MXPA00000608A - Hair conditioning compositions containing alpha or beta hydroxy acid esters - Google Patents

Abstract

A hair conditioner composition comprising, by weight of the total composition:0.1-20%of a cationic conditioning agent, 0.1-20%of esters of alpha or beta hydroxy acids, 0.1-30%of a fatty alcohol, 0.001-10%of a nonionic surfactant, and 5-95%water.

Description

HAIR CONDITIONER COMPOSITIONS WITH A CONTENT OF HYDROXYZED ALPHA OR BETA ESTERS TECHNICAL FIELD The invention is in the field of hair conditioning compositions.

BACKGROUND OF THE INVENTION Damage to hair can result from exposure to excessive heat or cold, such as with the dryer, and exposure to sun or wind. Chemical treatments such as permanent or coloring hair can also cause it to weaken or damage. Merchants of personal care products have commercialized multiple varieties of conditioners after shampoo that contain ingredients that exert a conditioning effect on the hair. Unfortunately, the ingredients that condition the hair also provide certain undesirable effects. Solid, non-volatile ingredients such as fatty alcohols, resins, waxes and oils are often used as conditioning agents. Although these materials exert a very beneficial effect on the hair, they also tend to favor oily hair, or form a sticky surface on the hair that attracts dust and other particles from the air. This makes the hair look dull and dirty, and can also make the hair look flat without body. The use of alpha hydroxy acids (AHA) in hair care products is known. However, AHAs are generally soluble in water, so they tend to be rinsed from the hair with water and do not remain on the hair to provide a significant, substantive hair conditioning effect. On the other hand, fatty alcohols provide a substantive conditioning effect for the hair, but may tend to cause the hair to become greasy, dull and bodyless. Unexpectedly, it has been discovered that hair care compositions containing alpha and / or beta hydroxy acid esters provide a good substantive conditioning effect for hair, improve shine, body, ease of combing and fullness, and at the same time they do not cause the hair to become greasy or sticky.

SUMMARY OF THE INVENTION The invention is directed to a hair care composition containing, by weight of the total composition: 0.1-20% cationic conditioning agent, 0.1-20% of one or more alpha or beta hydroxy acid esters, 0.1-30% fatty alcohol, 0.001-10% non-ionic surfactant, and 5-95% water. The composition is in the form of a conditioner for after the shampoo which is a water-in-oil or oil-in-water emulsion, preferably the latter.

DETAILED DESCRIPTION All percentages mentioned herein are percentages by weight unless stated otherwise.

