MXPA99004175A - Hair styling composition - Google Patents

Abstract

Disclosed are hair styling compositions comprising by weight:(a) from about 0.2%to about 5%of an anionic polymer;(b) from about 0.2%to about 5%of a cationic polymer;(c) from about 0.2%to about 5%of an amphoteric polymer;and (d) a solvent;whereein the total of components (a), (b), and (c)is from about 0.6 to about 15%, and wherein the level of the component comprised at the lowest level among components (a), (b), and (c) is at least about 5%of that of the component comprised at the highest level among components (a), (b), and (c).

Description

COMPOSICIOH FOR. The present invention relates to a composition for styling the hair that provides a flexible film texture and good combing retention. aM ECEDEMTES OF HAIR-HVSNTION The way of making the hair retain a particular shape is widely maintained. The most common methodology to achieve this is the application of a composition to moistened hair, or after washing with shampoo and / or conditioning, or to stylized and dry hair. These styling compositions provide temporary fixation benefits and can be removed with water or by shampooing. The materials used in the compositions to provide the fixing benefits have generally been resins and have been applied in the form of foams, gels, lotions or sprays. Additionally, these styling compositions are formulated for additional purposes, such as shampooing, conditioning, treatment, dyeing and combinations thereof. A major desire of the consumer with respect to The performance of styling compositions has been the ability to retain hair. Frequently, good retention has been associated with a strong and prolonged styling and / or fixation of the hair. However, it has also been observed that styling compositions having a retention capacity exceeding a certain magnitude can also give the hair a harsh feeling, making combing difficult, as well as being difficult to remove by shampooing. In addition, in recent years, some customers have expressed a desire to have hair styling products that allow the rearrangement of hair without compromising the capacity of hair retention. Since styling compositions with good retention capacity commonly provide a rigid film texture, it was difficult to provide a composition with a flexible film texture that would allow rearrangement of the hair. In this way, there is a desire to have hair styling compositions that have good retention without compromising the ability to rearrange the hair, can provide a soft and supple feeling to the hair, and can be easily removed from the hair in the wash with shampoo It has been known in the art that the mixing of Different types of polymers can result in a composition that lightens the disadvantages of the specific polymer. For example, anisic polymers can give good retention, however, they can also provide a harsh feel to the hair and are relatively difficult to remove in the shampoo wash. This is because the anionic polymers are generally less hydrophilic after film formation, and tend to reject shampoo compositions that usually have anionic charges. The cationic polymers can provide a soft and supple feel to hair and can also control the static generated by hair styling, etc., however, they are also relatively difficult to remove from shampooing. This is because they tend to deposit on negatively charged hair and, over time, can accumulate on the hair so that they can not be easily removed by washing with "shampoo." Amphoteric polymers, in general, can be removed further. Easily in shampooing than anionic polymers, and have less deposit / buildup problems than cationic polymers, however, when used alone, they have limited formulation compatibility to provide a flexible film texture and good retention The Japanese patent put to inspection No. 2-223509 discloses a water-soluble, soap-free hair styling composition comprising a polymer with both cationic and amphoteric units and an anionic polymer at a certain weight ratio. In the present invention, a hair styling composition comprising three different types of polymers has been developed; anionic polymer, cationic polymer, and amphoteric polymer; at certain levels and relationships with an appropriate solvent, which provides a flexible and good retention film texture, which can not be achieved by the individual use or combination of two of any of the three types of polymers mentioned above.

SUMMARY OF IMVEHCl? A The present invention relates to hair styling compositions comprising by weight: (a) from about 0.2% to about 5% of an anionic polymer; (b) from about 0.2% to about 5% of a cationic polymer; (c) from about 0.2% to about 5% of an amphoteric polymer; and (d) a solvent; where the total of components (a), (b), and (c) is from about 0.6% to about 15%, and wherein the level of the component comprised at the lowest level between components (a), (b), and (c) is at least about 5% of the component comprised in the highest level between components (a), (b), and (c). These compositions satisfy the need for a styling composition of the hair that provides a flexible film texture and good retention, thereby providing hair rearrangement ability-a soft and supple hair feel and good wash removal with shampoo, without "compromising the good capacity of hair retention." These compositions also meet the general requirement of a styling composition that can comprise a wide range of solvents, preservatives and propellants.

DETAILED DESCRIPTION OF THE INVENTION All percentages herein are expressed by weight of the compositions, unless otherwise indicated. All proportions are weight proportions unless otherwise indicated. The total of the components, except for the propellant, is hereinafter defined as a "concentrate". For non-aerosol products that do not contain propellant, the concentrate is equal to the complete composition. All the Percentages, proportions and ingredient levels referenced herein are based on the actual amount of the ingredient, and do not include solvents, bulking agents, or other materials with which it can be combined-the ingredient as commercially available products, unless Indicate otherwise. - The invention herein may comprise, consist of or consist essentially of the essential elements described herein as well as any of the preferred or optional ingredients also described herein. All publications, patent applications and patents issued hereinafter referred to herein are hereby incorporated by reference in their entirety.

