MXPA99010532A - Personal care compositions containing graft polymers - Google Patents

Abstract

Disclosed are personal care compositions comprising from about 0.1%to about 15%by weight of a graft polymer and from about 0.1%to about 99.9%by weight of a liquid carrier, wherein the graft polymer is made in accordance with the following process steps:(a) reacting copolymerizable monomers to form an organic polymeric backbone having a weight average molecular weight of from about 15,000 grams/mole to about 200, 000 grams/mole and a plurality of organic halide moieties covalantly bonded to and pendant from the polymeric backbone;and then (b) reacting copolymerizable monomers with the organic halide moeities of the polymeric backbone by atom transfer free radical polymerization in the presence of a catalytic amount of a Cu(I) salt or other transition metal species to form a plurality of polymeric side chains covalently bonded to and pendant from the polymeric backbone and having a weight average molecular weight of from about 500 grams/mole to about 200,000 grams/mole, wherein the polymeric back bone and the plurality of polymeric side chains form hydrophilic and hydrophobic graft polymers suitable for use in personal care compositions and having a weight average molecular weight of from about 16,000 grams/mole to about 10,000,000 grams/mole.

Description

COMPOSITIONS FOR PERSONAL CARE CONTAINING GRAFT POLYMERS TECHNICAL FIELD The present invention relates to an improved method for making graft, hydrophobic and hydrophilic polymers suitable for use in personal care compositions, and to hair styling compositions and other personal care compositions containing graft polymers.

BACKGROUND OF THE INVENTION Personal care compositions such as hair sprays, styling shampoos, cosmetics, skin care products and the like frequently contain film-forming polymers for various reasons. These film-forming polymers are especially useful in hair care compositions to provide the composition with a performance to style the hair. Film-forming polymers for use in these compositions include linear or graft-containing organic or silicone-containing copolymers, which contain various monomers in an alternating, random, block or homopolymer configuration.

Graft copolymers are well known for use as film-forming polymers in personal care and hair care compositions. These graft copolymers typically comprise a polymer structure and one or more macromonomers grafted to the structure, wherein the physical and chemical attributes such as the values of vitreous transition temperature (Tg), water solubility, and so on, are selected. so that the polymer structure and grafts of the macromonomer provide the desired film-forming properties and other chemical or physical properties of the copolymers in a personal care composition. Graft copolymers are especially versatile in that the polymer structure and the bound macromonomer grafts may have selected or different chemical or physical properties, which collectively provide the optimum performance formulation or profile for the proposed personal care composition, which will be used. The synthesis of the graft copolymers, however, is typically more difficult than the synthesis of many copolymers, especially linear polymers. Unlike the synthesis of linear polymers, the synthesis of graft copolymers typically comprises a separate polymerization step comprising the preparation of a macromonomer containing a reactive terminal group, the copolymerization of the macromonomer with a copolymerizable ethylenically unsaturated monomer, and then the completion of this last step of copolymerization to obtain the desired graft polymers. It has now been found that graft, hydrophobic and hydrophilic polymers can now be made by more effective and simpler synthesis methods, and that these new synthesis methods result in the formation of graft polymers that when applied to hair or hair Another surface forms a polymeric film or is welded having an improved adhesive or cohesive strength. These polymers are very useful when used as film-forming polymers in personal care compositions, especially when they are used as film-forming or combing polymers in hair styling compositions. The graft polymers in these hair styling compositions provide improved styling and / or conditioning performance, and are especially effective in providing improved styling durability and improved hair feel. Therefore, it is an object of the present invention to provide an improved method for making graft polymers, and to further provide a method for making graft polymers for use in personal care compositions, and further to provide a method for which comprises few steps of synthesis than other conventional methods for making graft polymers. It is yet another object of the present invention to provide hair styling compositions and other personal care compositions containing the graft polymers made according to the synthesis method of the present invention., wherein the graft polymers have a low polydispersity, and wherein the compositions contain low concentrations or reduced concentrations of polymeric contaminants such as ungrafted polymeric structure and / or unbound polymeric side chains or grafts.

SUMMARY OF THE INVENTION The personal care compositions of the present invention comprising from about 0.1% to about 15% by weight of a graft polymer, and from about 0.1% to about 99.9% by weight of a liquid carrier, in wherein the graft polymer is made according to the process comprising the steps of: (a) reacting copolymerizable monomers to form a polymeric structure Organic P928 having a weight-weighted molecular weight of from about 15,000 grams / mole to about 9,800,000 grams / mole and a plurality of halide, organic halides covalently bound to, and pendent of the polymeric structure; and then (b) reacting copolymerizable monomers with the organic halide portions of the polymer structure by free radical polymerization with transfer of atoms in the presence of a catalytic amount of a transition metal species, preferably a Cu salt ( I) and complex turn preferably to a ligand of suitable, to form a plurality of polymeric side chains covalently attached to, and pendants of the polymer structure having a weight-weighted molecular weight of from about 500 grams / mole to about 2000,000 grams / mole , wherein the polymeric structure and the plurality of polymeric side chains form graft polymers suitable for use in personal care compositions and having a weight-weighted molecular weight of from about 16,000 grams / mole to about 10,000,000 grams / mole. It has been found that the process limitations described above allow a more effective, simpler synthesis of the graft polymers using fewer process steps than conventional synthesis methods, and P928 also allows the synthesis of graft polymers without depending on the use of copolymerizable macromonomers, or a step of synthesis to make these macromonomers. It has also been found that personal care compositions containing these graft polymers contain low or reduced concentrations of polymeric contaminants such as non-graft polymeric structure and / or polymer grafts, unbound or side chains, wherein the graft polymers also they have a low or reduced polydispersity.

DETAILED DESCRIPTION OF THE INVENTION The process limitations of the present invention comprise two reaction steps, keys. In a first reaction step, the copolymerizable monomers are reacted together to form a polymer structure containing halide, organic halides covalently bound to, and pendant from the structure. In a second reaction step, subsequent, the polymer structure is reacted with copolymerizable monomers by polymerization with atom transfer radicals in the presence of a catalytic amount of a Cu (I) salt or other transition metal species, back preferably complete a suitable ligand. Each of these two process steps, P928, are described in detail later in this. The terms "hydrophilic" or "water soluble" as used herein, unless otherwise specified, are used interchangeably and refer to polymers (or salt forms of these polymers produced by neutralization or quaternization) of acidic or basic groups) or other materials which are soluble in distilled water, ethanol, N-propanol, isopropanol or combinations thereof, at 25 ° C and at a concentration of 0.2% by weight of this polymer or other material. The terms "hydrophobic" and "water insoluble" as used herein, unless otherwise specified, are used interchangeably and refer to the other polymers or materials that are not hydrophilic as defined in I presented. The method of the present invention may comprise, consist of, or consist essentially of, the essential elements or limitations of the invention described herein, as well as of any additional or optional elements or limitations described herein. All molecular weights as used herein, unless otherwise specified, are weight average molecular weights expressed as grams / mole. All percentages, parts and ratios are by weight of the total composition referred to, unless otherwise specified. All of these weights in that they correspond to the ingredients listed are based on the active level, and therefore, do not include solvents or by-products that can be included in commercially available materials, unless otherwise specified.

Synthesis Method The personal care compositions of the present invention comprise graft polymers made in accordance with the process limitations herein, a process comprising two essential reaction steps. In the first reaction step, the polymer structure of the graft polymers herein are prepared first. This is achieved by reacting copolymerizable monomers to form a polymeric structure containing a plurality of halide, organic halides covalently attached to, and pendent of, the polymeric structure, and including those polymers that generally conform to the formula: ÍA] atB) b C wherein "A" is a monomeric unit having a portion of halide, "C" linked organic, which is covalently linked, and pendant of the monomeric unit "A", and "B" is a monomeric unit which is copolymerizable with the monomeric unit "A", "a" is a positive integer having a value of 2 or greater, preferably a value of from about 2 to about 30 and "b" is a positive integer having a value of at least about 4 , preferably a value from about 10 to about 2000. The organic halide portion "C" includes any carbon structure, branched or cyclic (aromatic or other), linear, either substituted or unsubstituted, which also contains a halogen atom ( Fl, Cl, Br or I). In the first reaction step of the synthesis method herein, the monomer unit "A" with the halide, organic, "C" portion is preferably selected from the group of allyl monomers, vinyl acetate monomers, monomers of acid halide, styryl monomers, or combination thereof, and is most preferably selected from the monomeric units characterized by the following general structure (Groups IV): (?) (II) CH, -CH-O-C-X (III) v) (V) CH, = CH-O-R4-X wherein R is methyl or hydrogen, X is a halogen atom (Fl, Cl, Br, I); R1 and R2 are each selected in a dependent manner from methyl, hydrogen or methoxy; and R is an alkyl group having from 1 to 8 carbon atoms. The first reaction step of the process herein comprises any polymerization technique, conventional or otherwise known, such as ionic polymerization, Ziegler-Natta, free radical, group transfer or gradual growth, or combinations of the same. The first reaction step preferably comprises conventional free radical polymerization techniques. Once the first reaction is completed, or has progressed to the desired degree, the first reaction step is terminated or allowed to terminate depending on the selected polymerization method, the degree or extent of the desired polymerization, the reactivity of the selected monomer units. for use in the reaction, and so on. Any conventional or otherwise known technique of termination appropriate for the selected reaction and the reaction conditions can be used. For example, and most typically, after polymerization of the polymer structure by free radical polymerization, the reaction mixture is heated to about 120 ° C for about 15 minutes to consume or react any remaining free radical initiator, and subsequently the reaction mixture is cooled or allowed to cool to room temperature to allow the reaction to self-complete before the addition of the ingredients to initiate the second reaction step.

