:

Ri and R₂ are independently hydrogen or methyl,

R₃, R₄ and R₅ are Ci-C₄ alkyl radicals,

X is NH,

L is C_nH_2n ,

n is 3,

R⁷ and R⁸ are hydrogen or methyl,

R⁹ and R ⁰ are methyl or ethyl, especially methyl,

o and p are 1 ,

and X- is an anion derived from an organic or inorganic acid, such as a methosulphate anion or halide, such as chloride or bromide, ii) an α, β ethylenically unsaturated sugar monomer, for example the sugar monomers are ester derivatives and the sugars of the esters are selected from the group consisting of monosaccharides, oligosaccharides and sorbitol in an optically pure form or as a stereoisomer mixture. Further the esterifiable monosaccharides are selected from the group consisting of sorbitol, aldoses and ketoses, in particular aldopentoses and aldohexoses and ketopentoses and ketohexoses and the esterifiable derivatives thereof, in particular Ci-C₃₀- alkyl glycosides and (meth)acrylate sugar esters of sorbitol; iii) at least one anionic monomer selected from the group consisting of ethylenically unsaturated monocarboxylic and dicarboxylic acids and anhydrides of unsaturated dicarboxylic acids; and

(iv) optionally, a crosslinking monomer.

An alternative third embodiment is the conditioning polymer may be formed from i.) a cationic monomers selected from the group consisting of (meth)acryloyloxyethyl

Ν,Ν,Ν-trimethylammonium chloride, (meth)acryloyloxyethyl-N-ethyl-N,N- dimethylammonium monoethyl sulfate, (meth)acryloyloxyethyl-N,N,N-triethylammonium monoethyl sulfate, (meth)acrylamidopropyl-N,N,N-trimethylammonium chloride, (meth)acrylamidopropyl-N-ethyl-N,N-dimethylammonium monoethyl sulfate,

(meth)acrylamidopropyl-N,N-diethyl-N-methylammonium

chloride, (meth)acrylamidopropyl-N,N-diethyl-N-methylammonium monomethyl sulfate, diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallydimethylammonlum sulfate, diallydimethylammonium phosphate,

dimethyallydimethyammonium chloride, diethylallyldimethylammonium chloride, diallyldi(beta-hydroxyethyl)ammonium chloride and diallyldiethylammonium chloride and

mixtures thereof. ii) an α, β ethylenically unsaturated sugar monomer are ester derivatives of sugars and the sugars are selected from the group consisting of monosaccharides, oligosaccharides and sorbitol in an optically pure form or as a stereoisomer mixture. Further the esterifiable monosaccharides are selected from the group consisting of sorbitol, aldoses and ketoses, in particular aldopentoses and aldohexoses and ketopentoses and ketohexoses and the esterifiable derivatives thereof, in particular Ci-C₃₀-alkyl glycosides and (meth)acrylate sugar esters of sorbitol; iii) at least one anionic monomer selected from the group consisting of ethylenically unsaturated C₃-C₆ monocarboxylic and C₃-C₆ dicarboxylic acids and anhydrides of unsaturated dicarboxylic acids; and

(iv) optionally, a crosslinking monomer.

A fourth embodiment of interest is the conditioning polymer formed i.) a cationic monomers selected from the group consisting of (meth)acryloyloxyethyl-N,N,N- trimethylammonium chloride, (meth)acryloyloxyethyl-N-ethyl-N,N-dimethylammonium monoethyl sulfate, (meth)acryloyloxyethyl-N,N,N-triethylammonium monoethyl sulfate, (meth)acrylamidopropyl-N,N,N-trimethylammonium chloride, (meth)acrylamidopropyl-N- ethyl-N,N-dimethylammonium monoethyl sulfate, (meth)acrylamidopropyl-N,N-diethyl-N- methylammonium chloride, (meth)acrylamidopropyl-N,N-diethyl-N-methylammonium monomethyl sulfate and mixtures thereof, ii) an α, β ethylenically unsaturated sugar monomer; iii) an anionic monomer which is a compound of formula (VI) or the anhydrides thereof:

(VI)

R₁₂ and R₁₃ are hydrogen ,

R-I4 is hydrogen, methyl or a COOM group,

M is hydrogen, a monovalent or divalent metal ion, ammonium or an organic ammonium ion. and iv)optionally a crosslinking agent.

A fifth embodiment envisioned for the conditioning polymer is the polymer is formed from i.) a cationic monomers selected from the group consisting of (meth)acrylamidopropyl- Ν,Ν,Ν-trimethylammonium chloride, (meth)acrylamidopropyl-N-ethyl-N,N- dimethylammonium monoethyl sulfate, (meth)acrylamidopropyl-N,N-diethyl-N- methylammonium chloride, (meth)acrylamidopropyl-N,N-diethyl-N-methylammonium monomethyl sulfate and mixtures thereof or a cationic monomer selected from the group consisting of diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallydimethylammonlum sulfate, diallydimethylammonium phosphate, dimethyallydimethyammonium chloride,

diethylallyldimethylammonium chloride, diallyldi(beta-hydroxyethyl)ammonium chloride, diallyldiethylammonium chloride and mixtures thereof. ii) an α, β ethylenically unsaturated sugar monomer such as Ci-C₃₀-alkyl glycosides, for example CrC₆-alkyl glycosides, in particular methyl glycopyranosides or methyl-. alpha. -D- glucopyranoside ester or (meth)acrylate esters of sorbitol such as mono and

di(meth)acrylates of sorbitol; iii) an anionic monomer selected from the group consisting of monoethylenically

unsaturated C₃-C₆ monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 2-ethylpropenoic acid or ethylenically unsaturated C₄-C₆ dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid or the anhydrides thereof, for example maleic anhydride, or salts thereof; iv) optionally crosslinking agent, for example the crosslinking agent ranges from about 0.00002 to about 2% by weight based on the total weight of the conditioning polymer and v) optionally, a fourth monomer selected from group consisting of monoethylenically unsaturated imidazoles and their alkyl derivatives and quaternized products, esters and basic esters of a, β-unsaturated C₃-C₆ acids, basic amides of a, β-unsaturated C₃-C₆ acids, substituted and unsubstituted amides of a, β-unsaturated C₃-C₆ acids, diallyamine and derivative of diallyamines (other than formula (II)), vinylpyridine and their quaternized derivatives, vinyl ethers and Ci-C₆ hydroxy substituted alkyl (meth)acrylates .