ANOPHERAL POLYMER Amphoteric polymers are comprised at a level from about 0.2% to about 5% by weight of the concentrate. The amphoteric polymers useful for the present invention are chosen from the following polymers (1) to (5). (1) Useful herein are the dialkylaminoalkyl (meth) acrylate or dialkylaminoalkyl (meth) acrylamide polymers treated with betaine which they contain at least units of the formula: R1 i) t -tCH2-C] - I R3 II COYR2N + - * I c? 2 I coo- where RI denotes a hydrogen atom or a methyl group, R2 denotes an alkylene group having of 1 to carbon atoms, Y denotes O or -NH- and R3 and R * independently denote hydrogen or alkyl having 1 to 4 carbon atoms, and a cationic derivative consisting of a cationic surfactant agent containing ^ at least one hydrogen atom attached to one or more fatty chains and optionally quaternized, or consisting of a cationic polymer of the polyamine, polyaminopolyamide, or poly- (quaternary ammonium) type, the amine or the ammonium groups are part of the polymer chain or join it. These polymers usually have a molecular weight of 500 to 2,000,000. Amphoteric polymers containing units corresponding to the above formula (I) are generally in the form of copolymers containing, in addition to the units of the form (I) mentioned above, at least units of the formula: R1 (II) I - [CH2-C1- I COORS wherein R1 is as defined above and R5 represents an alkyl or alkenyl radical having from 4 to 24 carbon atoms or a cycloalkyl radical having from 4 to 24 carbon atoms carbon. It is also possible to use terpolymers, tetrapolymers or pentapolymers containing, in addition to the units (I) and (II) defined above, units of the formula: ## STR3 ## wherein R.sup.6 denotes preferably an an alkenyl or alkenyl group having from 1 to 3 carbon atoms and R1 is as defined above. The units of the formula (I) are preferably present in an amount of 25 to 45% by weight, the units of the formula (II) are preferably present in an amount of 5 to 55% by weight, and the units of the formula (III) are preferably present in an amount of up to 50% by weight relative to the weight total of the polymer. A particularly preferred polymer is the copolymer containing units of the formulas (I), (II), and (III) in which Y denotes an oxygen atom, R2 denotes the group -C,! ----, -, R1, R3 and R * denote methyl, R5 denotes an alkyl group having from 4 to 8 carbon atoms and ~ Rs denotes an alkyl group having from 1 to 3 carbon atoms. The average molecular weight of this polymer is preferably from 70,000 to 90,000. This polymer is sold under the trademark "Yukaformer" or "Diaformer" supplied by Mitsubishi Chemical Corporation. (2) Useful herein are polymers resulting from the copolymerization of a vinyl monomer having a carboxyl group, such as acrylic acid, methacrylic acid, maleic acid, or alpha-chloroacrylic acid, and a basic monomer which is a substituted vinyl compound which contains at least one basic nitrogen atom, such as methacrylates and dialkylaminoalkyl acrylates and dialkylaminoalkyl methacrylamines and acrylamides. (3) Useful herein are polymers containing units derived from i) at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen by an alkyl radical, ii) at least one acid comonomer containing one or more reactive carboxyl groups, and iii) at least one basic comonomer, such as esters , with substituents of primary, secondary and tertiary amines and quaternary ammonium substituents, of acrylic and methacrylic acids, and the product resulting from the quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate. The N-substituted acrylamides or methacrylamides which are more particularly preferred are the groups in which the alkyl radicals contain from 2 to 12 carbon atoms, especially N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide , N-decylacrylamide and N-dodecyl acrylamide and also the corresponding methacrylamides. The acid comonomers are chosen more particularly from among acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids and also the alkyl monoesters of maleic acid or fumaric acid in which the alkyl has from 1 to 4 carbon atoms. Preferred basic comonomers are aminoethyl, butylaminoethyl methacrylates, N, W- dimethylaminoethyl and N-tert-butylaminoethyl. (4) Useful herein are the crosslinked and alkylated polyaminoamides derived partially from polyaminoamides of the general formula: wherein R represents a divalent radical derived from a saturated dicarboxylic acid, from an aliphatic monocarboxylic or dicarboxylic acid with an ethylenic double bond, or from an ester of a lower alkanol having from the β carbon atoms and from these acids or from a radical derived from the addition of any of the acids of a bis-primary or bis-secondary amine, and Z denotes a radical of a bis-primary or mono- or bis-secondary polyalkylene-polyamine, and preferably represents: ) in proportions of 60 to XOO mole%, the radical - [NH- (CH2) -NH] - (II) wherein x is 2 and N [sic] is 2 or 3, or alternatively x is 3 and n is 2, this radical is derived from diethylenetriamine, triethylenetetraraine, or dipropylenetriamine; ii) in proportions of 0 to 40 mol%, the radical previous (II) where x is 2 and n is 1 and is derived from ethylenediamine, or the radical / \ -N? - \ / piperazine derivative; and iii) in proportions of 0 to 20 mole%, the "radical -? H- (CHj), -HH-, derived from hemamethylenediamine, these polyamides are crosslinked by the addition of a bifunctional crosslinking agent chosen from epihalogenhydrins, diepoxides, dianhydrides and bis-unsubstituted derivative, using 0.025 to 0.35 mol of crosslinking agent per amine group of the polyaminoamide, and alkylated by reaction with alkyl acid, chloroacetic acid, or an alkane-sultone or its salts. saturated carboxylic acids are preferably chosen from acids having from 6 to 10 carbon atoms, such as adipic acid, 2,2,4- and 2,4,4-trimethyladipic acids, terephthalic acid and acids with an ethylenic double bond, such as acrylic, methacrylic-and itaconic acids The alkane sulfones used in the alkylation are preferably propane- or butane-sultone and the salts of the alkylating agents are preferably the sodium or potassium salts. (5) Useful herein are polymers containing zwitterionic units derived from the formula: I I R1- i-C-3 X ~ N + - < CH2) -CQO- I I R3 H.5 wherein R1 denotes a polymerizable unsaturated group, such as an acrylate, methacrylate, acrylamide, methacrylamide, x and y group independently represent an integer from 1 to 3, R2 and R3 independently represent hydrogen, methyl, ethyl or propyl and R4 and Rs independently represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms of * and Rs does not exceed 10. Highly preferred amphoteric polymers include material commercially available as octylacrylamide-acrylates-butylaminoethyl methacrylate copolymers with the trademarks : AMPHOMER, AMPHOMER LV71, - And AMPHOMER LV47 supplied by National Starch & Chemicals, and methacryloyl-ethylene-betaine / acrylate copolymers with the trade names of: YUKAFORMER SM, YÜKA ORMER 301, YUKAFORMER 510, YUKAFORMER m-75, and YUKAFORMER R250S supplied by Mitsubishi Chemical Corporation.