Conditioning agent The composition of the invention contains 0.1-20%, preferably 0.5-15%, most preferably 1-12% by weight of the total composition of a cationic conditioning agent. Suitable cationic conditioning agents are cationic polymers, quaternary ammonium salts or salts of fatty amines. The quaternary ammonium salts have the formula: wherein, in Ri is an aliphatic group of 1 to 22 carbon atoms, or aromatic, aryl or alkaryl group having from 12 to 22 carbon atoms; R2 and R3 each independently are an aliphatic group having from 1 to 22 carbon atoms; and R 4 is an alkyl group of from 1 to 3 carbon atoms, and X is an anion selected from halogen, acetate, phosphate, nitrate and methylisulfate radicals. The aliphatic groups may contain, in addition to the carbon atoms, ether linkages as well as amido groups. Suitable quaternary ammonium compounds may be long-chain monoalkyl, long-chain dialkyl, long-chain trialkyl, and the like. Examples of the quaternary ammonium salts include behenalconium chloride, behentrimonium chloride, behentrimonium methosulfate, benzalkonium chloride, benzethonium chloride, benzyltriethylammonium chloride, cetalconium chloride, cetrimonium chloride, cetrimonium bromide, cetrimonium methosulfate, tosylate. of cetrimonium, cetylpyridinium chloride, dibehenyl chloride / diaraquidyl dimonium, dibehenildimonium chloride, dibehenildimonium methosulfate, dicapril / dicapryldildimonium chloride. Other quaternary ammonium salts useful as the cationic conditioning agent are the compounds of the general formula: ++ H3 $ x-wherein Ri is an aliphatic group having from 16 to 22 carbon atoms, R2, R3, R4, R5 and Re are the same or different and are selected from alkyls having from 1 to 4 carbon atoms and X is a anion as defined in the above. The amides having the general formula set forth below are also suitable conditioning agents: O o, RC - NXY or RC II-NH - (Cryñ-NXY wherein R is a saturated or unsaturated alkyl, straight or branched chain having from 6 to 30 carbon atoms, n is an integer from 1 to 4, and X and Y are each independently H, or lower alkyl of C1-6. An amide of the formula is preferred: O i! RC-NH ~. { CH2)? RNXY wherein R is a straight or branched chain alkyl of C12-22C n is an integer of 1 to 4 and X is lower alkyl, preferably methyl. Also suitable are amidoamine salts which are condensation products of fatty acids with polyfunctional amines, for example those having the formula RCONH (CH2) nNR? R2 where RCO is a fatty acyl group such as stearoyl, Ri and R2 are methyl or ethyl, and n is 2 or 3. Examples of these compounds include stearicide propyl dimethylamine. Particularly preferred are the amidoamine compounds complexed with a semidryeric acid, such as the dimer dilinoleate of di (behenamidopropyldimethylamine) or the dinoleate dinoleate di (linoleamidopropyldimethylamine) dimer. Both ingredients are marketed by Alzo, Inc. under the trade name NECON. Also, the quaternary imidazolinium salts having the following general formula, are suitable as the cationic conditioning agent: wherein R5 is hydrogen or C1-4alkyl; Rβ is C 1-4 alkyl; R7 is C8-22 alkyl; And s is hydrogen, or C? _22 / alkyl and X is an anion as defined above. Also suitable as the cationic hair conditioning agent are the salts of fatty, primary, secondary or tertiary amines, wherein the substituted groups have from 12 to 22 carbon atoms. Examples of these amines include dimethyl stearamine, dimethylamine, stearylamine, myristylamine, tridecylamine, ethylstaramine and so on. Also suitable as the cationic conditioning agent are cationic polymers such as: (a) Quaternary cellulose ether derivatives such as polymers marketed under the trademark JR-125, JR-400, JR-30M. (b) Vinylpyrrolidone copolymers having monomer units of the formula: i wherein R is hydrogen or methyl, preferably methyl; and is 0 or 1, preferably 1 2 R is O or NH, preferably NH; R3 is CxH2x where x is 2 to 18, or -CH-CHOH-CH2-, preferably CXH2X where x is 2; 4 R is methyl, ethyl, phenyl or phenyl substituted by C? _, Preferably methyl; and R is methyl or ethyl, preferably methyl. (c) The homopolymer of dimethyldiallylammonium chloride or copolymer of dimethyldiallylammonium chloride and acrylamide.