P928 In the second reaction step of the process of the present invention, the polymer structure described hereinabove is reacted with one or more copolymerizable monomers in the presence of a catalytic amount of a transition metal salt, preferably a salt of Cu (I) and preferably complete round to a suitable ligand. In this reaction step, the organic halide portions act as initiators in the presence of the copolymerizable monomers and the catalyst, resulting in the grafting of the monomers into the polymer structure by free radical polymerization with atom transfer, the monomers forming a plurality of chains lateral, polymeric covalently attached to, and hanging from the structure. Polymeric side chains are formed in the polymeric structure without the need to use copolymerizable macromonomers to achieve the pendant, polymeric graft chains. The catalyst for the second reaction step is a transition metal salt, preferably a Cu (I) salt, such as Cu (I) halide salts (Cl, Fl, Br, I) and which becomes complex preferably to a ligand which is suitable for solubilizing the Cu (I) salt in the reaction mixture, wherein the reaction mixture of the second reaction step comprises dissolved monomer or P928 partially dissolved, unreacted monomers, solvent and catalyst. Preferred ligands for use in the solubilization of the Cu (I) salts in the reaction mixture are aprotic bidendates such as diphosphates, 2, 2'-bipyridyl substituted with alkyl of 1 to 20 carbon atoms, and combinations of the same. More preferred is 2, 2'-bipyridyl rendered complex to a halide salt of Cu (I), especially Cu (I) Cl. Other conventional or otherwise known ligands may be used herein with the proviso that they do not substantially and unduly damage the polymerization reaction of the process herein, some examples of which are described in "The Use of Living Radical Polymerization" Synthesize Graft Copolymers "Dept. of Chemistry, Carnegie Mellon University. Pittsburgh, Pennsylvania, Simion Cocoa and Krzysztof Matyjaszews i, Polymer Preprints, Vol. 37 (1 °), pg. 571-572, 1996. "Alternating Copolymers of Methyl Acrylate with Isobutene and Isobutyl Vinyl Ether using ATRP" Dept. of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania; Timothy e. Patten et al. Polymer Preprints, Vol. 37 (1), pg. 573-574, 1996., "Radical Polymerization yielding Polymers with Mw / Mn ~ 1.05 by Homogeneous Atom Transfer Radical Polymerization" Carnegie Mellon University, Pittsburgh, Pennsylvania; TEA. Patten et al. Polymer Preprints, Vol.

P928 37 (1), pg. 575-576, 1996. "" The Synthesis of End functional Polymers by Living Radical Polymerization "Carnegie Mellon University, Pittsburgh, Pennsylvania, Y. Nakagawa et al., Polymer Preprints, Vol. 37 (1), pp. 577-578, 1996, publications that are incorporated herein by reference.

Graft Polymers The process limitations of the present invention are especially useful for making film-forming, hydrophobic or hydrophilic polymers, suitable for use in personal care compositions such as hair styling compositions. Graft polymers made according to these process limitations typically have a low or reduced polydispersity and contain reduced concentrations of polymeric contaminants such as polymeric, non-grafted structure and / or unbound polymer grafts or side chains once the two are finished. reaction steps of the synthesis. The graft polymers made according to the synthesis method herein are characterized by a polymeric, hydrophilic or hydrophobic structure with a plurality of hydrophobic or hydrophobic polymeric side chains, covalently attached to, and pendant from the P928 polymer structure, wherein the polymer structure represents from about 50% to about 99%, and preferably from about 60% to about 98%, more preferably from about 75% to about 95%. By weight of the graft polymer, and the plurality of side chains, polymeric represents from about 1% to about 50%, preferably from about 2% to about 40%, more preferably from about 5%, to about 25% , by weight of the graft polymer. The polymer side chains in the graft polymers have a weight-average molecular weight of at least about 500 grams / mol, preferably from about 1,000 grams / mol to about 200,000 grams / mol, more preferably from about 1,500 grams / mol to about 30,000 grams / mol, more preferably from about 3,000 grams / mol to about 25,000 grams / mol. These polymeric side chains may comprise monomer units arranged in an alternating, random, block or homopolymer configuration, and each of the polymer side chains may comprise the same or different monomers, arranged in the same or different P928 configuration - The graft polymers made according to the synthesis method herein have a weighted molecular weight of about 16, 000 grams / mole to about 10,000,000 grams / mole, preferably less than about 5,000,000 grams / mole, more preferably less than about 3,000,000. More preferred are the weighted molecular weights from about 50,000 grams / mole to about 2,000,000 grams / mole, more preferably from about 75,000 grams / mole to about 1,000,000 grams / mole, more preferably from about 75,000 grams / mole to about 750,000. grams / mol. The graft polymers made according to the synthesis method herein can have an individual Tg value and preferably are copolymers having at least two immiscible, distinct phases, wherein the polymer side chains are closely associated with each other and they exist in one phase and the polymer structure of the copolymer remains in a separate second phase. One consequence of this phase immiscibility is that the thermal separation between the included Tg values is very large, then the copolymers exhibit two glass transition temperatures.

P928 distinct, specifically a value of Tg for the structure and a value of Tg for the side chain. The copolymers can also exhibit a third glass transition temperature corresponding to any of the optional polysiloxane side chains in the graft copolymers. Whether this third value of Tg is observable depends on a number of factors including the percent silicone in the polymer, the number of polysiloxane side chains in the copolymer, the thermal separation between each of these values of Tg comprised, and other physical factors. The graft polymers made according to the synthesis method herein also preferably have a polydispersity of less than about 10, preferably less than about 5, even more preferably less than about 4. Suitable monomers for the use in the synthesis method herein may be hydrophilic or hydrophobic. In this context, the term "hydrophobic monomers" are those copolymerizable monomers which, when reacted together, form hydrophobic or insoluble homopolymers in water, and the term "hydrophilic monomers" refers to those copolymerizable monomers which, when reacted together, form P928 hydrophilic or water soluble homopolymers. The monomers suitable for use herein must be copolymerizable and have the necessary characteristics defined herein for use in the synthesis method. These copolymerizable monomers are preferably ethylenically unsaturated monomers, more preferably, copolymerizable vinyl monomers. The term "copolymerizable" as used herein means that a material can be reacted with another material in accordance with the first and / or second polymerization reaction steps of the synthesis method herein, whichever is appropriate. The term "ethylenically unsaturated" as used herein refers to monomers containing at least one polymerizable carbon-carbon double bond (which may be mono-, di-, tri-, or tetra-substituted). These copolymerizable monomers include the organic halogenide-containing copolymerizable monomers, described hereinabove, and also include the monomer units which are reacted with the organic halide-containing monomers in the first reaction step of the synthesis method, and also include the monomer units that are reacted with a polymer structure in the second step of P928 reaction of the synthesis method. The copolymerizable monomers for use in the first and second reaction steps of the synthesis method may be the same, or may include combinations of two of the different but copolymerizable monomers, including combinations of hydrophilic and hydrophobic monomers, combinations of copolymerizable monomers having glass transition temperatures different, but selected (Tg), combinations of polar and non-polar monomers, and so on, or combinations of two or more copolymerizable monomers from an individual chemical class or having otherwise similar physical or chemical characteristics . The graft polymers, therefore, may comprise the same or different monomer units and therefore, may be classified as homopolymers, copolymers, terpolymers and so on. The non-limiting classes of the monomers useful herein include monomers selected from the group consisting of unsaturated alcohols, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated anhydrides, alcohol esters of unsaturated monocarboxylic acids, alcohol esters of dicarboxylic acids, unsaturated, esters of alcohol of unsaturated anhydrides, esters alkoxylated of acids P928 monocarboxylic, unsaturated, alkoxylated esters of dicarboxylic acids, unsaturated esters, alkoxylated esters of unsaturated anhydrides, aminoalkyl esters of unsaturated monocarboxylic acids, aminoalkyl esters of unsaturated dicarboxylic acids, aminoalkyl ethers of unsaturated anhydrides, unsaturated monocarboxylic acid amides, unsaturated dicarboxylic acid amides, amides of unsaturated anhydrides, unsaturated monocarboxylic acid salts, unsaturated dicarboxylic acid salts, unsaturated anhydride salts, unsaturated hydrocarbons, unsaturated heterocycles and mixtures thereof. Representative examples of these monomers include acrylic acid (produced by hydrolysis of trimethylsilyl acrylate), methacrylic acid (produced by hydrolysis of trimethylsilyl methacrylate), trimethylsilyl acrylate, trimethylsilyl methacrylate, acrylamide, acrylate alcohols produced by hydrolysis of protected alcohol with trimethylsilyl, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride, vinyl pyrrolidone, vinyl ethers (such as methyl vinyl ether), maleimides, vinyl pyridine, vinyl imidazole, other polar vinyl heterocyclics, styrene sulfonate, allyl alcohol, vinyl alcohol (such as that produced by the hydrolysis of vinyl acetate after the P928 polymerization), vinyl caprolactam, methacrylic acid esters of alcohols of 1 to 18 carbon atoms, such as methanol, ethanol, methoxy-ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1 propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl- l-pentanol, 3-methyl-l-pentanol, t-butanol (2-methyl-2-propanol), cyclohexanol, neodecanol, 2-ethyl-l-butanol, 3-heptanol, benzyl alcohol, 2-octanol, 6- methyl-l-h-ethanol, 2-ethyl-1-hexanol, 3, 5-dimethyl-1-hexanol, 3, 5, 5-tri-methyl-1-hexanol, 1-decanol, 1-dodecanol, 1-hexadecanol, 1-octa-decanol, and the like, alcohols having from about 1-18 carbon atoms with the number of carbon atoms which is preferably from about 1-12; dicyclopentenyl acrylate; 4-biphenyl acrylate, pentachlorophenyl acrylate; 3,5-dimethyladamantyl acrylate, 3,5-dimethyladamantyl methacrylate, 4-methoxycarbonylphenyl methacrylate, trimethylsilyl acrylate, trimethylsilyl methacrylate, styrene; show us substituted with alkyl including alpha-methylstyrene and t-butylstyrene; vinyl ethers, including vinyl acetate, vinyl neononanoate, vinyl pivalate and vinyl propionate; vinyl chloride; vinylidene chloride; vinyl toluene; vinyl ethers of aleguilo, cgue include vinyl ether of P928 isobutyl and s-butyl vinyl ether; butadiene, cyclohexadiene, bicycloheptadiene; 2,3-dicarboxylmethyl-l, 6-hexadiene, ethylene; propylene, indene, norbornylene; β-pinene; a-pinene; salts of acid and amines listed above, and combinations thereof. The quaternized monomers can be quaternized either before or after copolymerization with other monomers of the graft copolymer. Preferred monomers include acrylic acid (produced by hydrolysis of trimethylsilyl acrylate), methacrylic acid (produced by hydrolysis of trimethylsilyl methacrylate), vinyl pyrrolidone, esters of acrylic or methacrylic acid of alcohols of 1 to 18 carbon atoms, acrylate of trimethylsilyl, trimethylsilyl methacrylate, styrene, alpha-methylstyrene, t-butylstyrene, vinyl acetate, vinyl propionate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, n-butyl methacrylate, isobutyl methacrylate, t-acrylate, butyl, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, and mixtures thereof. Suitable copolymerizable monomers described herein are proposed to include those copolymerizable monomers, correspondingly substituted or unsubstituted with one or more substituent groups, provided that these groups do not damage P928 unduly polymerization reactions of the synthesis method. Examples of suitable substituent groups include, without limitation, alkyl, aryl, carboxyl, halo groups and combinations thereof. Specific examples of hydrophilic graft polymers made according to the process limitations of the present invention include, but are not limited to: Poly (2-methoxyethyl acrylate-co-methacrylic acid-tert-butyl-co-acrylate-co-4-chloromethyl-styrene) -graft-poly (styrene-co-methacrylic acid); , molecular weight of 150,000 grams / mol, composition: 2-methoxyethyl acrylate (31.6%), methacrylic acid (22%), tert-butyl acrylate (28%) 4-chloromethyl-styrene (0.4%), styrene (18) %).