J-NONOMIC POLYMER Anionic polymers are comprised at a level from about 0.2% to about 5% by weight of the concentrate. The anionic polymers useful in the present invention are polymers containing units derived from a carboxylic, sulfonic or phosphoric acid and usually have a molecular weight of 500 to 5,000,000. These polymers are water-soluble polymers, it being possible for this solubility to be obtained by neutralization. The carboxylic acid groups can be provided by unsaturated monocarboxylic or dicarboxylic acids, such as those corresponding to the formula: R1 (A) n -COOH / C-C / R2R3 wherein n is 0 or an integer from 1 to 10, A denotes a methylene group optionally attached to the carbon atom of the saturated group, or the adjacent methylene group in the case where n is greater than -1, via an ether or atom, such as oxygen or sulfur, R1 denotes a hydrogen atom or a phenyl or benzyl group, RJ denotes an hydrogen, a lower alkyl group, or a carboxyl group and R3 denotes a hydrogen or hydrate, a lower alkyl group, CH2COOH, or a phenyl or benzyl group. According to the invention, the preferred anionic polymers containing carboxylic acid groups are: - (1) Homopolymers or copolymers of acrylic or methacrylic acid or salts thereof, and in particular, the products sold under the name VERSICOL E or K by BASF and under the name DARVAN No. 7 by Van der ilt; copolymers of acrylic acid / acrylamide sold in the form of its sodium salt under the name RETEN 421, 423 0 425 by HERCULES; and sodium salts of polyhydroxycarboxylic acids, sold under the name HYDAGEN F by HENKEL. - - (2) Copolymers of acrylic or methacrylic acid with a monoethylenic monomer, such as ethylene, styrene, a vinyl or allylic ester or ester of acrylic or methacrylic acid optionally inserted in a "polyalkylene glycol, such as polyethylene glycol, and optionally cross-linked. copolymers like that contain an N-alkylated acrylamide unit and / or N- " hydroxylated optionally in your chain, such as those sold under the name QUADRAMER 5 by American Cyanamid. (3) Copolymers derived from crotonic acid, such as those containing in their chain or units of vinyl acetate and propionate and, optionally, other monomers such as allyl or metalyl esters, a vinyl ether or a vinyl ester of a linear carboxylic acid or branched, saturated, with a hydrocarbon chain of at least 5 carbon atoms, in case these polymers are to be grafted or crosslinked, or else a vinyl, allyl or methallyl ester of an α- or β-cyclic carboxylic acid . Included in this class are those with the trade names RESYN 28-2930, "28-2913, and 28-1310 sold by National Starch &Chemicals. (4) Polymers derived from maleic, fumaric, and itaconic acids, or anhydrides with esters vinyl, vinyl ethers, vinyl halides, phenyl vinyl derivatives, acrylic acid and their esters, such as those sold under the name GANTREZ, SP, and ES by ISP Other polymers included in this class are copolymers of maleic, cyclic, and itaconic anhydride with a allyl or metalic ester optionally containing an acrylamido or methacrylamido group, or with an α-olefin, acrylic or methacrylic acid ester, acrylic or methacrylic acid or vinylpyrrolidone unit in its chain; Anhydrides can be monosterific or monsamidify. (5) Polyacrylamides containing carboxylate groups. Polymers comprising sulphonic groups include polymers containing vinylsulphonic, styrenesulphonic, lignosulphonic or naphnesulfonic units. These polymers are selected, in particular, from: i) Salts of polyvinylsulfonic acid having a molecular weight of 1,000 to 100,000, also copolymers with a comonomer ± unsaturated, such as acrylic or methacrylic acid or an ester thereof and also substituted or non-substituted acrylamide or methacrylamide, vinyl esters, vinyl ethers and vinylpyrrolidone ii) Salts of polystyrenesulfonic acids, such as sodium salt sold by National Starch &Chemical sold under the name of Flexan 500 and 130. iii) Alkali metal or alkaline earth metal salts of sulphonic acids derived from lignin and, more particularly, calcium lignosulfonates or sodium lignosulphonates, such as the product sold under the name Merasperse "C-21 by American Can Co. and products from 10 to 14 carbon atoms sold by Avebene. iv) Polymers containing salified alkylnaphthalenesulfonic acid units, such as the sodium salt sold under the name Darvan No. 1 by Van der Bilt.

The anionic polymers herein including anionic monomers are preferably used in the at least partially neutralized form, in order to assist in the removability of the liquid cosmetic compositions when shampooing the hair. In the compositions according to the present invention, the neutralization of a polymer can be achieved by the use of an inorganic base, preferably KOH. However, an organic base, preferably AMP (amino-methyl-propanol) and the mixture of organic and inorganic base, can also be used to effect the desired level of neutralization in hair styling compositions according to the present invention. . In total, it should be used with the base from about 50% to about 100%, preferably from about 70% to about 100%, most preferably from about 80% to about 100% of the acidic monomers of each polymer used Any conventionally used organic or inorganic base can be used for the neutralization of acidic polymers with the proviso that they are used as specified herein The hydroxides of alkali, alkaline earth and amine alcohols are "suitable neutralizers" for use in the present invention.