A sixth embodiment envisioned is the conditioning polymer formed from i.) the cationic monomer (meth)acrylamidopropyl-N,N,N-trimethylammonium salts or diallydimethyl ammonium salts ii.) an α, β ethylenically unsaturated sugar monomer, for example

iii) an anionic monomer selected from the group consisting of monoethylenically unsaturated C₃-C₆ monocarboxylic acids such as acrylic acid, methacrylic acid; and iv) optionally, a crosslinking agent. Use of the Conditioning Polymer

The conditioning polymer may be used in virtually any personal care composition. The conditioning polymer has been found to be especially useful in personal care compositions which are used on keratinous substrates such as hair, skin or nails.

Such products as shampoos, 2-1 shampoos, conditioners, rinse-off conditioners, coloring products, bleaching products, setting lotions, blow-drying lotions, restructuring lotions, perms and straightening products may incorporate the inventive conditioning polymer of the embodiments expressed above.

The conditioning polymer will typically comprise from about 0.05 to about 10 wt. %, about 0.1 to about 8 wt. %, about 0.3 to about 5 or 6 wt. %, wherein the wt. % is based on the total weight of the personal care composition. The most typical application rate is about 0.1 to about 1 wt. %.

For example the conditioning polymer may be added to personal cleansing compositions selected from the group consisting of 2-in-1 shampoos, a bodywash, a facial wash, a bubble bath, soapless cleansers, liquid and bar soap; a shower gel, xfoliating shower gel; a milk bath; moist towelletes; bath effervescent tablets (e.g., bubble bath); a bath/shower gel or a shower cream and may further comprises a detersive anionic surfactant which surfactant makes up about 2, 3, 4 or 5% to about 50%, from about 5% to about 30%, from about 10% to about 25% and especially about 12% to about 18%, by weight of the total weight of the composition.

Of particular interest are conditioning shampoos or 2-in-1 shampoos. These shampoos not only wash but also condition hair. Thus 2-in-1 shampoos are advantageous in that they do not require a second conditioning step after washing the hair. The use of the conditioning polymers in styling gels, rinse off conditioners and leave in conditioners is also contemplated.

When formulated as such, the conditioning polymers are able to form in situ coacervate complexes that deposit as a substantive and lubricious film on the hair surface. This deposition is key in improving the manageability and feel of hair, especially curly and multi- textured hair.

A further benefit of the proposed materials is the ability to increase the delivery of various benefit agents such as silicone, fatty quaternaries, etc., thereby providing superior conditioning to keratin substrates. The polymers may also offer hair styling and rheology modification benefits when formulated in personal care products.

Thus one of the important embodiment of this application is a personal cleansing composition comprising the conditioning polymer, wherein the cleansing composition is a 2- in-1 shampoo and the personal cleansing composition further comprises a detersive anionic surfactant from about 4 or 5 wt.% to about 50 wt. % and the wt. % is based on the total weight of the cleansing composition.

"Bodywash" encompasses all cleansing vehicles applied to the body. Exemplary forms of cleansing vehicles include, but are not limited to, liquid, bar, gel, foam, aerosol or pump spray, cream, lotion, stick, powder, or incorporated into a patch or a towelette. In addition, soapless cleansers may be used as well. The bodywash can be made into any suitable product form. Thus, as used herein, "bodywash" includes, but is not limited to, a soap including liquid and bar soap; a shower gel; including an exfoliating shower gel; a foaming bath product (e.g. gel, soap or lotion); a milk bath; including a gel cleanser, a liquid cleanser and a cleansing bar; moist towelletes; bath effervescent tablets (e.g., bubble bath); a bath/shower gel; a shower cream. These personal care compositions incorporating the conditioning polymer may also be keratinous conditioning compositions such as hand lotions, body lotion, a body spray, mist or gel, hair conditions rinses, shaving cream, an after-shave, after-shave moisturizer, a depilatory cream; a shaving product e.g. a shaving cream, gel, foam or soap, an aftershave, after-shave moisturizer; a hand and nail cream and combinations thereof, and any other composition used for post-cleansing application to the body, including the skin and hair.

Thus the personal care composition is a hand lotion, body lotion, a body spray, mist or gel, hair conditioning product in the form of a 2-in-1 shampoo, rinse off conditioner or stay on conditioner, shaving cream, gel, foam or soap, an after-shave, after-shave moisturizer, a hand and nail cream or a depilatory cream.

As implied above the personal care products can be in any form such as creams, ointments, pastes, foams, gels, lotions, powders, make-ups, sprays, sticks or aerosols.

Creams are oil-in-water emulsions containing more than 50% of water. The oil-containing base used therein is usually mainly fatty alcohols, for example lauryl, cetyl or stearyl alcohol, fatty acids, for example palmitic or stearic acid, liquid to solid waxes, for example isopropyl- myristate or beeswax and/or hydrocarbon compounds, such as paraffin oil. Suitable emulsifiers are surfactants having primarily hydrophilic properties, such as the

corresponding non-ionic emulsifiers, for example fatty acid esters of polyalcohols of ethylene oxide adducts, such as polyglycerol fatty acid ester or polyoxyethylenesorbitan fatty acid ether (Tween trademarks); polyoxyethylene fatty alcohol ether or their esters or the corresponding ionic emulsifiers, such as the alkali metal salts of fatty alcohol sulfonates, sodium cetyl sulfate or sodium stearyl sulfate, which are usually used together with fatty alcohols, such as cetyl alcohol or stearyl alcohol. In addition, creams contain agents which reduce water loss during evaporation, for example polyalcohols, such as glycerol, sorbitol, propylene glycol, and/or polyethylene glycols.

Ointments are water-in-oil emulsions which contain up to 70%, preferably not more than 20 to 50%, of water or of an aqueous phase. The oil-containing phase contains predominantly hydrocarbons, such as paraffin oil and/or solid paraffin which preferably contains hydroxy compounds, for example fatty alcohol or their esters, such as cetyl alcohol or wool wax for improving the water absorption. Emulsifiers are corresponding lipophilic substances, such as sorbitan fatty acid ester. In addition, the ointments contain moisturisers such as polyalcohols, for example glycerol, propylene glycol, sorbitol and/or polyethylene glycol as well as preservatives.

Rich creams are anhydrous formulations and are produced on the basis of hydrocarbon compounds, such as paraffin, natural or partially synthetic fats, for example coconut fatty acid triglycerides or preferably hardened oils and glycerol partial fatty acid esters.

Pastes are creams and ointments containing powdered ingredients which absorb secretions, for example metal oxides, such as titanium dioxide or zinc oxide, and also tallow and/or aluminium silicates which bind the moisture or the absorbed secretion.