Poly (2-methoxyethyl acrylate-co-methacrylic acid-tert-butyl co-acrylate-co-4-chloromethyl-styrene) -graft- [poly (styrene-acid-co-methacrylic); poly (di-ethylsiloxane)]; molecular weight of 150,000 grams / mol, Composition: 2-methoxyethyl acrylate (26.6%) methacrylic acid (22%), tert-butyl acrylate (28%) 4-chloromethyl-styrene (0.4%), poly (dimethylsiloxane) macromonomer ) (molecular weight 10,000 grams / mol) (5%), styrene (18).

P928 Poly (t-butyl acrylate-2-methoxyethyl acrylate-co-acrylic acid-co-4-chloromethyl-styrene) -in-ortho-poly (iso-butyl methacrylate-co-methacrylic acid); 80,000 grams / mol; Composition: t-butyl acrylate (22%), 2-methoxyethyl acrylate (31%), acrylic acid (18%), 4-chloromethyl-styrene (1%), isobutyl methacrylate (15%), methacrylic acid ( 13%).

Poly (vinyl acetate-co-vinyl-pyrollidone-co-chlorovinyl acetate) -graft-poly (styrene-acid-co-methacrylic); molecular weight 120,000 grams / mol; Composition: vinyl acetate (40%), vinyl pyrrolidone (39%), chlorovinyl acetate (1%), isobutyl methacrylate (10%), dimethylaminoethyl methacrylate (10%).

The hydrophilic graft polymers made according to the synthesis method herein may comprise acid functional groups, such as carboxyl groups, and are usually used in the at least partially neutralized form to promote the solubility or dispersibility of the polymer. In addition, the use of the neutralized form helps the hair styling compositions to be removed from the hair by shampooing. The degree of this neutralization varies from P928 about 10% to 100%, preferably from about 20% to about 90%, even more preferably from about 40% to about 85%, of neutralization of the acid functional groups of the graft polymer. The neutralization of hydrophilic graft polymers containing acid functional groups can be achieved by any functional or other known technique to affect this neutralization by using an organic or inorganic base material. Metal bases are particularly useful for this purpose. Suitable basic neutralizers include, but are not limited to, ammonium hydroxides, alkali metal hydroxides or alkaline earth metal hydroxide, preferably potassium hydroxide and sodium hydroxide. Examples of other suitable neutralizing agents include, without limitation, amines or aminoalcohols such as 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-ethyl-1,3-propanediol (AEPD). ), 2-amino-2-methyl-1-propanol (AMP); 2-amino-1-butanol (AB), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), monoisopropanolamine (MIPA), diisopropanolamine (DIPA), triisopropanolamine (TIPA) and dimethyl-stearamine (DMS) and combinations of the same. Preferred are amines and metal bases.

P928 The neutralization of hydrophilic polymers containing basic functionalities, for example, amino groups, are also preferable at least partially neutralized with an organic or inorganic acid, for example hydrogen chloride. Neutralization can be achieved by any conventional or other known technique to achieve this neutralization. The preferred degree of neutralization is the same as that described for the neutralization of acid functionalities. The solubility for any neutralized graft polymer made according to the synthesis method herein should be terminated only after the desired acidic or basic neutralization. Specific examples of the hydrophobic graft polymers made according to the process limitations of the present invention include, but are not limited to: Poly (2-ethylhexyl-co-chloromethyl-styrene-tert-butyl-co-methacrylate) -poly (n-butyl acrylate) acrylate; molecular weight 100,000 grams / mol; Composition: tert-butyl acrylate (54%), 2-ethylhexyl methacrylate (10%), 4-chloromethyl-styrene (6%), n-butyl acrylate (30%).

P928 Poly (t-butyl acrylate-2-methoxyethyl-co-4-chloromethyl-styrene-acrylate) -graft-poly (styrene) acrylate; molecular weight 100,000 grams / mol; Composition: t-butyl acrylate (25%); 2-methoxyethyl acrylate (50%), 4-chloromethyl-styrene (2%); Styrene (23%) Poly (vinyl acetate-co-vinyl-pyrrolidone-chlorovinyl co-acetate) -graft-poly (2-ethylhexyl acrylate; molecular weight 120,000 grams / mol; Composition: vinyl acetate (40%), vinyl-pyrrolidone ( 10%), chlorovinyl acetate (5%), 2-ethylhexyl acrylate (45%).