These compounds are marketed under the brand MERQUAT by Merck. (d) Homopolymers or copolymers derived from acrylic or methacrylic acid, selected from the monomeric units acrylamide, methacrylamide, diacetone-acrylamide, acrylamide or methacrylamide substituted in the nitrogen by lower alkyl, alkyl esters of acrylic acid and methacrylic acid, vinylpyrrolidone or vinyl esters . (e) Cationic silicones. As used herein, the term "cationic silicone" means any polymer or silicone oligomer having a silicon backbone, which includes polysiloxanes, having a positive charge on the silicone structure itself. The cationic silicones that can be used in the compositions of the invention include those corresponding to the following formula: (R) aG3-a-SÍ- (-OSÍG2) n- (0sÍGb (Ri) 2-6b) m ~ 0 -SYG3-a (R1) to which G is selected from the group consisting of H, phenyl, OH, alkyl C and preferably CH3; and a is 0 or an integer from 1 to 3, and preferably is .0; b is 0 or 1, preferably 1; the sum n + m is a number from 1 to 2,000 and preferably from 1 to 50 to 150; n is a number from 0 to 2,000, and preferably 50 to 150; and m is an integer of 1 to 2,000, and preferably 1 to 10; and Ri is a monovalent radical of the formula CqH2qL in which q is an integer from 2 to 8 and L is selected from the groups: -N (R2) CH2-CH2-N (R2) 2 -N (R2) 2 + -N (R2) 3A- + + -N (R2) CH2-CH2-NR3H2A- in which R2 is selected from the group consisting of H, phenyl, benzyl, a saturated hydrocarbon radical and is preferably an alkyl radical containing from 1 to 20 carbon atoms; and A is a halide ion. (f) Quaternary polymeric ammonium salts such as polyquaternium 31, 33, 34, 35, 36, 37, and 39. Also suitable are dicuternary polydimethylsiloxanes such as Quaternium-80, marketed by Goldschmidt Corporation under the trademark ABIL-Quat 3272. Examples of other cationic polymers that can be used in the compositions of the invention are described in U.S. Patent Nos. 5,240,450 and 5,573,709, which are incorporated herein by reference. Preferred compositions of the invention contain 0.5-15% by weight of a cationic conditioning agent which is selected from the group: (a) quaternary ammonium salts having the formula: wherein Ri is an aliphatic group of 1 to 22 carbon atoms , or aromatic, aryl or alkaryl group having from 12 to 22 carbon atoms; R2 is an aliphatic group having from 1 to 22 carbon atoms; R3 and R4 are each alkyl groups of 1 to 3 carbon atoms and X is an anion selected from halogen, acetate, phosphate, nitrate and methylisulfate radicals; (b) cationic silicones having the following formula: (R) aG3-a- "Si- (-OSÍG) n- (OSÍGb (Rl) 2-6b) m ~ 0 ~ SÍG3-a (Rl) a wherein G is H, phenyl, OH, C1- alkyl 10; a is 0 or an integer from 1 to 3, b is 0 or 1, the sum n + m is a number from 1 to 2,000, n is a number from 0 to 2,000, and m is an integer from 1 to 2,000; and Ri is a monovalent radical of the formula CqH2qL in which q is an integer from 2 to 8 and L is selected from the groups: -N (R2) CH2-CH2-N (R2) 2 ~ N (R2) 2 + -N (R2) 3 - + + -N (R2) CH2-CH2-NR3H2A- in which R2 is H, phenyl, benzyl, a saturated hydrocarbon radical and preferably is an alkyl radical containing from 1 to 20 carbon atoms; carbon, and A is a halide ion, and (c) an amide of the formula: RC-NH-íCHjjhn-NXY wherein R is a straight or branched chain alkyl, Ci2-22 r n is an integer of 1 to 4 and X is a lower alkyl, preferably methyl, (d) an amidoamine salt, and the semidimeric acids thereof. Particularly preferred is where the cationic conditioning agent is selected from: trimethylsilylmodimethicone, cetrimonium chloride, behentrimonium chloride, di (behenamidopropyldimethylamine) dinoleate dimer, di (linoleamidopropyldimethylamine) dinoleate dimer or mixtures thereof.