Foams are liquid oil-in-water emulsions in aerosol form. Hydrocarbon compounds are used, inter alia, for the oil-containing phase, for example paraffin oil, fatty alcohols, such as cetyl alcohol, fatty acid esters, such as isopropylmyristate and/or waxes. Suitable emulsifiers are, inter alia, mixtures of emulsifiers having predominantly hydrophilic properties, for example polyoxyethylenesorbitan fatty acid ester, and also emulsifiers having predominantly lipophilic properties, for example sorbitan fatty acid ester. Commercially available additives are usually additionally employed, for example preservatives.

Gels are, in particular, aqueous solutions or suspensions of active substances in which gel formers are dispersed or swelled, in particular cellulose ethers, such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose or vegetable hydrocolloid, for example sodium alginate, tragacanth or gum arabic. The gels preferably additionally contain also polyalcohols, such as propylene glycol or glycerol as moisturizers and wetting agents, such as polyoxyethylenesobitan fatty acid ester. The gels furthermore contain commercially available preservatives, such as benzyl alcohol, phenethyl alcohol, phenoxyethanol and the like.

As discussed above, the inventors have discovered that the conditioning polymer performs very well as a silicone deposition agent. That is when combined in shampoo, rinse off conditioner or bodywash containing silicone, the conditioning polymers effectively aids in the deposition of silicone onto keratinous surfaces such as hair and skin thus heightening conditioning effects.

The inventive polymer upon dilution with water and or oil may form a polymer/silicone aggregate or coacervate/ optional benefit agent (such as fatty amines, fatty amine oxides or quaternary amines, oily components, fatty acids, silicone or mixtures thereof) , thus physically depositing the aggregate onto the skin or hair where the conditioning benefit is desired. Conditioning Agents

In addition to the conditioning polymer fatty amines, fatty amine oxides and quaternary amines, other conditioning agents may be combined with the conditioning polymer. For example, conditioning agents useful herein include silicones, oily or fatty materials such as hydrocarbons, fatty ester, silicones and cationic fatty materials such as the fatty amines, fatty oxides, fatty quaternaries suggested above.

Silicones

The most commonly used conditioning agents are silicones. The present conditioning polymer is effective as a silicone deposition aid with virtually any silicone. The most commonly used silicones which are suitable for use in personal cleansing or personal care compositions are typically modified or unmodified polyorganosiloxanes, i.e.

polyorganosiloxane oils or polyorganosiloxane gums or resins, in their native form or in the form of solutions in organic solvents or alternatively in the form of emulsions or

microemulsions.

Among the polyorganosiloxanes which may be used in accordance with the present invention, mention may be made, in a non-limiting manner, of:

I. Volatile silicones: these have a boiling point of between 60C and 260C. They are chosen from cyclic silicones containing from 3 to 7 and preferably 4 to 5 silicon atoms. Examples of these are octamethylcyclotetrasiloxane sold under the name VOLATILE SILICONE 7207" by Union Carbide or SILBIONE 70045 V2 by Rhone-Poulenc, decamethylcyclopentasiloxane sold under the name VOLATILE SILICONE 71581 1 by Union Carbide, SILBIONE 70045 V5 by Rhone-Poulenc, as well as mixtures thereof. Mention is also made of cyclocopolymers such as dimethylsiloxane/methylalkylsiloxane, for instance VOLATILE SILICONE FZ3109 sold by the company Union Carbide, which is a dimethylsiloxane/methyloctylsiloxane cyclocopolymer.

II. Non-volatile silicones: these consist mainly of: (i) polyalkylsiloxanes; among the polyalkylsiloxanes which may mainly be mentioned are linear polydimethylsiloxanes containing trimethylsilyl end groups, such as, for example, and in a non-limiting manner, the SILBIONE oils of the 70047 series sold by Rhodia Chimie; the DC200 oils and Silicone emulsions such as DC-1664 from Dow Corning, and PDMSs containing hydroxydimethylsilyl end groups;

(ii) polyarylsiloxanes;

(iii) polyalkylarylsiloxanes; mention may be made of linear and branched

polymethylphenylsiloxanes, polydimethylmethylphenylsiloxanes and

polydimethyldiphenylsiloxanes, such as, for example, the oil RHODORSIL 7631 1 from Rhodia Chimie;

(iv) silicone gums; these are polydiorganosiloxanes with a molecular mass of between 200,000 and 5,000,000, which are used alone or as a mixture in a solvent chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, methylene chloride, pentane, dodecane, tridecane, tetradecane or mixtures thereof; mention is made, for example, of the following compounds: polydimethylsiloxane, poly[(dimethylsiloxane)/(methylvinylsiloxane)], poly[(dimethylsiloxane)/(diphenylsiloxane)], poly[(dimethylsiloxane)/(phenylmethylsiloxane)], poly[(dimethylsiloxane)/(diphenylsiloxane)/(methylvinylsiloxane)];

mention may also be made, for example, in a non-limiting manner, of the following mixtures:

1 ) mixtures formed from a polydimethylsiloxane hydroxylated at the end of a chain

(Dimethiconol according to the CTFA nomenclature) and from a cyclic polydimethylsiloxane (Cyclomethicone according to the CTFA nomenclature), such as the product Q2 1401 sold by the company Dow Corning; 2) mixtures formed from a polydimethylsiloxane gum with a cyclic silicone, such as the product SF 1214 Silicone Fluid from General Electric, which is an SE 30 gum of molecular weight = 500,000 is dissolved in SF 1202 Silicone Fluid (decamethylcyclopentasiloxane);

3) mixtures of two PDMSs of different viscosity, in particular of a PDMS gum and of a PDMS oil, such as the products SF 1236 and CF 1241 from General Electric;