Optional Silicone Grafts The process limitations of the present invention may further comprise the copolymerization of silicone macromonomers with other copolymerizable monomers described herein during the first reaction step of the synthesis method of the present invention., to thereby form a polymer structure comprising one or more side chains, grafted with silicone and a plurality of halide, organic, attached and pendant portions of the polymer structure. The polymeric structure, grafted with silicone, is then subjected to a second reaction step of the process as described hereinabove, thereby producing graft copolymers - comprising a plurality of polymeric side chains that do not contain silicone in combination with one or more macromonomer grafts containing silicone. The optional silicone macromonomer is grafted to the polymer structure or polymerized therein by any conventional or otherwise known method for making the silicone graft copolymers. More typically, these polymers are formed from the random copolymerization of vinyl or other copolymerizable monomer units, some or all of which have bound organic halide portions, and polysiloxane containing macromonomer units containing a polymeric portion and a portion of copolymerizable vinyl with the monomer units. At the end of the polymerization, the polymeric siloxane portion of the macromonomeric unit forms the graft copolymer polysiloxane side chains. The other copolymerizable monomer units and the portion of the macromonomer units form the polymer structure. The copolymerizable monomer and the polysiloxane-containing macromonomer can be selected from a wide variety of structures as long as the copolymer has P928 the necessary properties described herein, which include having the organic halide portions, which act as initiators in a second reaction step of the synthesis method herein. Examples of related silicone graft copolymers, and methods for making them, are described in detail in U.S. Patent No. 4,693,935, Mazurek, issued September 15, 1987, U.S. Patent No. 4,728,571. , of Clemens et al., granted on March 1, 1988, both of which are incorporated herein by reference. Additional silicone-grafted polymers are also disclosed in EPO application 90307528.1, published as EPO application 0 408 311 A2 on January 11, 1991, by Hayama, et al., U.S. Patent No. 5,061,481, issued in US Pat. October 29, 1991, Suzuki et al., U.S. Patent No. 5,106,609 to Bolich et al., Issued April 21, 1992, U.S. Patent No. 5,100,658, to Bolich et al. March 31, 1992, U.S. Patent No. 5,100,657, to Ansher-Hackson, et al., Issued March 31, 1992, U.S. Patent No. 5,104,646, to Bolich, et al., Issued the April 14, 1992, U.S. Patent Application Serial No. 07 / 758,319, Bolich et al., Filed August 27, 1991, and U.S. Patent Application Serial No. 07 / 758,320, by Torgerson et al., Filed August 27, 1991, the disclosures of which are incorporated herein by reference . The silicone graft copolymers made according to the synthesis methods herein can comprise from zero to about 50%, preferably from about 2% to about 40%, and more preferably from about 10% to about 30%. %, of macromonomeric polysiloxane units by weight of the graft polymer. The macromonomeric polysiloxane units are copolymerizable with the other monomers selected for use in the first reaction step of the synthesis method, the polysiloxane macromonomers having a vinyl portion or another copolymerizable for the reaction with the selected, different monomer. Either an individual type of macromonomeric polysiloxane unit or combinations of two or more siloxane macromonomer units can be used in the first reaction step. In this context, the term "copolymerizable" means that the polysiloxane macromonomers can be reacted with the other selected monomers, including monomers containing organic halide, P928 according to the first reaction step of the synthesis method in the present, which results in the polymeric structure necessary for use in the second reaction step of the synthesis method in the present. The polysiloxane macromonomers which are useful herein contain a polymer portion and a copolymerizable portion which is preferably an ethylenically unsaturated portion. Typically, the preferred macromonomers are those that are capped at the end with the vinyl portion. By "topping off at the end", as used herein, is meant that the vinyl portion is in a terminal position of the macromonomer or about the same. The polysiloxane macromonomers can be synthesized using a variety of conventional or other familiar synthetic techniques familiar to the polymer chemist of ordinary skill in the art. Additionally, these polysiloxane macromonomers can be synthesized by starting from commercially available polymers. Typically, the weight average molecular weight of the polysiloxane macromonomer to be used in the first reaction step is from about 1,000 grams / mole to about 50,000 grams / mole. _ _L ° _§L polysiloxane macromonomers suitable for P928 use in the present include those that conform to the general formula: X (Y) Yes (R), Z wherein X is a vinyl group copolymerizable with the vinyl monomer units; And it's a divalent link group; each R is independently selected from the group consisting of hydrogen, hydroxyl, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkylamino of 2 to 6 carbon atoms, styryl, phenyl, alkyl of 1 to 6 carbon atoms or phenyl substituted with alkoxy; Z is a polymeric monovalent siloxane portion having a number average molecular weight of at least about 1000 and which is essentially non-reactive under polymerization conditions; n is an integer that has a value of 0 or 1; and m is an integer having a value from 1 to 3. The polysiloxane macromonomer has a weight-weighted molecular weight of from about 1,000 grams / mole to about 50,000 grams / mole, preferably from about 5,000 grams / mole to about 30,000 grams / mol, preferably from about 8,000 grams / mol to about 25,000 grams / mol. Preferably, the macromonomer of P928 polysiloxane has a formula selected from the following formulas I-III (I) (II) X-CHj- (CH3) s-Si (R ') 3.m-Zn (III) 0 or X-C-0- < CH2) q- (0) p-S¡ (R!) 3-m2m where s is an integer that has a value from 0 to 6; preferably 0, 1 or 2, more preferably 0 or 1; m is an integer having a value of 1 to 3, preferably 1; p is an integer that has a value of 0 or 1; q is an integer having a value from 2 to 6, each R1 is independently selected from the group consisting of hydrogen, hydroxyl, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkylamino of 2 to 6 carbon atoms, phenyl, phenyl substituted by alkoxy or alkyl of 1 to 6 carbon atoms, preferably alkyl of 1 to 6 carbon atoms, or phenyl substituted by alkyl or alkoxy of 1 to 6 carbon atoms, most preferred alkyl of 1 to P928 6 carbon atoms, even more preferably methyl, R2 is selected from the group consisting of alkyl of 1 to 6 carbon atoms or phenyl substituted with alkyl of 1 to 6 carbon atoms, preferably methyl; n is an integer having a value from 0 to 4, preferably 0 or 1, more preferably 0; X is R3-: H = I * wherein R3 is hydrogen or -COOH, preferably R3 is hydrogen; R4 is hydrogen, methyl or -CH2C00H, preferably R4 is methyl; Z is wherein R5, R6 and R7, are independently selected from hydrogen, hydroxyl, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkylamino of 2 to 6 carbon atoms, styryl, phenyl, phenyl substituted with alkoxy or alkoxy of 1 to 6 carbon atoms, hydrogen or hydroxyl, preferably Rs, R6 and R7 are alkyls of 1 to 6 carbon atoms; more preferably methyl; and r is an integer that has a P928 value from about 14 to about 700, preferably about 60 to about 400, more preferably about 100 to about 170.

Compositions for Personal Care Graft polymers made according to the methods herein are especially useful when used as film-forming polymers in personal care compositions. These compositions comprise the graft polymers made in accordance with the methods herein in combination with a suitable liquid carrier for dissolving or dispersing, preferably dissolving, the graft polymer in the personal care composition. The personal care compositions of the present invention include skin care compositions, shampoo styling or conditioning compositions, cosmetic compositions, or other similar compositions, many of which will additionally comprise one or more optional ingredients as described below at the moment. Preferred are hair care compositions such as conditioners, shampoos for styling and / or conditioning, hair sprays, and creams, P928 tonics, gels or lotions to stylize. The film-forming graft polymer for use in these compositions and which is made according to the synthesis method herein, provides the compositions with conditioning performance for the hair or skin or performance for styling the hair. The personal care compositions may be formulated as solids or liquids, single or multiple phase systems, emulsions, dispersions, solutions, gels, suspensions, or other formulation suitable for application to hair or skin. The personal care compositions of the present invention comprise the graft polymers made in accordance with the methods herein, at concentrations effective to provide the desired film-forming properties. These concentrations generally range from about 0.1% to about 15%, more preferably from about 0.5% to about 15%, still more preferably from about 0.5% to about 8%, even more preferably from about 1% up to about 8%, by weight of the personal care composition, wherein the concentration of the liquid carrier varies in general from about 85% to about 99.9%, so P928 preferably from about 92% to about 99.5%, still more preferably from about 92% to about 99%, by weight of the personal care composition. Compositions for personal care, - especially when formulated as hair styling compositions, they can be distributed as sprayed or sprayed liquids from aerosol or pump spray cans. The aerosol compositions comprise one or more conventional propellants or otherwise known aerosol propellants. Suitable propellants include any liquefiable gas that is known or otherwise effective for use in this manner, examples of which include propellants of volatile hydrocarbons such as liquefied lower hydrocarbons having 3 or 4 carbon atoms such as propane, butane, isobutane, or combinations thereof. Other suitable propellants include hydrofluorocarbons such as 1,2-difluoroethane, and other propellants such as dimethyl ether, nitrogen, carbon dioxide, nitrous oxide, atmospheric gas, and combinations thereof. Preferred are hydrocarbon propellants, particularly isobutane when used alone or in combination with other hydrocarbon propellants. The concentrations of the propellant must be sufficient to provide the distribution or application P928 desired composition for the personal care of the skin or hair, whose concentrations typically vary from about 10 to about 60%, preferably from about 15% to about 50%, by weight of the composition. Pressurized aerosol dispensing apparatuses can also be used when the propellant is separated from contact with the hair styling composition, an example of which would be a two-compartment container available from the American National Can Corp., with SEPRO trademark: The appropriate, different aerosol dispensing apparatuses are those characterized by the propeller which is compressed air that can be filled into the dispensing device, by means of a pump or equivalent device before use. described in U.S. Patent No. 4,077,441, U.S. Patent No. 4,077,441 and U.S. Patent Application Serial No. 07 / 839,648, the disclosures of which are hereby incorporated by reference. spray, non-aerosol pump, conventional, or atomizers are also suitable for use in the present.