Examples of suitable organic neutralization agents which can be included in the compositions of the present invention include amines, especially amino alcohols such as 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amine- 2-ethyl-l, 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), dimethyltearamine (DMS) and amino-methylpropanol (AMP) and mixtures thereof. Preferred neutralizing agents for use in hair styling compositions of the present invention are potassium and sodium hydroxides. Highly preferred anionic polymers including commercially available material such as copolymers of vinyl acetate / crotonic acid / vinyl neodecanoate and vinyl acetate / crotonic acid copolymer with the trade names RESYN 28-2930", RESYN 28-2913, and RESYN 28-1310 supplied by National Starch &Chemicals, and acrylate / acrylamide acrylate copolymer copolymers with the trade names LUVIMER 100P, ULTRAHOLD 8, and ULTRAHOLD STRONG supplied by BASF Corporation.

POLYMER C-VGIOHIC? The cationic polymers are comprised with levels from about 0.2% to about 5% by weight of the concentrate. The cationic polymers useful in the present invention are: (1) vinylpyrrolidone / acrylate "or quaternized dialkylaminoalkyl methacrylate copolymers, such as those sold under the tradename Gafquat 734 and 755N by the Gaf Corp. (2) Cellulose-ether derivatives which contain quaternary ammonium groups. - (3) Cationic polysaccharides. (4) Cationic polymers chosen from the group containing: -A-Z'-A-Z2- (I) wherein A denotes a radical containing two amino groups, preferably a piperazinyl radical, and Z1 and Z2 independently denote a divalent radical which is a straight or branched chain alkylene radical containing up to about 7 carbon atoms in the main chain, substituted or unsubstituted with one or more hydroxyl group and may also contain one or more hydrogen, nitrogen or sulfur, and one to three heterocyclic and / or aromatic rings, the oxygen, nitrogen and sulfur atoms are generally present in the form of an ether or thioether, sulfoxide, sulfone, sulfonium, amine, alkylamine, alkenylamine group , benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane; ii) polymers containing units of the formula: -A-Z'-A-Z'- (II) wherein A denotes a radical containing two amiho group, preferably a piperazinyl radical, and Z 'denotes _ the symbol Z3 and Z4, while denoting the symbol z' at least once; Z3 denotes a divalent radical which is a straight or branched chain alkylene or hydroxyalkylene radical having up to 7 carbon atoms in the main chain, and Z * is a divalent radical which is a straight chain or branched alkylene radical having up to 7 carbon atoms in the main chain, unsubstituted or substituted with one or more hydroxyl radicals and interrupted by one or more nitrogen atoms, the nitrogen atom is substituted by an alkyl chain having from 1 to 4 carbon atoms, preferably 4 carbon atoms, and is optionally interrupted by an oxygen atom and optionally contains one or more hydroxyl group; and iii) The alkylation products with alkyl and benzyl halides of 1 to 6 carbon atoms, - tosylates or alkyl mesylates and the oxidation products of the polymers of formulas (I) and (II) indicated above in i) and ii). (5) Polyamino-polyamines prepared by "the polycondensation of an acid compound with a polyamide The acid compound can be organic dicarboxylic acid, monocarboxylic acid and aliphatic dicarboxylic acid containing double bond, ester of the acids mentioned above, preferably the esters with lower alkanols having from 1 to 6 carbon atoms, and mixtures thereof. The polyamine is a bis-primary or mono- or bis-secondary polyalkylene-polyamine, wherein up to forty mole percent of this polyamide can be a bis-primary amine, preferably ethylene diamine, or a bis-secondary amine, preferably piperazine, and up to 20 mol% can be hexamethylenediamine. (6) The polyamino-polyamides mentioned above can be alkylated and / or crosslinked. The alkylation can be carried out with glycidol, ethylene oxide, propylene oxide or alkylamide. The crosslinking is carried out by means of a crosslinking agent as: i) epihalogenohydrins, diepoxides, dianhydrides, unsaturated anhydrides and bis-saturated derivatives, in a proportion of 0.025 to 0.35 mol of "crosslinking agent per amine group of the polyamino-polyamide; ii) bis-halogenohydrins, bis-acetydinium compounds, bishalogen-acyldiamines and bis- (alkyl halides); iii) Oligomers obtained by reacting a compound selected from the group comprising bis-halogenhydrins, bis-acetidinium compounds, bis-halogenoacyl-diamines, bis- (alkyl halides), epihalogenhydrins, diepoxides and bis-unsaturated derivatives, with another compound which is difunctional and reactive with the compound; and iv) the quaternization product of a compound selected from compounds ii) and oligomers iii) and containing one or more tertiary amino groups, which may be wholly or partially alkylated with an alkylating agent selected preferably from mesylates, tosylates, Methyl or ethyl bromides, iodides, sulfates and chlorides, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol, the crosslinking is carried out by means of 0.025 to 0.35 mol, in particular 0.025 to 0.2 mol and more particularly 0.025 to 0.1 mol, of the cross-linking agent by amine group of the polyamino-polyamide. (7) Polyamino-polyamide derivatives resulting from the condensation of a polyalkylene polyamine with a polycarboxylic acid, followed by alkylation by means of bifunctional agents, such as the dialkylaminohydroxyalkyl dialkylenetriamine adipic acid copolymers, in which the alkyl radical it contains from 1 to 4 carbon atoms and preferably denotes ethyl, methyl or propyl. Useful polymers are copolymers of adipic acid / dimethylaminohydroxypropyl-diethylenetriamine sold under the name of Cartaretine F, F1 or Fa by SANDOZ. (8) The polymers obtained by reacting polyalkylene polyamine containing two primary amine groups and at least one secondary amine group, with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms, molar ratio of the polyalkylene polyamine to the dicarboxylic acid which is from 0.8: 1 to 1.4: 1, and