(v) silicone resins; preferably crosslinked siloxane systems containing R2Si02/2, RSi03/2 and Si4/2 units in which R represents a hydrocarbon group containing 1 to 6 carbon atoms or a phenyl group. Among these resins, mention may be made of the product sold under the name Dow Corning 593; (vi) organomodified polyorganosiloxanes; i.e. silicones as defined above, comprising in their general structure one or more organofunctional groups directly linked to the siloxane chain or linked via a hydrocarbonbased radical; mention is made, for example, of silicones comprising: a) polyethylenoxy and/or polypropylenoxy groups optionally comprising alkyl groups, such as the product known as dimethicone copolyol, sold by the company Dow Corning under the name DC 1248, and alkyl (C12) methicone copolyol sold by the company Dow Corning under the name Q2 5200; b) (per)fluoro groups such as trifluoroalkyl groups, such as, for example, those sold by the company General Electric under the names FF.150 FLUOROSILICONE FLUID; c) hydroxyacylamino groups, such as those described in European patent application EP-A- 0 342 834, and in particular the silicone sold by the company Dow Corning under the name Q2-8413; d) thiol groups, such as the silicones X 2-836 from Dow Corning or GP 72A and GP 71 from Genesee; e) substituted or unsubstituted amine groups, such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company Genesee, or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amine groups are, in particular, C1 -C4 aminoalkyi or amino (C1 -C4) alkylamino (C1 -C4)alkyl groups. The silicones known as amodimethicone and

trimethylsilylamodimethicone according to the CTFA name (1997) are used more particularly; f) carboxylate groups, such as the products described in European patent EP 186 507 from Chisso Corporation; g) hydroxyl groups, such as the polyorganosiloxanes containing a hydroxyalkyl function, described in patent application FR-A-2 589 476; h) alkoxy groups containing at least 12 carbon atoms, such as the product SILICONE COPOLYMER F 755 from SWS Silicones; i) acyloxyalkyl groups containing at least 12 carbon atoms, such as, for example, the polyorganosiloxanes described in patent application FR-A-2 641 185; j) quaternary ammonium groups, such as in the product ABIL K 32701 from the company Goldschmidt; k) amphoteric or betaine groups, such as in the product sold by the company Goldschmidt under the name ABIL B 9950;

I) bisulfite groups, such as in the products sold by the company Goldschmidt under the names ABIL S 201 and ABIL S 255;

(vii) block copolymers containing a linear polysiloxane-polyalkylene block as repeating unit; the preparation of such block copolymers used in the context of the present invention is described in European patent application EP 0 492 657 A1 , the teaching of which is included by way of reference in the present description;

(viii) grafted silicone polymers, containing a non-silicone organic skeleton, consisting of a main organic chain formed from organic monomers containing no silicone, onto which is grafted, within the said chain as well as, optionally, on at least one of its ends, at least one polysiloxane macromonomer; in particular those chosen more preferably from those described in U.S. Pat. Nos. 4 963 935, 4 728 571 and 4 972 037 and patent applications EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578, the teachings of which are included in their entirety in the present description by way of non-limiting references;

(ix) grafted silicone polymers, containing a polysiloxane skeleton grafted with non-silicone organic monomers, comprising a main polysiloxane chain onto which is grafted, within the said chain as well as, optionally, on at least one of its ends, at least one organic

macromonomer containing no silicone; examples of such polymers, and the particular method for preparing them, are described in particular in patent applications EP-A-0 582 152, WO 93/23009 and WO 95/03776, the teachings of which are included in their entirety in the present description by way of non-limiting references; (x) or mixtures thereof.

The polyorganosiloxanes preferably used according to the invention are non-volatile polyorganopolysiloxanes and preferably polydimethylsiloxane oils or gums that are optionally aminated, arylated or alkylarylated.

Copending U.S. Serial No. 12/286,260 herein incorporated entirely by reference describes a modified silicone. The present conditioning polymer may be used in combination with the therein taught silicone derivatives as an effective deposition aid in personal care

compositions.

The polyorganosiloxanes are used in the compositions of the invention in proportions of between 0.01 % and 20% by weight and preferably between 0.1 and 10% by weight, relative to the total weight of the personal care composition.

Non-silicone Conditioning Agents

Compositions according to the present invention may comprise a dispersed, non-volatile, water-insoluble oily non-silicone conditioning agent.

Suitable oily or fatty materials are selected from hydrocarbon oils, fatty esters and mixtures thereof.

Straight chain hydrocarbon oils may for example contain from about 12 to about 30 carbon atoms. Also suitable are branched chain hydrocarbon oils will preferably contain from about 12 to about 42 carbon atoms. Also suitable are polymeric hydrocarbons of alkenyl monomers, such as C₂-C₆ alkenyl monomers.

Specific examples of suitable hydrocarbon oils include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, and mixtures thereof. Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used. Another suitable material is polyisobutylene .

Suitable fatty esters are characterised by having at least 10 carbon atoms, and include esters with hydrocarbyl chains derived from fatty acids or alcohols, Monocarboxylic acid esters include esters of alcohols and/or acids of the formula R COOR in which R* and R independently denote alkyl or alkenyl radicals and the sum of carbon atoms in R^f and R is at least 10, preferably at least 20. Di- and trialkyl and alkenyl esters of carboxylic acids can also be used. The viscosity of the conditioning oil itself (not the emulsion or the final hair conditioning composition) is from 350 to 10,000,000 mrr^Asec^"1 at 25°C.

The oily or fatty material is suitably present at a level of from 0.05 to 20, preferably from 0.2 to 10, more preferably from about 0.5 to 5 percent by weight of the composition.

Humectants and Moisturizers The compositions of the present invention can contain one or more humectant or moisturizing materials. A variety of these materials can be employed and each can be present at a level of from about 0.1 % to about 20%, more preferably from about 1 % to about 10% and most preferably from about 2% to about 5%. These materials include urea;

guanidine; glycolic acid and glycolate salts (e.g. ammonium and quaternary alkyl ammonium); lactic acid and lactate salts (e.g. ammonium and quaternary alkyl ammonium); aloe vera in any of its variety of forms (e.g., aloe vera gel); polyhydroxy alcohols such as sorbitol glycerol, hexanetriol, propylene glycol, butylene glycol, hexylene glycol and the like; polyethylene glycols; sugars and starches; sugar and starch derivatives (e.g., alkoxylated glucose); hyaluronic acid; lactamide monoethanolamine; acetamide monoethanolamine; and mixtures thereof. Preferred humectants and moisturizers are glycerol, butylene glycol, hexylene glycol, and mixtures thereof.

Detersive Surfactants

These conditioning polymers of the invention are particularly compatible with detersive anionic surfactant-containing products such as those used in shampoos or personal cleansing products, generally providing clear formulations without the loss of conditioning properties described above but are also compatible with cationic, nonionic, zwitterionic or amphoteric surfactants.

Suitable anionic detersive surfactant components for use in the shampoo composition herein include those which are known for use in hair care or other personal care cleansing compositions. The concentration of the anionic detersive surfactant component in the shampoo composition should be sufficient to provide the desired cleaning and lather performance, and generally for example in the range from about 5% to about 50%, from about 8% to about 30%, from about 10% to about 25% and from about 12% to about 18%, by weight of the composition.