A) Polymeric compositions of inert, hydrophilic P928 The personal care compositions of the present invention preferably comprise a hydrophilic graft polymer made in accordance with the methods of synthesis herein, and which is used in combination with a miscible or water-soluble or hydrophilic liquid carrier, suitable for solubilizing or dispersing the hydrophilic graft polymer in the personal care composition. These preferred compositions are especially useful when used as hair styling or hair spray compositions. Hydrophilic liquid carriers suitable for use herein include, without limitation, water, ethanol, n-propanol, isopropanol, and combinations thereof, preferably a combination of an alcohol and water wherein the water content of the composition ranges from about 0.5% to about 99%, preferably from about 0.5% to about 50%, by weight of the composition, and the alcohol content ranges from about 0.5% to about 99%, preferably from about 50 % up to about 95%, by weight of the composition. The hydrophilic graft polymers preferably have at least two different vitreous transition temperatures (Tg), the first of which is associated P928 with the polymeric structure and the second of which is associated with a plurality of polymeric side chains attached thereto. The polymer structure preferably has a Tg value of less than about 35 ° C, more preferably less than about 25 ° C, still more preferably less than about 10 ° C, wherein the plurality of polymer side chains have a Tg value preferably greater than about 50 ° C, more preferably greater than about 60 ° C, even more preferably greater than about 70 ° C. Other suitable hydrophilic graft polymers made in accordance with the methods herein include those having a Tg value for the polymer structure of more than about 30 ° C, more preferably more than about 40 ° C, and even more preferably more than about 50 ° C, wherein the plurality of polymeric side chains has a value of Tg preferably of less than about 10 ° C, more preferably less than about 0 ° C, even more preferably less than about -20 ° C. These personal care compositions, especially when formulated as hair spray compositions, preferably contain reduced concentrations of organic compounds, P928 volatile, including volatile organic solvents. In this context, volatile organic compounds or solvents are those organic compounds or solvents that contain less than 12 carbon atoms or have a vapor pressure greater than 0.1 mm of mercury. The water concentrations in these preferred concentrations are typically at least about 10% by weight of the composition, preferably from about 10% to about 50% by weight of the composition, wherein the concentration of the volatile organic compound or solvent is typically less than about 90%, preferably from about 20% to about 80%, more preferably from about 40% to about 70%, even more preferably from about 40% to about 60%, by weight of the composition. _______ Hydrophobic Graft Polymer Compositions Another embodiment of the personal care compositions of the present invention are those comprising a hydrophobic graft polymer made in accordance with the synthesis methods herein, in combination with a liquid carrier, insoluble in water or hydrophobe suitable to solubilize or disperse or otherwise carry the hydrophobic graft polymer in the P928 composition for personal care. These modalities are especially useful when used as conditioning compositions for hair or skin, some non-limiting examples of which include skin care compositions, conditioning shampoos, and hair conditioners. Hydrophobic liquid carriers, suitable for graft polymers, hydrophobic include volatile, hydrophobic liquids such as branched chain, volatile hydrocarbons, silicones and combinations thereof. The concentration of these liquid carriers in the composition preferably ranges from about 0.1% to about 75%, more preferably from about 0.2% to about 25%, and even more preferably from about 0.5% to about 15%, by weight of the composition, wherein the weight ratio of the hydrophobic graft polymer to the hydrophobic liquid carrier is generally from about 1: 100 to about 5: 1, preferably from about 1:10 to about 1: 1, in the form more preferably from about 1: 8 to about 2: 3. The hydrophobic liquid carrier e's preferably a volatile liquid that exhibits a significant vapor pressure at ambient conditions (eg, a P928 atmosphere 25 ° C). In this context, the term "volatile" refers to solvents or liquid carriers having a boiling point at an atmosphere of 260 ° C or less, preferably 250 ° C or less, preferably 230 ° C or less, more preferably 225 ° C or less. In addition, the boiling point of the hydrophobic liquid carrier will generally be at least about 50 ° C, preferably at least about 100 ° C. The term "non-volatile" as used in this context refers to solvents or liquid carriers having a boiling point at an atmosphere of more than 260 ° C. The hydrophobic graft polymer is preferably soluble in the selected hydrophobic liquid carrier. In this context, the term "soluble" refers to the solubility of the hydrophobic graft polymer in the hydrophobic liquid carrier at 25 ° C at a concentration of 0.1%, preferably 1%, more preferably 5%, in most preferred form even at 15%, by weight of the liquid, hydrophobic carrier. Preferred liquid, hydrophobic carriers include hydrophobic, volatile, branched-chain hydrocarbons, preferably saturated hydrocarbons containing from about 10 to about 16, preferably from about 12 to about 16, more preferably from P928 about 12 to about 14 carbon atoms. Examples of these preferred branched chain hydrocarbons include isoparaffins of the above chain sizes. Isoparaffins are commercially available from Exxon Chemical Co.; examples include Isopar ™ H and K (isoparaffins of 11 to 12 carbon atoms), and Isopar ™ L (isoparaffins of 11 to 13 carbon atoms). Other suitable branched chain hydrocarbons are isododecane and isohexadecane. Isododecane is preferred and commercially available from Preperse, Inc. (South Plainfield, NJ, USA) as Permethyl ™ 99A. Preferred hydrophobic silicone carriers include volatile, hydrophobic siloxanes such as phenyl-pentamethyl-disiloxane, phenylethyl-pentamethyl-disiloxane, hexamethyl-disiloxane, methoxypropyl-heptamethyl-cyclotetrasiloxane, chloropropyl-pentamethyl-disiloxane, hydroxypropyl-pentamethyl-disiloxane, cyclomethicones. , including octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane), and mixtures thereof. Preferred hydrophobic silicone solvents are cyclomethicones, preferably octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane. It is understood that hydrophobic liquid carriers can be used in combination with liquid carriers, hydrophilic in the care compositions P928 personnel, and that the hydrophobic graft polymers can also be used in combination with the hydrophilic injurious polymers in the personal care composition. These combinations are suitable for use in the personal care composition with the condition that they are physically and chemically compatible with the ingredients selected in the composition and do not substantially or unduly damage the performance of the product.

Optional Ingredients The personal care compositions described herein may additionally comprise one or more optional ingredients known or otherwise effective for use in compositions for styling hair or other personal care compositions. These optional ingredients may be used to improve or otherwise modify the aesthetics, performance or stability of the compositions to style the hair. The concentrations of these optional ingredients will vary with the type of material added and their proposed performance, but will typically and collectively vary from about 0.005% to about 50%, more typically from about 0.05% to about 30% by weight of the composition.

P928 The plasticizers for the graft copolymer are especially useful in the personal care compositions herein. Suitable plasticizers include any known or otherwise effective plasticizer suitable for use in hair care or personal care compositions, non-limiting examples of which include glycerin, diisobutyl adipate, butyl stearate, propylene glycol, citrates of tri-C2-C8, including triethyl citrate and tri-propyl, -butyl, -pentyl, etc., analogs of triethyl citrate. Triethyl citrate is preferred. Plasticizers are typically used at levels from about 0.01% to about 10%, by weight of the composition, preferably from about 0.05% to about 3%, more preferably from about 0.05% to about 1%. Preferably, the weight ratio of the graft polymer to the plasticizer is from about 1: 1 to about 40: 1, preferably from about 2: 1 to about 30: 1, more preferably from about 3: 1. up to about 25: 1. Other optional ingredients include an effective amount of a resistance modifier system Ionic p928, not active on the surface to reduce the viscosity of the personal care composition, especially when formulated as a hair spray composition. Preferred compositions vary from at least about 0.01%, by weight of the composition. The upper limit depends on the maximum amount of the ionic strength modifiers which may be present in the compositions herein such that the hair fixing resins remain solubilized or dispersed. As will be understood by those skilled in the art, as the ionic strength of the composition increases, the resin will eventually fall out of the solution, or otherwise it will no longer remain solubilized and dispersed in the hydrophilic liquid carrier. The upper limit of the level of the ionic strength modifier system will vary depending on the particular ionic strength modifiers, liquid carrier, resin, and other ingredients present in the composition. Thus, for example, the maximum amount of ion concentration modifiers that can be used will tend to be lower for compositions with liquid carriers containing less water, as compared to compositions with more water. The concentrations of the ionic strength modifier, optional, will typically vary from P928 about 0.01% to about 4%, preferably from about 0.01% to about 2%, more preferably from about 0.01% to about 0.1%, by weight of the composition. The optional ionic resistance modifier system comprises a mixture of cations and monomeric anions. The anions of the ionic resistance modifier system herein are not surface active, ie they do not have a significantly reduced surface tension. For purposes of the present, a non-active surface must mean that the ions, which at a concentration of 0.5% aqueous solution, reduce the surface tension by no more than 5.0 dynes / cm2. In general, the ions the ionic strength modifier system of the present will be characterized as having at most four or less carbon atoms per charge, preferably two or less carbon atoms, in an organic aliphatic chain or hetero chain. Straight or branched chain. The optional ionic strength modifier system comprises monomeric ions of the type which are products of the acid-base ratios. In this way, the basic ions and acids OH "and H + are not part of the ionic strength modifier system of the present, P928 although they may be present in the composition. The ions of the present are incorporated into the composition in a form such that a composition can exist as free ions, i.e. in dissociated form. It is not necessary that all the added ions exist in the composition as free ions, but must be at least partially soluble or dissociated from the composition. Ion resistance modifiers can be incorporated into hair styling compositions, for example, by the addition of soluble salts, or by the addition of mixtures of acids and bases, or by a concentration thereof. It is a necessary aspect of the invention that both the anions and the cations of the ionic strength modifier system are included in the composition. Non-limiting examples of the optional cations, suitable for use in the compositions are alkali metals, such as lithium, sodium, and potassium and alkaline earth metals, such as magnesium, calcium and strontium. The preferred of the divalent cations is magnesium. The preferred monovalent metal ions are lithium, sodium and potassium, more preferably sodium and potassium. Suitable means of addition to the compositions herein include, for example, addition as bases, for example, hydroxides, sodium hydroxide and potassium hydroxide, and salts that are soluble in the P928 liquid carrier, for example, salts of monomeric anions such as those described below. Other non-limiting examples of suitable cations include organic ions, such as quaternary ammonium ions and cationic amines, such as mono-, di-, and triethanolamines of ammonium, triethylamine, morpholine, in methyl propanol (AMP), aminoethyl propanediol, etc. Ammonium and amines are preferably provided in the form of salts, such as hydrochloride salts. Monomeric anions that can be used include halogen ions, such as chloride, fluoride, bromide and iodide, particularly chloride, sulfate, ethyl sulfate, methyl sulfate, cyclohexyl sulfamate, thiosulfate, toluene sulfonate, xylene sulfonate, citrate , nitrate, bicarbonate, adipate, succinate, saccharinate, benzoate, lactate, borate, isethionate, tartrate, and other monomeric anions that may exist in a dissociated form in the composition to stylize the hair. The anions can be added to the compositions of the present invention, for example, in the form of acids or salts that are at least partially soluble in the leguid carrier, for example, sodium and potassium salts of acetate, citrate, nitrate, chloride, sulfate, etc. Preferably, these salts are completely soluble in the vehicle.