BATHROOM ALPHA OR BETA STEREOS The hair care composition of the invention contains 0.001-20%, preferably 0.01-10%, most preferably 0.05-5% of at least one alpha and / or beta hydroxy acid. The esters of the alpha hydroxy acids present the following general formula: wherein Ra and Rb each are independently H, F, Cl, I, Br, alkyl, aralkyl or aryl group of straight or branched chain isomeric or nonisomeric, saturated or unsaturated or cyclically, having from 1 to 30 carbon atoms carbon; and in addition to Ra and Rb can carry OH, CHO, COOH or alkoxy group having from 1 to 10 carbon atoms; and Rc is a saturated or unsaturated straight or branched chain alkyl having from 6 to 30 carbon atoms; and m and n each are independently integers from 0 to 2 with the proviso that n and m can not both be zero. Preferably Ra and Rb each are independently C alquilo-αalkyl or OH, CHO or COOH group carrier, or zero, with the proviso that n and m can not both be zero, ie, there is at least one group Ra or Rb; and Rc is a saturated or unsaturated, straight or branched chain alkyl of C12-22 / co or can be lauryl, myristyl, palmityl, stearyl, isostearyl, cetyl, linoleyl, oleyl or linolenyl. Particularly preferred is where Ra is selected from CH2CHOHCOOH, CHOHCH3 and CH2OH; and Rb is selected from 0 or CH2OH; and Rc is a branched chain alkyl. Examples of these compounds are isostearyl lactate, isostearyl glycolate, isostearyl citrate, and mixtures thereof. Also suitable are the beta hydroxy acid esters formed by the reaction of a carboxylic acid having beta hydroxy functionality, with an altic alcohol, preferably an altic alcohol with 6 to 30 carbons. Included within this group are the beta hydroxy acids having the general formula: (Ra>) ír ~ (Rb) RRr rCH - CHz-- íCf - ORc where Ra, Rb and m and n are as defined above. A malic acid ester is preferred. More preferred is a mixture of alpha and beta hydroxy acid stems, in particular, a mixture of malate, lactate, glycolate and isostearyl citrate. This material is marketed by Alzo, Ine, with the trademark Dermol ALFA, which is a reaction product of a mixture of alpha and beta hydroxy acids obtained from natural sources and isostearyl alcohol.

FAT ALCOHOLS The composition of the invention contains 0.1-20%, preferably 0.5-10%, most preferably 1-8% of a fatty alcohol having the formula RCJH2OH, wherein R is a saturated or unsaturated alkyl, straight chain or branched having at least about 6 to 30 carbon atoms. Examples of suitable fatty alcohols for use include behenyl alcohol, C9-15 alcohols, caprylic alcohol, cetearyl alcohol, cetyl alcohol, coconut alcohol, decyl alcohol, lauryl alcohol, cetyl alcohol, [sic], myristyl alcohol, oleyl alcohol , palm alcohol, stearyl alcohol, bait alcohol, and the like. Preferred compositions of the invention include a mixture of cetyl and stearyl alcohols.

NON-IONIC SURFACTANT The compositions of the invention contain 0.001-10%, preferably 0.01-8%, most preferably 0.01-5% of a non-ionic surfactant or emulsifier. Suitable nonionic surfactants include alkoxylated alcohols or ethers, formed by the reaction of an alcohol with an alkylene oxide, usually ethylene or propylene oxide. Preferably, the alcohol is a fatty alcohol having from 6 to 30 carbon atoms, and a saturated or unsaturated, branched or linear carbon chain. Examples of these ingredients include Beheneth 5-30, which is formed by the behenyl reaction and ethylene oxide where the number of repeated ethylene oxide units is from 5 to 30; Ceteareth 2-100, formed by the reaction of a mixture of cetyl and stearyl alcohol with ethylene oxide, where the number of repeating ethylene oxide units in the molecule is from 2 to 100; Ceteth 1-45 which is formed by the reaction of cetyl alcohol and ethylene oxide, and the number of repeating units of ethylene oxide is from 1 to 45, and so on. Particularly preferred is Ceteareth 20, which is the reaction product of a mixture of cetyl and stearyl alcohol with ethylene oxide, and the number of repeating units of ethylene oxide in the molecule is 20. Acidic non-ionic surfactants are also suitable alkoxylated carboxylic acids which are formed by the reaction of a carboxylic acid with an alkylene oxide or with a polymeric ether. The resulting products have the general formula: doijde RCO is a radical carboxylic ester, X is hydrogen or lower alkyl and n is the number of polymerized alkoxy groups. In the case of diesters, the two RCO- groups do not need to be identical. Preferably, R is a saturated or unsaturated alkyl, straight or branched chain, of C6-30 and n is 1-100. Also suitable as the non-ionic surfactant are the monomeric, homopolymer and block copolymer ethers. These ethers are formed by the polymerization of monomeric alkylene oxides, generally ethylene or propylene oxide. These polymeric ethers have the following general formula: wherein R is H or lower alkyl, and n is the number of repeating monomer units, and the range is from i to 500. Other suitable nonionic surfactants include alkoxylated sorbitan and alkoxylated sorbitan derivatives. For example, alkoxylation, in particular, ethoxylation of sorbitan provides polyalkoxylated sorbitan derivatives. The esterification of polyalkoxylated sorbitan provides sorbitan esters such as polysorbates. Examples of these ingredients include polysorbates 20-85, sorbitan oleate, sorbitan palmitate, sorbitan sesquiistearate, sorbitan stearate and others.