Preferred anionic surfactants suitable for use in the shampoo compositions are the alkyl and alkyl ether sulfates. These materials have the respective formulae ROS0₃M and

RO(C₂H₄0)_xS0₃- M, wherein R is alkyl or alkenyl of from about 8 to about 18 carbon atoms, x is an integer having a value of from 1 to 10, and M is a cation such as ammonium, alkanolamines, such as triethanolamine, monovalent metals, such as sodium and potassium, and polyvalent metal cations, such as magnesium, and calcium.

R typically has from about 8 to about 18 carbon atoms, from about 10 to about 16 carbon atoms, from about 12 to about 14 carbon atoms, in both the alkyl and alkyl ether sulfates. The alkyl ether sulfates are typically made as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms. The alcohols can be synthetic or they can be derived from fats, e.g., coconut oil, palm kernel oil, tallow. Lauryl alcohol and straight chain alcohols derived from coconut oil or palm kernel oil are preferred. Such alcohols are reacted with between about 0 and about 10, about 2 to about 5, about 3, molar proportions of ethylene oxide, and the resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.

Other suitable anionic detersive surfactants are the water-soluble salts of organic, sulfuric acid reaction products conforming to the formula [R₁--SO₃-M] where Ri is a straight or branched chain, saturated, aliphatic hydrocarbon radical having from about 8 to about 24, about 10 to about 18, carbon atoms; and M is a cation described hereinbefore.

Still other suitable anionic detersive surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil or palm kernel oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil or palm kernel oil.

Typical specific anionic detersive surfactants for use in the personal cleansing compositions include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, and combinations thereof.

Suitable amphoteric or zwitterionic detersive surfactants may be used in the personal cleansing compositions and herein include those which are known for use in hair care or skin care cleansing composition, and which contain a group that is anionic at the pH of the cosmetic (such as a shampoo) composition. Concentration of such amphoteric detersive surfactants range for example from about 0.5% to about 20%, from about 1 % to about 10%, by weight of the composition. Amphoteric detersive surfactants suitable for use in the personal cleaning compositions are well known in the art, and include those surfactants broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group such as carboxy, sulfonate, sulfate, phosphate, or phosphonate.

Zwitterionic detersive surfactants suitable for use in personal cleaning composition are well known in the art, and include those surfactants broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group such as carboxy, sulfonate, sulfate, phosphate or phosphonate. Zwitterionics such as betaines are also envisioned.

The personal cleaning compositions of the present invention may further comprise additional surfactants for use in combination with the anionic detersive surfactant component described hereinbefore. Suitable optional surfactants include nonionic surfactants, cationic surfactants, and combinations thereof. Any such surfactant known in the art for use in hair or personal care products may be used, provided that the optional additional surfactant is also chemically and physically compatible with the essential components of the personal cleaning composition, or does not otherwise unduly impair product performance, aesthetics or stability. The concentration of the optional additional surfactants in the personal cleaning composition may vary with the cleansing or lather performance desired, the optional surfactant selected, the desired product concentration, the presence of other components in the composition, and other factors well known in the art. Non limiting examples of other anionic, zwitterionic, amphoteric or optional additional surfactants suitable for use in the personal cleansing or shampoo compositions are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co. which descriptions are incorporated herein by reference.

Benefit agents Benefit agents may be combined with the inventive ter-polymer and optionally include conditioning agents such as hydrocarbon oils, fatty esters, silicones, fatty amines, fatty amine oxides and fatty quaternaries. Further benefit agents possible may also include such ingredients as sunscreens, anti dandruff agents, proteins, minerals, herbal extracts, pediculocides, vitamins and UV absorbers.

Optional Ingredients

Further, it is common for personal care preparations to contain suspending agents, viscosity modifiers, dyes, nonvolatile solvents or diluents (water soluble and insoluble), pearlescent aids, foam boosters, additional surfactants or nonionic cosurfactants, pH adjusting agents, perfumes, preservatives, chelants, skin active agents, minerals, herbal/fruit/food extracts, sphingolipids derivatives or synthetical derivative, and clay.

Anti-dandruff agents are of particular interest as cationic polymers are well known as aids for depostion of anti-drandruff agents such as pyridinethione salts. For example, U.S.

Publication Application Nos. 2008/0206355 teaches cationic homopolymers in combination pyrithione. Thus the compositions of the present invention may also contain an anti-dandruff agent.

Suitable, non-limiting examples of anti-dandruff particulates include: pyridinethione salts, azoles, selenium sulfide, particulate sulfur, and mixtures thereof. Preferred are

pyridinethione salts. Such anti-dandruff particulate should be physically and chemically compatible with the essential components of the composition, and should not otherwise unduly impair product stability, aesthetics or performance.

Pyridinethione anti-dandruff particulates, especially 1-hydroxy-2-pyridinethione salts, are highly preferred particulate anti-dandruff agents for use in compositions of the present invention. The concentration of pyridinethione anti-dandruff particulate typically ranges from about 0.1 % to about 4%, by weight of the composition, preferably from about 0.1 % to about

3%, more preferably from about 0.3% to about 2%. Preferred pyridinethione salts include those formed from heavy metals such as zinc, tin, cadmium, magnesium, aluminum and zirconium, preferably zinc, more preferably the zinc salt of 1-hydroxy-2-pyridinethione

(known as "zinc pyridinethione" or "ZPT"), more preferably 1-hydroxy-2-pyridinethione salts in platelet particle form, wherein the particles have an average size of up to about 20 microns, preferably up to about 5 microns, more preferably up to about 2.5 microns. Salts formed from other cations, such as sodium, may also be suitable.

The personal care or personal cleansing compositions containing the conditioning polymer may additionally contain further polymers. The further polymer may for example, be:

- homopolymer of polyacrylamide of molecular weight ranging from about 1 ,000,000 to about 30,000,000, about 2,000,000 to about 8,000,000 or about 2,000,000 to about 5,000,000.

- a cationic copolymer different than the inventive ter-polymer. For example, the cationic copolymer may be a copolymer of acrylamide and cationic monomers such as

(meth)acryloyloxyethyl-N,N,N-trimethylammonium chloride, -(meth)acryloyloxyethyl-N-ethyl- Ν,Ν-dimethylammonium monoethyl sulfate, (meth)acryloyloxyethyl-N,N,N-triethylammonium monoethyl sulfate, -(meth)acryloylaminopropyl-N,N,N-trimethylammonium chloride, (meth)acryloylaminopropyl-N-ethyl-N,N-dimethylammonium monoethyl sulfate,

(meth)acryloylaminopropyl-N,N-diethyl-N-methylammonium chloride or

(meth)acryloylaminopropyl-N,N-diethyl-N-methylammonium monomethyl sulfate or mixtures thereof.