P928 The use of optional ionic strength modifiers is especially useful in compositions with low volatile organic solvent content. Other optional ingredients include surfactants (which may be anionic, cationic, amphoteric, or zwitterionic and including surfactants, fluorinated and silicone copolyols), propellants, hair conditioning agents (eg, silicone fluids, fatty ethers, fatty alcohols, long chain hydrocarbons, cationic surfactants, etc.); emollients; lubricants and penetrants such as various lanolin compounds; protein hydrolysates and other protein derivatives; ethylene and polyoxyethylene-cholesterol adducts; dyes, colorants, bleaches, reducing agents or other dyes; pH adjusting agents; sun blockers; preservatives, thickening agents (for example, polymeric thickeners, xanthan gum); and perfume.

Method of Use The personal care compositions of the present invention are used in conventional ways to provide the desired benefit for personal care.

For compositions for styling hair or other hair spray, the composition is used in a manner Conventional P928 to provide the desired styling / hair setting benefits of the present invention, which typically comprises applying an effective amount of the composition to dry, lightly moistened, or wet hair before and / or after the hair is fixed to a desired type of hairstyle. The composition is then dried or allowed to dry on the applied surface. The term "effective amount" as used in this context means an amount of the composition for personal care or hair composition and styling sufficient to provide the desired benefit. In the case of hair spray compositions and other hair styling compositions, an effective amount of the composition is applied to the hair to provide the desired fixation and styling benefits considering the length and texture of the hair. In general, from about 0.5 g to about 30 g of the hair spray composition or other hair styling compositions are applied to the hair, depending on the particular formulation of the product, type of dispensing apparatus, hair length, type of style of the hair, and so on.

EXAMPLES The following non-limiting examples illustrate P928 the specific embodiments of the process limitations of the present invention, the graft polymers made according to these process limitations, and the hair styling compositions and other personal care compositions comprising these graft polymers. However, it is understood that various additions or modifications of the exemplified, specific embodiments may be made, without departing from the spirit and scope of the invention. It is proposed to cover all of these modifications within the scope of the present invention in the appended claims.

EXAMPLE 1 The hydrophilic graft polymers 1.1 and 1.2 described in the following example are prepared according to the process limitations of the present invention. The specific modalities of these process limitations are described for each of the hydrophilic graft polymers.

Graft Polymer 1.1 Poly (2-methoxyethyl acrylate-co-methacrylic acid-tert-butyl co-acrylate-co-4-chloromethyl-styrene) -graft-poly (styrene-co-methacrylic acid) In a bottom flask round, purged with argon, P928 equipped with mechanical stirrer and a reflux condenser is added butyl acetate (1L), trimethylsilyl methacrylate (18.4g, 0.116 mol), tert-butyl acrylate (27.2g, 0.212 mol), 2-methoxyethyl acrylate (31.4 g, 0.241 mol) and chloromethyl-styrene (0.4g, 0.003 mol). The solution is heated to 60 ° C, then initiated with AIBN (azobisisobutyronitrile) (Og, 0.006 mol) and allowed to undergo polymerization by free radicals for 10 hours. The resulting solution is then heated to 100 ° C and allowed to cool. When the solution reaches room temperature, trimethylsilyl methacrylate (22.Og, 0.139 mol), styrene (18.Og, 0.173 mol), 2,2'-dipyridyl (1.4g, 0.009 mol), and Cu (I) are added. ) CI (0.3g, 0.003 mol). The solution is then heated to 120 ° C with stirring for 6 hours. The solution is then cooled to room temperature and the catalyst is removed by vacuum filtration. The filtrate is diluted with acetone (200 ml) and water (10 ml) and stirred for 2 hours. The resulting solution is precipitated in hexanes and the graft polymer is collected and dried.

Graft Polymer 1.2 Poly (2-methoxyethyl acrylate-co-methacrylic acid-tert-butyl co-acrylate-co-4-chloromethyl-styrene) -grafting- [poly (styrene-co-methacrylic acid); cop- P928 (dimethylsiloxane)] In a round bottom flask, purged with argon, equipped with mechanical stirring and a reflux condenser, is added butyl acetate (1L), trimethylsilyl methacrylate (18.4g, 0.116 mol), tert-butyl acrylate. (27.2g, 0.212 mol), 2-methoxyethyl acrylate (24.6g, 0.203 mol), polydimethylsiloxane macromonomer (10,000 molecular weight) (available from Chisso Corp., Tokyo, Japan) (5g), and chloromethyl-styrene (0.4 g, 0.003 mol). The solution is heated to 60 ° C, then initiated with AIBN (1.00 g, 0.006 mol) and allowed to undergo polymerization by free radicals for 10 hours. The resulting solution is then heated to 100 ° C, then allowed to cool. When the solution reaches room temperature, trimethylsilyl methacrylate (22.Og, 0.139 mol), styrene (18.0g, 0.173 mol), 2, 2'-dipyridyl (1.4g, 0.009 mol), and Cu (I) are added. Cl (0.3g, 0.003 mol). The solution is heated to 120 ° C with stirring for 6 hours. The solution is then cooled to room temperature and the catalyst is removed by vacuum filtration. The filtrate is diluted with acetone (200 ml) and water (10 ml) and stirred for 2 hours. The resulting solution is stirred in hexane and the graft polymer is harvested and dried.

P928 EXAMPLE 2 The hydrophobic graft polymer 2.0 described in the following example is prepared according to the process limitations of the present invention. The specific embodiments of the process limitations are described for each of the hydrophobic graft polymers.

Graft Polymer 2.0 Poly (tert-butyl acrylate ______ ethylhexyl-co-c-oromethyl-styrene) -graft-poly (n-butyl acrylate) In a round bottom flask, purged with argon, equipped with mechanical stirring and a reflux condenser; butyl acetate (1L), tert-butyl acrylate (54g, 0.417 mol), 2-ethylhexyl methacrylate (10Og, 0.050 mol) and chloromethyl-styrene (6g, 0.039 mol) are added. The solution is heated to 60 ° C, then initiated with AIBN (0.6 g, 0.004 mol) and allowed to undergo polymerization by free radicals for 12 hours. The resulting solution is then heated to 100 ° C then allowed to cool. When the solution reaches room temperature, n-butyl acrylate (30g, 0.211 mol), 2, 2'-dipyridyl (18.3, g, 0.117 mol), and Cu (I) Cl (3.9g, 0.039 mol) are added. . The solution is heated to 120 ° C with stirring for 6 hours.

P928 The solution is then cooled to room temperature and the catalyst is removed via vacuum filtration. The filtrate is diluted with acetone (200 ml) and water (10 ml) and stirred for 2 hours. The resulting solution is precipitated in hexanes and the graft polymer is collected and dried.

EXAMPLES 3-10 The following Examples 3-10 depict non-aerosol hair spray modes of the compositions of the present invention.

E jes Rio. Component 3 6 7 10 (% by weight) Copolymer of 4 .00 5.00 6.00 4.00 graft 1.1 Copolymer of - 3.00 3.50 2.50 4.00 graft 1.2 Isododecano1 1 .00 1.0 2.0 Adipate of 0 .40 090 0.55 0.40 diisolbutyl Hydroxide of 0.96 1.20 1.44 1.20 1.35 sodium2 Hydroxide --- 1.21 1.00 0.70 potassium3 Perfume 0 .10 0.10 0.10 0.10 0.10 0.15 0.10 0.15 Benzoate of --- 0.10 0.10 0.10 sodium Ethanol4 76.54 71.95 81.56 71.25 79.40 69.26 78.00 55.00 Water c.b.p. c.b.p. c.b.p. c.b.p. c.b.p. c.b.p. c.b.p. c.b.p. 100 100 100 100 100 100 100 100 P928"TPERMETHYL 99A, from Presperse, Inc., South Plainfield, NJ, USA 2 Sodium hydroxide is 30% active 3 Potassium hydride is 45% active 4SDA 40 (100% ethanol) EXAMPLES 11-16 The following examples 11-16 depict aerosol spray patterns of the compositions of the present invention.