the resulting polyamine which is reacted with epichlorohydrin in a molar ratio of epichlorohydrin to the secondary amine groups of the polyamine from 0.5: 1 to 1.8: 1. Useful polymers are those sold under the name HERCOSETT 57 by Hercules Incorporated, and those sold under the name PD 170 or DELSETTE 101 by " Hercules. (9) Cyclic polymers having in general a molecular weight of 20,000 to 3,000,000 such as homopolymers which contain, as the main constituent of the chain, units corresponding to formula (III) or "(III ') .CH2) P (III) ) / \ <CH2 > fc-RnC CR "-CH2- 1 1 H2C CH2 \ / N + y- / \ RR 'ÍCH2) P (rrx'i / \ (CH2) tR" C CR. "- CH2- H2C CH2 \ / N in which p and t are 0 or 1, and p + t = l, R "- denotes hydrogen or methyl, and R 'independently denote a alkyl having from 1 to 22 carbon atoms, a hydroxyalkyl in which the alkyl group preferably has from 1 to 5 carbon atoms, or a lower amidoalkyl group, and R and R 'may denote together with the other nitrogen atom the which are joined, heterocyclic groups such as piperidinyl- or morpholinyl, and Y is bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. Polymers containing units of formulas III and III 'may also contain units derived from. acrylamide or diacetone acrylamide. Among the quaternary ammonium polymers of the type defined above, those which are preferred are the dimethyldialkyl ammonium chloride homopolymer sold under the name MERQUAT 100 and having a molecular weight of 100,000, and the dimethyldialkyl ammonium chloride / acrylamide copolymer and have a molecular weight "of more than 500,000 sold under the name of MERQUAT 550 by CALGON Corporation. (10) Poly- (quaternary ammonium) compounds of the formula R1 I I - [- N + A N + B-] n- 2X- (IV) R2 * wherein R1, R2, R3 and R4 are independently aliphatic, alicyclic or arylaliphatic radicals containing a maximum of 20 carbon atoms, or lower hydroxyaliphatic radicals, or alternatively, with the nitrogen atoms to which they are attached form heterocyclic rings containing optionally a second hetero atom other than hydrogen, or alternatively R1, R2, R3 and R * represent a group CH2CHR'3R'4 wherein R'3 denotes hydrogen or lower alkyl and R * 4 denotes SO, CN, CON (R's) 2 , COOR * ', "" COR5, C00R', D, O C0NHR''D; R'S denotes lower alkyl, R's denotes hydrogen or lower alkyl, R'1 denotes alkylene and D denotes a quaternary ammonium group; A and B independently represent a polymethylene group containing from 2 to 20 carbon atoms, which may be linear or branched, saturated and unsaturated and may contain, inserted in the main chain one or more -CH.-Y-CH. Groups, - where Y denotes benzene, oxygen, sulfur, SO, SO ,,, SS, NR '", N * (R") -X1", CHOH, NHCONH, CONR'8 OR COO; X1"denoting an anion derived from mineral or organic acid, R '" denoting hydrogen or lower alkyl and R, 9 denotes lower alkyl or, alternatively, A and R 1 and R 3 form a piperazine ring with the two nitrogen atoms to which they are attached. If A denotes a hydroxyalkylene or alkylene radical, branched linear, saturated or unsaturated, B denotes a group: - (CH 2) a-CO-D-OC- (CH 2) n-; wherein n is selected so that the molecular weight is generally between 1,000 and 100,000; and D denotes: i) a glycol radical of the formulas -OZ-0, in which Z denotes a linear or branched hydrocarbon radical or a group corresponding to the formula: - [CH.-CHj-OI ^ -CH. -CH, - or - [CH.-CtCHjJH-Ol? CI ^ -CÍCH ^ H- where x and y denote an integer from 1 to 4, which represents a defined and unique degree of polymerization; ii) a bis-secondary diamine radical, such as a piperazine derivative; iii) a bis-primary diamine radical of the formula: -N-H-Y-NH-, in which Y denotes a linear or branched hydrocarbon radical or the divalent radical -OL-CIL-S-S-CHj-CH, -; or iv) a ureylene group of the formula -N-H-CO-NH- (11) Homopolymers or copolymers derived from acrylic or methacrylic acid and containing at least one unit of: Rl Rl I I I -CH2-C- (V) CH2-C- (V) -CHa-C-. { V ') I I c-o c-o c «o I I I o o NH I I I A. A I I N R2-N + -R * R2-N ++ - R4 / \ I I R5 R3 R3 X "R3 X wherein R1 is H or CH3, A is a linear or branched alkyl group having from 1 to 6 carbon atoms or a hydroxyalkyl group having from 1 to 4 carbon atoms, R2, R3 and R4 independently denote an alkyl group which has from 1 to 18 carbon atoms or a benzyl group, R5 and R6 denote H or alkyl having 1 to 6 carbon atoms and X denotes methosulfate or halide, such as chloride or bromide. The comonomer or comonomers that can be used typically correspond to the family comprising: acrylamide, methacrylamine, diacetone-acrylamide, acrylamide and methacrylamide substituted on the nitrogen by one or more lower alkyl, alkyl esters of acrylic and methacrylic acids, vinylpyrrolidone and vinyl esters . Useful polymers are Quatemium 38, 37, 49 and 42 defined in CTFA, acrylamide / beta-methacryloyloxyethyltrimethylammonium methosulfate copolymers sold under the names Teten 205, 210, 22"0 and 240 by Hercules, and the aminoethyl acrylate phosphate / acrylate copolymer sold under the catrex name by National Starch & Chemicals, and cross-linked cationic graft polymers having a molecular weight of from 10,000 to 1,000,000, and preferably from 15,000 to 500,000, and resulting from the copolymerization of: at least one cosmetic monomer, dimethylaminoethyl methacrylate, polyethylene glycol and an agent of polyunsaturated crosslinking, such as those mentioned in the CTFA dictionary under the name AMODIMETHICONE, as the product sold as a mixture with other ingredients under the name 929 of the DOW CORNING cationic emulsion. (12) Other cationic polymers that can be used are polyalkyleneamines, in particular polyethyleneimines, polymers containing vinylpyridine units or vinylpyridinium units in the chain, condensates of polyamines and epichlorohydrin, poly- (quaternary ureylenes) and chitin derivatives. Highly preferred cationic polymers include commercially available material such as Polyquaternium 4 under the names CELQUAT H100 and CELQÜAT L200 supplied by National Starch Chemicals and Poliqua ernium 11 _ sold under the name GAFQUAT 755N supplied by ISP.