The second cationic copolymer will typically contain from 0.1 to about 25 weight percent, 4 to about 20 or about 5 or about 20 weight percent cationic monomer based on the total weight of the copolymer.

Preparation of the Conditioning Polymer

The conditioning polymers can be prepared in the conventional manner, e.g., by mass or solution polymerization. The polymerization may take place in an aqueous, solvent or aqueous-solvent mixed environment but it is preferred that the reaction be carried out in a substantially aqueous environment. Possible solvents are DMSO, THF, DMF, ethyl, propyl, butyl, acetate, benzene, toluene, xylene, N-butanol, isobutanol, isopropanol, MEK, MIBK, acetone, etc.

The polymerization is typically carried out in the absence of oxygen. The monomers may be polymerized using a radical reaction, by addition of peroxides or azo initiators.

The initiator may generally comprises one or more polymerization initiators. Such polymerization initiators are generally known and usually are of the azo or peroxide type. Useful azo initiators are for example 2,2-azobis-(N,N'-dimethylene-isobutyramidine) dihydrochloride, 2,2'-azobis -(2-amidinopropane) dihydrochloride (V-50), 4,4'-azobis-(4- cyanopentane-carboxylic acid), 2,2'-Azobis[2-(5-methyl-2-imidazolin-2- yl)propane]dihydrochloride; 2,2'-Azobis[N-(2-carboxyethyl)-2- methylpropionamidine]tetrahydrate; 2,2'-Azobis[2-(3,4,5,6-tetrahydropyrimidin-2- yl)propane]dihydrochloride; and 2,2'-Azobis{2-methyl-N[2-(1-hydroxybuthyl)]propionamide.

Useful peroxide initiators are for example tert.-butylhydroperoxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, or redox catalyst in combination with reducing agents such as iron(ll)-ammonium sulfate, ascorbic acid, sodium methyl sulfinate, disodium disulfite, sodium hydrogen sulfite, sodium phosphite, potassium phosphite or hydrogen phosphite, sodium hypophosphite or potassium hypophosphite. These initiators can be used either alone or in combination with one another. Thus the rate of peroxide decomposition can be adapted, for example, to the particular polymerization temperature selected. Preferred redox catalysts are those from one or several peroxides in combination with a reducing agent.

Other suitable radical initiators may include salts or derivatives of percarbonic acid (such as isopropyl percarbonate) and salts or derivatives of perphosphonic acid. The above- mentioned radical initiators may be used alone or in combination with various reducing agents to form redox initiator systems.

Initiators such as ammonium persulfate are ideal as this initiator is highly water soluble.

The polymerization initiators are generally used in amounts ranging from 0.1 to 5% by weight and preferably greater than 1.0% by weight, based on the net amount of monomers employed. Most preferably the initiator is used at a concentration of greater than about 1.2% by weight to about 5%. The initially charged polymerization initiators may comprise mixtures of various types such as combinations of water soluble azo initiator(s) and peroxide initiator(s) or combinations of different initiators exhibiting different half life properties. For example two different initiators may be initially charged, the first initiator is active at the step ii) temperature and the second initiator is active at the step iii) temperature.

The polymerization time of the conditioning polymer depends on the temperature and the desired final product properties but is preferably within the range of from 0.5 to 10 hours at temperatures ranging from about 50 °C to about 190 °C. The polymerization can be carried out continuously, discontinuously or semicontinuously. If it is preferred to obtain a polymer chain having random distribution of monomers, all of the monomers together will be preferably added to the reaction mixture. This may be done in one portion or metered over time to control the rate of the reaction.

On the basis of the reactivity of the monomers, which is known, a skilled artisan can control the polymerization so as to obtain the desired distribution.

EXAMPLES

Abbreviations

APTAC - acrylamidopropyl-N,N,N-trimethylammonium chloride MAPTAC -methacrylamidopropyl-N,N,N-trimethylammonium chloride DADMAC - diallydimethylammonium chloride

TMAEMC - Trimethyl ammonium ethyl methacrylate chloride MAGA - Glycoside acrylate

AA -Acrylic Acid

SDA- Sorbitol diacrylate

Polyquaternium -10 is quaternized carboxyethylcellulose

MBA - methylene bis acrylamide (crosslinking agent) Determination of average molecular weight is carried out by size exclusion gel permeation chromatograph or the more simple viscosity determaintions via K-values.

The di(meth)acrylate of sorbitol is formed by reacting a (meth)acrylic acid or (meth)acrylate with sorbitol.

The acrylate of methyl-. alpha. -D-glucopyranoside ester is obtained according to U.S Patent Number 7,767,425.

Synthesis of Conditioning Polymer

The reactor is charged with water, the chelating agent and a partial charge of the monomers. The reactor is purged with nitrogen and heated to 90 °C

The initial charge is followed by:

Feed 1 contains the water soluble monomers (ie. APTAC, DADMAC, AA, sugar

(meth)acrylate) additional water and crosslinker if used;

Feeds 2 and 3 each comprise initiator solutions in different concentrations. Feed 1 is begun and added over a 2 hour period.

Feed 3 is added after addition of feeds 1-2 are complete and the reaction is stirred for an additional 30 minutes.

Once the reaction is complete, a nitrogen purge is carried out with cool down to room temperature. Then steam distillation for 1 hour.

Example 1 Amount in grams Substance Wt. % of total reaction

Initial Reactor 5.33 APTAC 0.96

Charge

2.65 MAGA 0.48

1.00 EDTA 0.18

200.00 Dl Water 36.12

Feed 1 101.33 APTAC 18.30

50.33 MAGA 9.09

6.00 MBA 1.08

100.00 Dl Water 18.06

Feed 2 (optional 4.00 Isobutyvinyl ether 0.72 feed)

50.00 Ethyl acetate 9.03

Feed 3 30.00 Ammonium 5.42

persulfate

Feed 4 3.00 Ammonium 0.54

persulfate

All polymers are formed analogously to example 1 but the ratios of components and monomer components are varied.

Conditioning Polymers Formed According to Example 1

2 APTAC/SDA/AA (50/30/20) No 127.000

3 APTAC/MAGA (90/10) No 109.000

4 APTAC/SDA (90/10) No NA

5 MAPTAC/MAGA (70/30) No 62.000

Yes (300 ppm and 1000

6 MAPTAC/MAGA (90/10) ppm MBA) 290,000

7 TMAEMC/MAGA (90/10) No 270,000

8 APTAC/MAGA (70/30) No 100,000

Yes (300 ppm and 1000

9 APTAC/MAGA (90/10) ppm MBA) 1 10,000

1. Represents weight percent of monomer in final conditioning polymer. The weight percent basis is on the formed conditioning polymer.