Example No - = Component 11 12 13 14 15 16 (% by weight) Graft copolymer 5.00 4.00 3.50 1.1 Graft copolymer 4.00 3.00 4.00 1. 2 Isododecano1 0.50 0.50 Triethyl citrate 0.21 Diisolbutyl adipate 0.70 0.45 0.40 0.25 0.35 Propylene glycol 0.30 Sodium hydroxide3 - 1.00 _ 1.0 Potassium hydroxide4 - 0.94 1.20 1.04 - 1.20 Perfume 0.10 0.10 0.10 0.10 0.10 0.10 Sodium Benzoate 0.10 0.10 0.10 0.20 Ethanol5 56.69 57.42 72.0 50.0 30.0 54.5 Propellant-isobutane 7.02 15.00 10.00 P928 Propellant-n-butane 10.00 Propellant-dimethyl ether 10.00 15.00 15.00 Propellant-25.0 15.98 32.32 hydrofluorocarbon 152a7 Water c.b. c.b.p. c.b.p. c.b.p. c.b.p. c.b.p. 100 100 100 100 100 10"• PERMETHYL 99A, from Presperse, Inc., South Plainfield, NJ, USA. 2CITROFLEX-2, from Morf Lex, Inc., Greensboro, NC, USA. 3 Sodium hydroxide is 30% active. 4 Potassium hydroxide is 45% active. 5SDA 40 (100% ethanol) 5DYMEL-A, from Dupont 7DYMEL, 152a, from Dupont.

Each of the exemplified personal care compositions (Examples 3-16) are hair styling or hair spray modalities of the compositions of the present invention, and comprise the graft polymer as a styling or film forming polymer. elaborated according to the synthesis methods of the present invention. Each of the compositions can be formulated by conventional or other known techniques of formulation and mixing.

For example, each of the graft polymers is first mixed with ethanol, neutralizing the polymer with sodium or potassium hydroxide, then added sequentially (as P928 is applicable) with mixing, isododecane, plasticizers, perfume and water. If sodium benzoate is used, it is added after the addition of water. More preferably, a premix of water and sodium benzoate is made and then added after the addition of water. The propellants for the aerosol compositions are charged to the conventional aerosol containers after the remainder of the prepared composition has been added.

EXAMPLE 17 The following represents a hair styling gel embodiment of the composition of the present invention.

Ingredients% weight Graft copolymer 1.2 2.50 Water c.b. for 100% Carbomer 940 0.50 Hydroxide solution of 0.80 Sodium (30% by weight) Panthenol 0.05 Polysorbate 80 0.20 Perfume 0.20 This product is prepared by dispersing graft copolymer and carbomer 940 in water and adding P928 sodium hydroxide. The mixture is added for approximately 0.5 hours before adding the remaining ingredients.

EXAMPLE 18 The following represents a spray applied gel form of the composition of the present invention.

Incrredientes% peso Water c.b.p. 100% Ethanol 15.00 Panthenol 0.05 Potassium Hydroxide solution (45% 0.50 by weight) Perfume 0.20 Graft copolymer 1.1 2.00 The compositions are prepared by dissolving the graft copolymer 1.1. in ethanol and then add water and potassium hydroxide solution to facilitate the incorporation of the polymer in the solvent. The mixture is stirred for approximately 0.5 hours before adding the remaining ingredients.

P928 EXAMPLE 19 The following represents a modality of hair styling cream of the composition of the present invention.

Ingredients% weight Water c.b.p. 100% Lauramine oxide 0.20 Panthenol 0.05 Perfume ~~ 0.05 Copolymer 1.2 3.00 Hydroxide solution 1.00 Sodium (30% by weight) Isobutane 7.00 This composition is prepared by dissolving the graft copolymer 1.2 in water and then adding sodium hydroxide solution with mixing for about 0.5 hour. The other ingredients, except isobutane, are added and mixed for an additional 10 minutes. The aluminum aerosol cans are then loaded with 93 parts of this batch, fixed with a valve that is tightened in position, and finally charged with pressure with 7 parts of isobutane. This composition is useful for hair application to provide conditioning, styling and fixation.

P928 EXAMPLE 20 The following example represents a topical, sunscreen filtration mode of the composition of the present invention.

Ingredients% weight Water c.b.p. 100% Carbomer 1342 [1] 0.16 Octyl-methoxycin ato 0.50 Dimethicone-copolyol 0.10 Tocopheryl acetate 0.10 Sodium hydroxide (30% solution by weight) 1.50 Ethanol 40.0 Copolymer 1.2 4.00 [] Available as Carbopol ® 1342 from B.F. Goodrich.

The water, ethanol, sodium hydroxide solution and polymer 4 are mixed for half an hour. The remaining ingredients are added and mixed for an additional half hour. This composition is prepared by combining and mixing the graft copolymer 1.2 and water, ethanol, sodium hydroxide solution. The remaining ingredients are then added to the mixture.

P928 EXAMPLE 21 The following example represents a topical skin care modality of the composition of the present invention.

Ingredients% by weight Graft copolymer 1.2 2.00 Water c.b. 100% Ethanol (SDA 40) 40.00 Carbomer 940 0.75 Hydroxide solution of n 90 sodium (30% by weight) Salicylic acid 2.00 The composition is prepared by mixing water, ethanol, graft copolymer, and carbomer together for about 10 minutes. The remaining ingredients are added and the mixture is stirred for an additional 30 minutes. This composition is useful for application to the skin to provide improved resistance to water and is useful in the treatment of acne.

EXAMPLE 22 The following example represents a modality of nail polish of the composition of the present invention.

P928 - The composition is prepared by combining and mixing all the listed ingredients until they are dispersed evenly throughout the composition.

Ingredients% by weight Graft copolymer 1.1 15.00 Ethanol 42.00 Acetone 40.00 NaOH solution, 30% 3.00 EXAMPLE 23 The following example represents a skin care modality, topical of the composition of the present invention. The topical composition is proposed for use in the treatment, prevention or otherwise reduction of the appearance of wrinkles in human skin. The composition is prepared by combining and mixing all the listed ingredients until dispersing them evenly throughout the composition.

Ingredients% weight Graft copolymer 1.1 6. 00 NaOH solution, 30% 2. 10 Water DRO (purified by double inverted osmosis) c. b. p.

P928 EXAMPLE 24 The following example represents a hair styling lotion of the composition of the present invention. The graft copolymer is dissolved in ethanol and then added and mixed with the remaining ingredients until it is dispersed evenly throughout the composition.

Ingredients% weight Graft copolymer 1.1 4.00 Natrosol 250HH1 0.50 Solution of_NaOH, 30% 1.35 Kathon CG 0.3 Ethanol 8.00 Water DRO c.b.p. ^ atrasol 250HH-Hydroxyethylcellulose offered by Aqualon.

EXAMPLE 25 The following example represents the mode for shaving after the composition of the present invention. The composition is prepared by combining and mixing all the listed ingredients until dispersed uniformly throughout the composition.

P928 Ingredients% weight Graft copolymer 1.2 2.00 NaOH solution, 30% 0.60 Ethanol 50.00 perfume 0.20 Menthol 0.20 Water DRO c.b.

EXAMPLES 26-28 The following examples represent combing / conditioning rinsing modalities for the hair of the compositions of the present invention.

Composition E j ussa No. Premix of conditioner 26 27 28 Water c.b.p. c.b.p. c.b.p.

Citric acid 0.02 0.02 0.02 Sodium Citrate 0.09 0.09 0.10 Cetyl alcohol 0.12 0.12 0.12 Stearyl alcohol 0.08 0.08 0.08 Natrosol Plus CS Grade D-671 1.02 1.00 0.99 Xanthan gum 0.25 0.25 0.25 Polymer styling premixes Graft polymer 2.0 1.75 1.75 1.75 Permethyl 9A 8.54 8.54 8.54 P928 Trimethylsiloxysilicate 0.11 0.11 0.11 Kathon CG 0.03 0.03 0.03 Perfume 0.33 0.33 0.33 Silicone premix Water DRO 9.48 9.48 8.57 Adopt 47O4 0.70 0.60 0.93 Adopt 4715 0.05 0.15 0.07 Decamethyl rubber - 1.67 1.67 2.33 Cyclopentasiloxane / polydimeti1-siloxane3 Triethylsilyl-Amodimethicone (Dow 0.10 0.10 0.10 Corning Q2-8220) Surfactant premix Water DRO 5770 5.70 5.70 Stearalkonium Chloride 0.30 0.30 0.30 Hydrophobically modified hydrophobic cellulose from Aqualon Corp. 2 Xanthan rubber readily available 3SE-76 rubber available from General Electric. 'Di-dimethyl-onium chloride, Sherex Chemical Co. , Dublin, Ohio, USA, 75% aqueous solution. 5 Tallow-trimethyl ammonium chloride, Cherex Chemical Co., 50% aqueous solution.