Also suitable as non-ionic surfactants are silicone surfactants, which are defined as silicone polymers having at least one hydrophilic radical and at least one lipophilic radical. The silicone surfactant used in the compositions of the invention are organosiloxane polymers which can be a liquid or solid at room temperature. The organosiloxane surfactant is generally a water-in-oil or oil-in-water surfactant that is, and has a hydrophilic / lipophilic balance (HLB) of 2 to 18. Preferably, the organosiloxane is a non-ionic surfactant having a HLB of 2 to 12, preferably from 2 to 10, more preferably from 4 to 6. The HLB of a non-ionic surfactant is the balance between the hydrophilic and lipophilic portions of the surfactant and is calculated according to the following formula: HLB = 7 + 11 . 7 x log M¡ ^ / M0 where Mw is the molecular weight of the portion of the hydrophilic group and MD is the molecular weight of the portion of the lipophilic group. The term "organosiloxane polymer" means a polymer containing a polymer backbone that includes repeating siloxy units that may have linear or branched cyclic repeating units, for example, di (alkyl) (lower) siloxy units, preferably dimethylsiloxy units. The hydrophilic portion of the organosiloxane is generally obtained by substitution on the polymer backbone of a radical that confers hydrophilic properties on a portion of the molecule. The hydrophilic radical may be substituted in one term of the polymeric organosiloxane, or in any one or more repeating units of the polymer. In general, the dimethylsiloxy repeating units of the modified polydimethylsiloxane emulsifiers are lipophilic in nature due to the methyl groups, and impart lipophilicity to the molecule. In addition, the larger chain alkyl radicals, the hydroxy-polypropyleneoxy radicals, or other types of lipophilic radicals may be substituted on the siloxy backbone to further confer lipophilicity and organocompatibility. If the lipophilic portion of the molecule is due in whole or in part to a specific radical, this lipophilic radical may be substituted in one term of the organosilicone polymer, or in any one or more repeating units of the polymer. It should also be understood that the organosiloxane polymer according to the invention should have at least a hydrophilic portion and a lipophilic portion. The term "hydrophilic radical" means a radical which, when substituted on the polymeric organosiloxane backbone, imparts hydrophilic properties to the substituted polymer portion. Examples of the hydrophilicity-imparting radicals are hydroxy-polyethyleneoxy, hydroxyl, carboxylates and mixtures thereof. The term "hydrophilic radical" means an organic radical which, when substituted on the polymeric organosiloxane backbone, confers lipophilic properties on the substituted polymer portion. Examples of the organic radicals which will confer lipophilicity are straight or branched chain alkyl of C? _o, fluorine, aryl, aryloxy, hydrocarbyl acyl of C 1-40, hydroxy-polypropyleneoxy or mixtures thereof. The C? -40 alkyl can be interrupted or not interrupted by one or more oxygen atoms, or a benzene ring, amides, esters or other