The various conditioning polymers are added to a 2-in-1 shampoo formulation at 0.5 wt. % with and without silicone ingredient as in Table 1 and 2. Table 1. Shampoo with Conditioning Polymer

Ingredient Weight Percent

Sodium laureth-2 sulfate 12.0

Cocamidopropyl betaine 3.0

Conditioning polymer (Examples 1 -15 in Table 3) 0.5 (active polymer)

Sodium chloride 1.2

25% Citric acid solution pH 5.5 ± 0.5

Water q.s.

Table 2. Shampoo with Conditioning Polymer and Silicone

Ingredient Weight Percent

Sodium laureth-2 sulfate 12.0

Cocamidopropyl betaine 3.0

Conditioning polymer (Examples 16-22 in Table 3) 0.5 (active polymer)

Silicone DC-1664 (Dow Chemical) 1.0 (active silicone) Sodium chloride 1.2

25% Citric acid solution pH 5.5 ± 0.5

Water q.s.

Conditioning performance was evaluated by measuring the reduction in work or energy associated with combing wet, one cycle bleached European hair (Table 3). One gram hair swatches were washed with 12% sodium laureth-2 sulfate prior to testing, and then soaked in 35^°C tap water for 30 minutes (Tables 1 and 2).

Combing force was measured by a Zwicki Z2.5 Dynamic Testing Machine (Zwick Roell, Germany) before and after treatment with the test product. The treatment protocol consisted of two cycles of applying 0.25 gram product per gram hair for five minutes followed by a one minute rinse with 35^°C tap water. The percent change in combing work was then calculated as the ratio of the difference between post and pre-treatment combing work to pretreatment combing work as shown below. As such, negative values indicate a reduction in combing work due to the treatment (conditioning) and positive values indicate an increase in combing work due to the treatment.

Change in combing work (%) = (Treated - Untreated) ^χ 100

Untreated

The data indicate that the polymers are capable of improving the manageability of hair both alone and in combination with silicone. The inventive polymers provide comparable conditioning alone and in combination with silicone; therefore, they may be viewed as silicone replacements. This is not true of Polyquaternium-10 and similar materials whose main conditioning mechanism is via silicone (or other benefit agent) deposition rather than standalone conditioning.

Table 3. Effect of Conditioning Polymers

Body Wash

Moisturizing Hand Lotion

Isopropyl Myristate 4.0

Conditioning Polymer (examples 2-8) 0.25 (active polymer)

Tween 60 2.6

PEG-20 Methyl Glucose 1.50

White Ceresine Wax 0.4

Triethanolamine 0.20

Arlacel 60 3.0

Water Qs

Liquid Soap

Ingredient Wt %

Sodium laureth sulfate 10-15.00

Cocamidoproyl Betaine 15-20

Silicone DC-1664 (Dow) 2.0

Sunflower Seed Oil 2.0

Conditioning Polymer (examples -8) 0.25 (active polymer)

Sorbitan monolaurate 1-3

Hydantoin (preservative) 0.2

Fragrance 1.0 Styrene Acrylate (opacifier) 0.4

Water Qs

Shower Gel

Ingredient Wt %

Sodium Lauroamphoacetate 7

Sodium Laureth Sulfate 14

Cetyl Acetate and Acetylated Lanolin .5

Alcohol

Laurie acid 2.5-3.0

Sunflower Seed Oil 3.0

Vitamin E 1.0

Conditioning Polymer (examples 2-8) 0.25 (active polymer)

Cocamide Monoethanol amide 2

Guar Hydroxypropyl trimonium chloride 0.5

Glycerin 2

Hydantoin (preservative) 0.2

Fragrance 1.0

Titanium dioxide 0.2

Water Qs Rinse-off hair conditioner

Styling gel Ingredient Wt. %

VP/VA copolymer 7.0

Tetrahydroxypropylethyldiamine 0.9

Acrylates/C 10-30 alkyl acrylate crosspolymer 0.5

Conditioning polymer 5.0 (active polymer)

Propylene glycol 0.1

Preservative 0.1

Water q.s.

Claims

Claims

1. A keratin conditioning polymer formed from i.) a cationic monomer defined by formula (I) or formula (II)

(I) (ll)

in which: R and R² are independently hydrogen or methyl,

R³, R⁴ and R⁵ are independently linear or branched C Cao alkyl radicals,

X is NH, NR⁶ or oxygen,

R₆ is Ci-C₆ alkyl,

L is C_nH_2n, n is an integer from 1 to 5,

R⁷ and R⁸, independently of each other, represent a hydrogen atom or a linear or branched Ci -C₆ alkyl group,

R⁹ and R ⁰, independently of each other, represent an alkyl, hydroxyalkyi group wherein the alkyl group is a linear or branched d -C₆ chain, o and p are integers between 1 and 3; and

X^" represents a counterion; ii) an α, β ethylenically unsaturated sugar monomer; iii) optionally at least one anionic monomer or potentially anionic monomer selected from the group consisting of ethylenically unsaturated carboxylic acid and ethylenically unsaturated sulfonic acid containing monomers; and

(iv) optionally a crosslinking monomer.

2. The conditioning polymer according to claim 1 , wherein

R and R² are independently hydrogen or methyl, R³, R⁴ and R⁵ are C₁-C4 alkyl radicals, X is NH,

n is 3,

R⁷ and R⁸ are hydrogen or methyl, R⁹ and R¹⁰ are methyl or ethyl, especially methyl, o and p are l , and ii) is an α, β ethylenically unsaturated sugar monomer, wherein the sugar monomers are ester derivatives and the sugars of the esters are selected from the group consisting of monosaccharides and oligosaccharides in an optically pure form or as a stereoisomer mixture.