SOLVENT The solvents used in the present invention are selected depending on variables such as the rest of the components, viscosity and desired foaming characteristics of the composition. The non-limiting examples and solvents useful in the present invention are: water, lower alcohols having from 1 to 6 carbon atoms such as ethanol- and isopropanol, and polyhydric alcohols such as polyethylene glycol, hexylene glycol, glycerin and propanediol, and mixtures thereof thereof. For foam- and solvent compositions, it comprises at least about 80%. water, more preferably at least about 90% water. The solvent is preferably comprised at a level by weight of from about 60% to about 99%, more preferably from about 80% to about 99%, and most preferably from about 85% to about 98% of the concentrate .

NON-IONIC SURFACTANT AGENTS _ When the styling composition of the present invention is in the form of a foam, the composition preferably comprises an agent non-ionic surfactant having a HLB value by the Griffin method of minus 12. Non-ionic surfactants are particularly preferred-since they provide softness to the foam. In the present invention, the HLB value is measured by the Griffin method as follows: For polyhydric alcohols and fatty acid esters, the HLB value is calculated by the following calculated general formula: HLB = 20 (1-S / A) in where S is the "saponification value of the esters, and A is the acid value of the fatty acids; For surfactants of which the saponification value is not clear, the HLB value is calculated by the following formula: HLB = (E + P) / 5 where E is the percentage by weight of ethylene oxide, and P is the weight percentage of the polyhydric alcohol, and For surfactants where the polyoxyethylene is the only hydrophilic group, the HLB value is calculated by the following general formula: HLB = E / 5 where E is a percentage in peeo of ethylene oxide. The styling composition of the present invention preferably comprises a nonionic surfactant selected from the group consisting of a polyoxyethylene, a polyoxypropylene- and mixtures thereof having a total HLB value by the Griffin method of at least 12. Another embodiment of the styling composition of the present invention may comprise a first nonionic surfactant selected from the group consisting of the general formulas identified above (I), (II), (III) and mixtures thereof. , and a second nonionic surfactant agent selected from the group consisting of the general formulas (I), (II), (III), (TV), (V), (VI) and mixtures thereof. Non-limiting examples of nonionic surfactants for use in the styling composition of the present invention are as follows: (1) Polyoxyethylene alkyl ethers which are polyethylene glycol ethers and alkyl alcohol having the following general structure: CH, - (CH2) a- (OCHjCHj ^ -OH (I) where a has an average value of 9 to 21 rn has a average value of 2 to -200; (2) Polyoxyethylene alkenyl ethers having the following general structure: CH3- (CH2) b-CH = CH (CH2) c- (OCH2CH2) n-OH (II) _ wherein b has an average value of from 1 to 10 , c has an average value of 1 to 10, n has an average value of 2 to 200; (3) Alkyl or alkenyl or iso-alkyl or iso-alkenyl ethers of polyoxypropylene, or of methyl polysiloxane having the following general structure: R 1 - [OCH (CH 3) CH 2] x- (OCH 3 CH -) _ OH (III) wherein R1 is selected from the group consisting of alkyl, alkenyl, isoalkylalkenyl, and dimethylpolysiloxane derivatives, x has an average value of 2 to 100; and has an average value of 2 to 100; (4) An ether derived from benzene or long-chain alkyl polyoxyethylene acid or having the following general structure: R2- (OCH2CH2) - OH (IV) wherein R2 is selected from the group consisting castor oil triglyceride ricinolate, cholesterol, coconut oil triglyceride cocoate, alkylphenol, glyceryl laurate, glyceryl oleate, glyceryl cocoate, glyceryl isostearate, glyceryl stearate, hydrogenated ricinolate. triglyceride of hydrogenated castor oil, hydrogenated lanolin, nonyl phenyl derivatives and dimethylpolylylosan, and n has an average value of 2 to 200; "(5) Alkyl or alkenyl ether &polyoxyethylene having the following general structure: R3-C (0) - (OCH2CH2)? L-0-C (0) -R * (V) wherein R3 and R4 are independently selected from the group consisting of alkyl, ie-alkyl and alkenyl and n having an average value of a 200: (6) Long chain alkyl or iso-alkenyl fat, alkylglyceryl and polyoxypropylene ether having the following general structure: R- [OCH (CH3) CH2] nOH (VI) wherein R5 is selected from the group which consists of alkyl, iso-alkyl and alkenyl, and n has an average value of 2 to 200.