functional groups. The polymeric organosiloxane surfactant used in the invention may have any of the following general formulas: MxQy, or MxTy, or MDXD 'and D "zM wherein each M is independently a substituted or unsubstituted trimethylsiloxy cap or capitate unit. or more of the hydrogens in the methyl groups are substituted, or one or more methyl groups are substituted with a substituent which is a lipophilic radical, a hydrophilic radical or a mixture of both, T is a trifunctional siloxy unit having the empirical formula RR 'SiO? .5 or RRSÍO1.5.Q is a quadrifunctional siloxi unit having the empirical formula SÍÜ2 and D, O ', D ", xyyz are as set forth below, with the proviso that the compound contains at least one hydrophilic radical and at least one lipophilic radical, A linear silicone of the formula: MDXD' and D" zM in where M = RRRSiO? / 2 D and D = RRXSi02 2 D "= RRSi02 / 2 X, y, yz each are independently 0-1000, where R is methyl or hydrogen, and R 'is a hydrophilic radical or a lipophilic radical With the proviso that the compound contains at least one hydrophilic radical and at least one lipophilic radical, it is more preferred where M = trimethylsiloxy D = Si [(CH3)] [(CH2) nCH3] 02/2 where n = 0 -40, D 'Yes [(CH3)] [(CH2) o0-PE)] 02/2 where PE is (-C2H0) a (-C3H60) bH, or = 0-40, a = 1-100 and b = 1-100, and D 'Si (CH3) 202/2 More specifically, suitable silicone surfactants have the formula: wherein p is 0-40, preferably 12-20, most preferably 15, and PE is (-C2H4?) to (-C3H6O) b ~ H, where x, y, z, a and b are such that the molecular weight Maximum polymer is approximately 50,000. Another type of preferred organosiloxane emulsifier, suitable for use in the compositions of the invention, are the emulsifiers marketed by Union Carbide under the Silwet ™ brand. These emulsifiers are represented by the following generic formulas: (Me3Si) y_2 [(OsiMe2) x yO-PE] and where PE = - (EO) m (PO) nR R = lower alkyl or hydrogen Me = methyl Eo is polyethyleneoxy PO is polypropyleneoxy M and n each independently are 1-5,000 X and Y each independently are 0-5,000, and Me3SiO (Me2SiO) x (MeSiO) andSiMe3 PE where PE = -CH2CH2CH20 (EO) m (PO) nZ Z = lower alkyl or hydrogen, and Me, m, n, .x, y, EO and PO are as already described, with the proviso that the molecule contains a lipophilic portion and a hydrophilic portion. Again, the lipophilic portion can be supplied by a sufficient number of methyl groups on the polymer. Also suitable as non-ionic silicone surfactants are silicones substituted with hydroxy such as dimethiconol, which is defined as a dimethylsilicone substituted with terminal hydroxy groups. Examples of silicone surfactants are those marketed by Dow Corning 3225C Formulation Aid. Dow Corning 190 Surfactant, Dow Corning 193 Surfactant, Dow Corning Q2-5200, and the like are also suitable. In addition, the surfactants marketed under the brand Silwet by Union Carbide, and the surfactants marketed by Troy Corporations under the Troysol trademark, to those marketed by Taiwan Surfactant Co. With the Ablusoft trademark, those marketed by Hoechst under the Arkophob trademark, are also suitable for use in the invention.