3. The conditioning polymer according to either claim 1 or 2, wherein the cationic monomer of i) is selected from the group consisting of (meth)acryloyloxyethyl-N,N,N- trimethylammonium chloride, (meth)acryloyloxyethyl-N-ethyl-N,N-dimethylammonium monoethyl sulfate, (meth)acryloyloxyethyl-N,N,N-triethylammonium monoethyl sulfate, (meth)acryloylaminopropyl-N,N,N-trimethylammonium chloride, (meth)acryloylaminopropyl- N-ethyl-N,N-dimethylammonium monoethyl sulfate, (meth)acryloylaminopropyl-N,N-diethyl- N-methylammonium chloride, (meth)acryloylaminopropyl-N,N-diethyl-N-methylammonium monomethyl sulfate and mixture thereof, preferably (meth)acryloylaminopropyl-N,N,N- trimethylammonium chloride, (meth)acryloylaminopropyl-N-ethyl-N,N-dimethylammonium monoethyl sulfate, (meth)acryloylaminopropyl-N,N-diethyl-N-methylammonium chloride, (meth)acryloylaminopropyl-N,N-diethyl-N-methylammonium monomethyl sulfate,

(meth)acryloyloxyethyl Ν,Ν,Ν-trimethylammonium chloride, (meth)acryloyloxyethyl-N-ethyl- Ν,Ν-dimethylammonium monoethyl sulfate, (meth)acryloyloxyethyl-N,N,N-triethylammonium monoethyl sulfate, (meth)acrylamidopropyl-N,N,N-trimethylammonium chloride,

(meth)acrylamidopropyl-N-ethyl-N,N-dimethylammonium monoethyl sulfate,

(meth)acrylamidopropyl-N,N-diethyl-N-methylammonium chloride, (meth)acrylamidopropyl- N,N-diethyl-N-methylammonium monomethyl sulfate, diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallydimethylammonlum sulfate, diallydimethylammonium phosphate, dimethyallydimethyammonium chloride,

diethylallyldimethylammonium chloride, diallyldi(beta-hydroxyethyl)ammonium chloride, diallyldiethylammonium chloride and mixtures thereof.

4. The conditioning polymer according to anyone of claims 1 to 3, wherein the unsaturated sugar monomer of component ii) is (meth)acrylate ester of C Cao-alkyl glycosides or (meth)acrylate esters of sorbitol.

5. The conditioning polymer according to any one of the preceding claims, wherein component iii) is an anionic monomer which is a compound of formula (VI):

(VI)

R₁₂ and R₁₃ are hydrogen, Ri4 is hydrogen, methyl or a COOM group,

M is hydrogen, a monovalent or divalent metal ion, ammonium or an organic ammonium ion.

6. The conditioning polymer according to any one of claims 1 to 5, wherein the molar ratio of the monomer units of components i) and iii) varies from 12:1 to 3: 1 , preferably 10:1 to 4: 1 in the formed polymer.

7. The conditioning polymer according to anyone of claims 1 to 6, wherein the conditioning polymer is crosslinked and the crosslinking agent/monomer ranges from about 0.00002 to about 2% by weight based on the total weight of the conditioning polymer.

8. The conditioning polymer according to anyone of claims 1 to 7, wherein the the cationic monomer i) is at least about 30 to about 96 wt. %, about 40 to about 95 wt. %, or about 45 to about 92 weight % of the formed conditioning polymer.

9. The conditioning polymer according to anyone of claims 1-8, wherein the sugar monomer of component ii) is at least about 5 to about 50 weight %, about 7 to about 40, and about 8 to about 30 or about 20 weight % based on the total weight of the conditioning polymer.

10. The conditioning polymer according to anyone of claims 1 to 9, wherein the conditioning polymer has a weight average molecular weight of 10,000 to about 18,000,000, about

25,000 to about 5,000,000, typically about 35,000 to about 1 ,800,000, from about 15,000 to about 1 ,000,000 or about 10,000 or about 20,000 to about 800,000. For example, about 100,000 to about 1 ,000,000 or about 120,000 to about 800,000 are envisioned.

1 1. The conditioning polymer according to anyone of claims 1 to 10, wherein the

conditioning polymer is formed from components i), ii), optionally (iii) and optionally (iv) and a monomer of a component v) selected from the group consisting of monoethylenically unsaturated imidazoles and their alkyl derivatives and quaternized products, esters and basic esters of a, β-unsaturated C₃-C₆ acids, basic amides of a, β-unsaturated C₃-C₆ acids, substituted and unsubstituted amides of a, β-unsaturated C₃-C₆ acids, diallyamine and derivative of diallyamines (other than formula (II)), vinylpyridine and their quaternized derivatives, vinyl ethers and C^-C_e hydroxy substituted alkyl (meth)acrylates, for example of particular interest are vinyl ethers and Ci-C₆ hydroxy substituted alkyl (meth)acrylates .

12. The conditioning polymer according to anyone of claims 1 to 1 1 , wherein the conditioning polymer is formed form components i), ii), iii), optionally component iv) and a monomer of a component v) selected from the group consisting of vinyl ethers.

13. A personal care composition comprising the conditioning polymer according to any one of claims 1 to 12, wherein the conditioning polymer is dispersed or solublilized in a cosmetically acceptable vehicle other than water.

14. The personal care composition according to claim 13 which further comprises at least one surfactant chosen from anionic, amphoteric, nonionic and zwitterionic surfactants.

15. The personal care composition according to claims 13 or 14 is a personal cleansing composition.

16. The personal cleansing composition according to claim 15, wherein the cleansing composition is a 2-in-1 shampoo, a bodywash, a facial wash, a bubble bath, soapless cleansers, liquid and bar soap; a shower gel, xfoliating shower gel; a milk bath; moist towelletes; bath effervescent tablets (e.g., bubble bath); a bath/shower gel or a shower cream and further comprises a detersive anionic surfactant from about 5% to about 50%, from about 8% to about 30%, from about 10% to about 25% or about 12% to about 18%, by weight of the composition.

17. The personal care composition according to any one of claims 12 to 16, wherein the personal care composition is a hand lotion, body lotion, a body spray, mist or gel, hair conditioning rinse, shaving cream, gel, foam or soap, an after-shave, after-shave moisturizer, a hand and nail cream or a depilatory cream.

18. A process for conditioning a keratinous substrate comprising the steps of applying an effective amount of a composition t comprising the conditioning polymer according to anyone of claims 1 to 12 to the keratinous substrate.

19. The process according to claim 18, wherein the keratinous substrate is human or animal skin, hair or nails.

20. A method for enhancing the deposition of silicone to skin, hair or nails comprising the steps of topically applying a composition comprising a) the conditioning polymer according to anyone of claims 1 to 12, and b) at least one silicone compound .

21. A personal care composition comprising the conditioning polymer according to any one of claims 1-12 and a second cationic polymer, wherein the second polymer is different than the conditioning polymer.

22. The personal care composition according to claim 15, wherein the cleansing

composition is a 2-in-1 shampoo further comprises a detersive anionic surfactant and the detersive surfactant is about 2% to about 50% by weight of the total weight of the 2-in-1 shampoo.