Each of the exemplified compositions will be prepared as follows. A premix is prepared with silicone when combined and mixed (in a separate container) P928 water, Adopt 470 and Adop 471 at 85 ° C. Cool to 71 ° C and add the silicone rubber / decamethylcyclopentasiloxane and amodimethicone solution and mix until homogeneous. Cool to 38 ° C while using a homogenizer (such as Tekmar). Prepare the surfactant mixture by combining and mixing (in a second separate container) water and stearalkonium chloride at 38 ° C. Prepare the premix of the conditioner by combining and mixing (in a third separate vessel) DRO water heated to 71 ° C, citric acid, sodium citrate, cetyl alcohol, stearyl alcohol and Natrosol Plus CG grade D-67, and even disperse evenly, and then add xanthan gum and mix until dispersed evenly. Prepare the polymeric styling premix by combining and mixing the Permethyl 99A graft polymer, and trimethylsiloxysilicate until a uniform mixture is obtained. Combine and mix the polymer premix, styling, Kathon CG and perfume until homogeneous. Disperse additionally with an inline homogenizer (such as the Teckmar homogenizer) and then cool the mixture to 38 ° C. Finish the conditioner by mixing the premix of conditioner, the premix of silicone and the premix of surfactant at 38 ° C. Mix until homogeneous, then cool the composition to 25 ° C.

P928 When the compositions defined in Examples 26-28 are applied to the hair in the conventional manner, they provide effective hair conditioning / combing / retention benefits, without leaving the hair feeling sticky / stiff.

EXAMPLE 29 Polymer premix with drying aid Ingredients% weight Graft copolymer 2.0 16.83 Permethyl 99A 82.17 Trimethylsiloxysilicate 1.00 This polymer premix is prepared by adding the graft copolymer to the solvents while mixing. The mixture is heated between 80 ° C and 84 ° C in a covered container while mixing and then cooled between 23 ° C and 27 ° C before trimethylsiloxysilicate is added while mixing.

EXAMPLE 30 Polymer premix with drying aid Ingredients% weight P928 Graft copolymer 2.0 15.00 Isododecane 83.50 Polydimethylsiloxane2 1.50 2Polidimethylsiloxane, Dow Corning, Dow Corning 200 Fluid (20 csk) This polymer premix is prepared by adding the graft copolymer to the solvents while stirring. The mixture is heated between 80 ° C and 84 ° C in a covered container while mixing, then cooled between 23 ° C and 27 ° C before adding trimethylsiloxysilicate while mixing.

EXAMPLE 31 The following example represents a conditioning condition for the hair of the composition of the present invention.

Ingredients% P e s B Premix of the styling agent Premix of the copolymer of example 30 10.00 10.00 Silicone premix Silicone rubber, GE SE762 0.30 0.30 Octamethyl-cyclotetrasiloxane 1.70 1.70 P928 Main mixture c.b.p. c.b.p Water for 100 100 Cetyl Alcohol 1.00 Quaternium 183 0.85 0.85 Stearyl alcohol 0.70 Hydroxethyl-cellulose 0.50 Cetyl-hydroxyethyl-cellulose41.25 Ceteareth-20 0.35 Fragrance 0.20 0.20 Dimethicone-copolyol 0, .20 Citric acid 0, .13 0.13 Methylchloroisothiazolinone (y) 0.04 Methylisothiazolinone 0.04 Sodium chloride 0.01 0.01 Xanthan gum 0.20 Each of the compositions is prepared by co-mixing all the ingredients of the main mixture, by heating the resulting mixture to about 60 ° C with the mixed. The heated mixture is then cooled to about 45 ° C with colloidal grinding (Example A) or mixed (Example B). At this temperature, the two premixes are added separately with moderate agitation and the resulting conditioner is allowed to cool to room temperature. This composition is useful as a rinse hair conditioner.

P928 2Commercially available from General Electric. 3 Dimethyl di (hydrogenated tallow) -ammonium chloride. 'Commercially available as Polysurf D-67 from Agualon.

EXAMPLE 32 The following example represents a shampoo mode of the composition of the present invention.

Ingredients% weight Styling agent Copolymer premix of Example 30 15.00 Premix Silicone rubber 0.50 Dimethicone, 350 is fluid 0.50 Main mixture Water c.b.p. for 100 ammonium lauryl sulfate 11.00 Cocamide MEA 2.00 Ethylene glycol distearate 1.00 Xanthan Gum 1.20 Methylchloroisothiazolinone (y) 0.04 Methylisothiazolinone Citric acid at pH 4.5 as necessary.

The main mixture is prepared by dissolving P928 first xanthan gum in water with conventional mixing. The remaining ingredients of the main mixture are added and the main mixture is heated to 150 ° F with stirring for about 0.5 hours. The styling agent and the premix are then sequentially added with about 10 minutes of agitation between the additions, and the whole mixture is stirred while the batch is cooled to room temperature. For a varied particle size, the styling agent and the premix can be added at different times using either high cut (high speed disperser) or normal agitation mix, or both. This shampoo composition is useful for cleaning the hair and for providing a styling benefit.

P928

Claims (10)

1. CLAIMS 1. Composition for personal care comprising: (a) from 0.1% to 15% by weight of a graft polymer made in accordance with the following process steps: (i) reacting copolymerizable monomers to form a polymeric structure organic having a weight-average molecular weight of 15,000 grams / mol to 9,800,000 grams / mol and a plurality of organic halide portions covalently attached to the polymer structure and hanging therefrom; and then (ii) reacting copolymerizable monomers with the organic halide portions of the polymer structure, by polymerization of free radicals with transfer of atoms, in the presence of a catalytic amount of a Cu (I) salt, to form a plurality of polymeric side chains covalently attached to the polymer structure and hanging therefrom, the polymer side chains have an average molecular weight from 500 grams / mol to 200,000 grams / mol; wherein the "polymeric structure and the plurality of polymeric side chains form graft polymers having a weight-weighted molecular weight from 16,000 grams / mol to 10,000,000 grams / mol; P928 (b) from 0.1% to 99.9% by weight of a liquid carrier. The composition according to claim 1, wherein the graft polymer is hydrophilic and the liquid carrier is selected from a group consisting of water, ethanol, n-propanol, isopropanol and combinations thereof. 3. The composition according to any of the preceding claims, wherein the Cu (I) salts are selected from a group consisting of thiocyanate of Cu (I) Br, Cu (I) Cl, Cu (I) I and Cu ( I) and combinations thereof and wherein the reaction step (a) is the free radical polymerization of the copolymerizable monomers. The composition according to any of the preceding claims, wherein the Cu (I) salt is in the form of a ligand complex, wherein the ligand is an aprotic bidendate selected from the group consisting of 2, 2 '. -dipyridyl, diphosphates, 4,4'-di-5-nonyl-2, 2 'bipyridine, 4,4'-di-tert-butylbipyridine, 4,4'-diheptyl-2, 2'-bipyridine and combinations thereof . The composition according to any of the preceding claims, wherein the copolymerizabide monomers of step (a) comprise a vinyl monomer containing organic halide and a second monomer selected from the group consisting of acid P928 acrylic produced by hydrolysis of trimethylsilyl acrylate, methacrylic acid produced by hydrolysis of trimethylsilyl methacrylate, vinyl pyrrolidone, acrylic acid esters of alcohols of 1 to 18 carbon atoms, methacrylic acid esters of alcohols of 1 to 18 carbon atoms carbon, trimethylsilyl acrylate, trimethylsilyl methacrylate, styrene, alpha-methylstyrene, t-butylstyrene, vinyl acetate, vinyl propionate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, n-butyl methacrylate isobutyl methacrylate, acrylate of t-butyl, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, salts thereof and mixtures thereof. The composition according to claim 5, wherein the vinyl monomer containing organic halide of step (a) is selected from the group consisting of: R1 I CHa = C CH-X P92? (II) (ni) R I CH- = c- -x I! or (IV) (V) CH, = CH-O-R4-X and combinations thereof, wherein R is methyl or hydrogen, X is a halogen atom; R, R1 and R2 are each independently methyl, hydrogen or methoxy; and R 4 is an alkyl group having 1 to 8 carbon atoms. The composition according to any of the preceding claims, wherein the polymer structure represents 50% to 99% by weight of the polymer Graft P928, and the plurality of polymeric side chains represent from 1% to 50% by weight of the graft polymer. 8. The composition according to any of claims 1, 2, 3 or 4, wherein the graft polymer has a polymeric structure and has a Tg value of less than 10 ° C and a plurality of polymeric side chains having a Tg value greater than 70 ° C. The composition according to any of claims 1, 2, 3 or 4, wherein the graft polymer has a polymer structure having a Tg value greater than 50 ° C and a plurality of polymeric side chains having a Tg value of -20 ° C. The composition according to any one of claims 1, 2, 3 or 4 wherein the graft polymer is hydrophobic and the liquid carrier comprises a hydrophobic liquid potter selected from the group consisting of branched, branched chain hydrocarbons, having 12 to 16 carbon atoms, liquid carriers of silicone and combinations thereof, wherein the liquid silicone carrier is selected from a group consisting of phenyl-pentamethyl-disiloxane, phenylethyl-pentamethyl-disiloxane, hexamethyl-disiloxane, methoxypropyl -heptamethyl cyclotetrasiloxane, chloropropyl-pentamethyl disiloxane, hydroxypropyl- P928 pentamethyl disiloxane, cyclomethicones, including octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and mixture thereof. P928