OPTIONAL COMPONENTS Other components may be included in the hair styling compositions of the present invention, depending on the needs of the product. Non-limiting examples of these "optional components include conditioning agents, preservatives, perfumes, absorption and filtering agents of ultraviolet and infrared light, dyes, pH adjusters, polymers-no additional ionics, additional surfactants, dyes, vitamins, proteins , plant extracts and nutrients.

Conditioning agents The conditioning agents may be comprised in the hair styling and composition of the present invention. Suitable conditioning agents include fatty alcohols, fatty acids and hydrocarbons. Fatty alcohols useful herein are those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and most preferably from about 16 to about 22 carbon atoms. These fatty alcohols can be straight chain alcohols or branched and may be saturated and unsaturated. Non-limiting examples of fatty alcohols include decyl alcohol, undecyl alcohol, dodecyl alcohol, mipstyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, isocetyl alcohol, behenyl alcohol, linalool, oleyl alcohol, cholesterol, cis-4-t-butylcyclohexanol, myristic alcohol and mixtures thereof. Especially preferred fatty alcohols are those selected from the group consisting of cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol and mixtures thereof. The fatty acids useful herein are those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and more preferably from about 16 to about 22 carbon atoms. These fatty acids may be straight or branched chain acids and may be saturated or unsaturated. They also include diacids, triazides and other multiple acids that satisfy the requirement for the carbon numbers herein. Also included herein are salts of these fatty acids, non-limiting examples of fatty acids include lauric acid, palmitic acid, stearic acid, behenic acid, arachidonic acid, oleic acid, isostearic acid, acid sebacic and mixtures thereof. Especially preferred for use herein are the fatty acids selected from the group consisting of palmitic acid, stearic acid, and mixtures thereof. same. The hydrocarbons are useful herein as conditioning agents. - Useful hydrocarbons include straight chain hydrocarbons, cyclic and branched chain hydrocarbons that may be saturated and unsaturated. The hydrocarbons will preferably have from about 12 to about 40 carbon atoms, more preferably from about 12 to about 30 carbon atoms, and more preferably from about 12 to about 22 carbon atoms. Also encompassed herein are the polymeric hydrocarbons of alkenyl monomers, such as polymers of alkenyl monomers of 2 to 6 carbon atoms. These polymers can be straight or branched chain polymers. The straight chain polymers will typically be of relatively short length, with a "total number of carbon atoms as described above in this paragraph." Branched chain polymers can have substantially larger chain lengths. These materials can vary widely, but it will typically be up to about 500, preferably from about 200 to about 400, and more preferably from about 300 to about 350. Also useful herein are the various grades of mineral oils Mineral oils are liquid mixtures of hydrocarbons Specific examples of suitable hydrocarbon materials include paraffin oil, mineral oil, dodecane, isododecates, hexadecane, isohexadecane, eicosene, ioceicosine, tridecane, tetradecane, polybutene, polyisobutene, and mixtures thereof. Isododecane, isohexadecane, - and isoeicosene are commercially available as Permethyl 99A, Permethyl 101A, and Permethyl 1082, from Presperse, South Plainfield, NJ. A polymer of is-obutene and normal butene is commercially available as Indopol H-100 from Amoco Chemical. Preferred for use herein are the hydrocarbon conditioning agents selected from the group consisting of mineral oil, isododecane, isohexadecane, polybutene, polyisobutene, and mixtures thereof When included, these two conditioning agents are comprised at a weight level from about 0.01% to about 2% of the concentrate.

Conservative Lae hair styling compositions of the present invention may additionally comprise a preservative. This preservative is preferably included at a weight level of up to about 5%, more preferably up to about 3% of the concentrate. Non-limiting examples of preservatives useful in the present invention are hydantoin DMDM (dimethylol-dimethyl-hydantoin), Katon CG (mixture of methylchloro-isothiazolinone and methyl-isothiazolinone), imidazolidinyl urea, phenoxyethanol EDTA and salts, benzyl alcohol and parabens , such as methyl paraben, propyl paraben, butyl paraben and Liquapar oil (mixture of isobutylparaben, isopropyl paraben, and butyl paraben).

Propellent Propellants can be used for hair spraying and foam compositions. The propellants when used in the present invention are selected depending on variables such as: the rest of the components, the packaging and the product is designed to be used stationary or inverted. When it is comprised in foams, the propellant is preferably comprised of a level of up to about 60% preferably up to approximately 30% of the complete composition. When comprised in sprays, the propellant is preferably comprised at a level from about 15% to about 80%, preferably from about 20% to about 60% of the complete composition. When the propellant is not used, the styling composition of the hair is usually provided in a package equipped with an air or gas mixing device. Non-limiting examples of propellants useful in the present invention are: fluorohydrocarbons such as difluoroethane 152a (supplied by Dupont), dimethyl ether and hydrocarbons such as propane, isobutane, n-butane and mixtures of hydrocarbons such as LPG (liquefied petroleum gas).

Other optional components The hair styling compositions of the present invention may additionally comprise a variety of optional components. These optional components include: thickeners and viscosity modifiers such as long chain fatty acid diethanolamides, sodium chloride and sodium sulfate, ultraviolet light absorbing agents such as ethyl salicylate, pH adjusting agents, such as citric acid, succinic acid , sodium hydroxide and triethanolamine, agents dyes, hair oxidizing agents, such as hydrogen peroxide, perborate salts, persulfate salts, hair reducing agents such as thioglycollates, perfume, perfume solubilizing agents such as polyethylene glycol fatty acid esters, sequestering agents, polymer plasticizing agents as glycerin and propylene glycol and volatile and non-volatile low molecular weight silicone fluids. These optional ingredients are typically included in the pee level of up to about 20%, preferably up to about 10% of the concentrate.

COMPOSITION The hair styling composition of the present invention comprises a certain minimum amount of each of: an anionic polymer, a cationic polymer and an amphoteric polymer. The level of the preferred component at the lowest level between these polymers is at least about 5% of the polymer comprised at the highest level. Without this minimum amount of each polymer the desired benefits of the present invention can not be achieved. The total amount of the amphoteric polymer, anionic polymer and cationic polymer by weight "of the concentrate is from about 0.6% to about 15%, more preferably from about 0.6% to about 10%, most preferably about 0.6% to about 10%. The amount of each polymer and the relationships between them are selected by the technician depending on the characteristics of the desired product. The tree types of polymers are preferably included in the composition in a manner where they are easily dispersed and mixed with other components to produce a stable end product. It is known in the art that by directly mixing the anionic polymers and the cationic polymers there may be precipitations that are difficult to disperse. This is particularly problematic for sprays and foams for hair where the final product is applied to the hair - as foams or fine mist.A suitable and preferable way to add the three types of polymers is to add them in an order "so that the The anionic polymer and the cationic polymer do not have direct contact with each other.

EXAMPLES The following examples further describe and demonstrate the embodiments within the scope of the present invention. The examples are given only to illustrate the invention and should not be construed as limiting the invention, since it is possible to make many variations thereof without departing from the spirit and scope of the invention. The ingredients are defined by the chemical name or with the CTFA nomenclature or "as they define otherwise later.

Method of Preparation Examples I and II are foam composition embodiments, and Examples III and IV are hair spray composition embodiments of the present invention that can be prepared by any conventional method well known in the art. The appropriate method is as follows: First, the anionic polymer is neutralized in an aqueous medium. For this the amphoteric polymer is added with caution to avoid agglomeration. Then, the remaining ingredients except the cationic polymer are added. Finally, the cationic polymer or an aqueous medium containing the cationic polymer is added, and the mixture obtained is mixed until homogeneous. The concentrate is packaged in aerosol cans with propellant to make a foam or spray composition.

QUANTITY (%) EXAMPLE No. 2_ 3 COMPONENTS COMPOSED Concentrate 94.0 92.0 65.0 55.0 Propellant L.P.G. 6.0 8.0 35.0 45.0 Total composition 100 100 100 100 COMPONENTS IN CONCENTRATE Amphomer LV71 -1 3.50 -_ JÍ.00 3.00 Yukaformer SM '2 - 10.0 - - Luvimer 36D "3 - 4.17 2.78 - Resyn 28-2913" 4 1.00 - - 2.00 Celquat H100 '_ 0.50 0-.5O 0_20 0.13 Aminomethylpropanol - - 0.79 0.75 1.03 0.79 Lauryl ether PEO (21) 0.22 0.28 - Lauryl ether PEO (4.2) 0.18 0.23 - Phenyltrimeticana 0.50 0.50 0.50 - Lauramide diethanolamine 0.10 0.10 - - Stearic alcohol > 0.10 - - - - Tego betaina f "'- 0.33 - - Methyl paraben 0.15 0.15 - - Phenoxyethanol 0.25 0.25 0.25 0.25 EDTA Disodium 0.10 0.10 0.10 0.10 Permethyl 99A "'0.05 - - 0.10 Propylene glycol 0.25 0.25 .D.25 0.10 Perfume 0.05 0.07 ~ "0.07 0.07 Ethanol 190 test - - 20.0 25.0 Water DI _ c.s c.s c.s c.s " Total Concentrate 100 100 100 100 * 1 Amphomer LV71: Octyl acrylamide / acrylates / butylaminoethyl / methacrylate copolymer, supplied by National Starch &; Chemical * 2 Yukaformer SM: Copolymer of Methacryloylethylbetaine / acrylates, supplied by Mitsubishi Chemical Corporation * 3 Luvmer 36D: Acrylate copolymers, supplied by BASF Corporation * 4 Resyn 2913: vinyl acetate / crotonic acid / vinylneodecanoate copolymer, supplied by JSational Starch &; Chemical * 5 Celquat H100 Policuaternium 4, supplied by National Starch & Chemical * 6 Tego Betaina F: Cocamidopropyl betaine, supplied by Gold Schmidt * 7 Permethyl 99A: Isodecane, supplied by Presperse

Claims (3)

1. KEIVIHDIA-CIOtl-ES i _ 1. A hair styling composition comprising, by weight of the concentrate: (a) from about 0.2% to about 5% of an amphoteric polymer; (b) from about 0.2% to about 5% of an anionic polymer; (c) from about 0.2% to about 5% of a cationic polymer; and (d) a solvent; where the total of components (a), (b), and (c) is from about 0.6% to about 15%, "and where the level of the component comprised at the lowest level among components (a), ( b), and (c) is about 5% of the component comprised at the highest level between components (a), (b), and (c)
2. 2. The styling composition of the hair according to claim 1, wherein the The composition is in the form of a foam further comprising from about 0.02% to about 1% by weight of the concentrate of a nonionic surfactant having a total HLB value by the Griffin method of at least 12.
3. 3. The composition of hair styling according to claim 1, wherein the composition is in the form of a hair spray.