In the preferred compositions of the invention, the nonionic surfactant is an alkoxylated alcohol, or ether, formed by the reaction of a fatty alcohol with ethylene oxide; alone or in combination with dimethicone substituted with hydroxy. Particularly preferred is Ceteareth-20, which is the reaction product of a mixture of cetyl and stearyl alcohol with ethylene oxide, and the number of repeating units ethylene oxide in the molecule is 20 and dimethiconol. Particularly preferred is a nonionic silicone known as trimethylsilyl imaticone, having the following formula: where x and y are 1-100,000.

OTHER INGREDIENTS To improve the effects and provide other benefits it is possible to add other ingredients to the conditioning compositions. It is possible to use a variety of these materials.

SILICONES It may also be desirable to include silicones in the hair conditioning compositions of the invention. These silicones are known to improve the ease of combing in wet and dry hair, exert conditioning effects and improve shine and hair management. Suggested silicone ranges are 0.01-20%, preferably 0.05-15%, most preferably 0.1-10% by weight of the total composition, suitable silicones include linear and cyclic volatile polydimethylsiloxanes, and non-volatile, linear polydimethylsiloxanes, organosiloxane surfactants and silicone resins. Volatile silicones are linear or cyclic silicones having a measurable vapor pressure, which is defined as a vapor pressure of at least 2 mm of mercury at 20 ° C. Examples of volatile silicones are cyclic silicones having the general formula: wherein n = 3-7 Likewise, the volatile, linear silicones that can be used in the compositions of the invention have the general formula: (CH3) 3SÍ-0- [Su (CH3) 2-0] n "YES (CH3) 3 where n = 0-7, preferably 0-5.The silicone can contain water-insoluble, non-volatile silicone fluids including polyalkyl siloxanes, polyarylsiloxanes, polyalkylaryl siloxane copolymers and mixtures thereof These silicones have the following general formula : wherein R and Rf each are independently alkyl, aryl, and x and Y are each independently 0-100,000, with the proviso that there is at least one x or y, and A is a siloxy capacete unit. It is preferred where A is methyl and R and R 'are methyl. The silicone resins are also suitable for use in the compositions of the invention. The silicone resins are siloxy silicate polymers having the following general formula: [< RR'R ") 3Si01 / 2]? Js, O2 | wherein R, R 'and R" are each independently a straight or branched chain alkyl of C? _? O or phenyl, and yy are such that the ratio of the units (RRXR ") 3SiO? / 2 to units Si02 is 0.5 to 1 to 1.5 to 1. Preferably, R, R ', and R" are an alkyl of C? _6, and most preferably are methyl, andxy are such that the ratio of the units (CH3) 3SiO? / 2 to the SiO2 units is from 0.75 to 1. More preferred is the trimethylsiloxy silicate containing 2.4 to 2.9% by weight of hydroxyl groups that are formed by the reaction of the salt of sodium of silicic acid, chlorotrimethylsilane and isopropyl alcohol. The manufacture of trimethylsiloxy silicate is set forth in U.S. Patent Nos. 2,676,182; 3,541,205; and 3,836,437, all of which are incorporated herein by reference. Trimethylsiloxy silicate as described is available from Dow Corning Corporation under the trademarks 2-0749 and 2-0747, which is a mixture of about 40-60% volatile silicone and 40-60% trimethylsiloxy silicate. Dow Corning 2-0749 in particular is a fluid containing about 50% trimethylsiloxy silicate and about 50% cyclomethicone. The fluid has a viscosity of 200-700 centipoise at 25 ° C, a specific gravity of 1.00 to 1.10 at 25 ° C and a refractive index of 1.40-1.41. Also suitable are graft or block copolymers of silicone, such as vinyl silicone copolymers having the general formula: wherein G5 is a monovalent portion which may independently be the same as different [sic] selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and -ZSA; where A is a polymeric vinyl segment consisting essentially of a polymerized monomer, polymerizable by free radicals, and Z is a divalent linking group. Useful divalent linking groups Z include alkylene of Cl-10, alkylarylene, arylene and alkoxyalkylene. Preferably Z is methylene or propylene; and wherein G6 is a monovalent portion that can be independently the same or different, and is alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and -ZSA; and where G2 is A; and G4 is A; and Rj_ is a monovalent portion that is independently the same or different, and is selected from alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and hydroxyl. Preferably Ri is a monovalent portion which is C1-4 alkyl and hydroxyl, more preferably methyl. R 2 may independently be the same or different, and is a divalent linking group such as alkylene, arylene, Ci-io alkarylene and alkoxyalkylene. R3 is a monovalent portion which can be independently the same or different and is alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen or hydroxyl. R 4 may independently be the same or different and are divalent linking groups including C 1-10 alkylene, arylene, alkarylene and alkoxy alkylene. The designation x is an integer of 0-3, ~ y is an integer of 5 or greater, and q is an integer of 0-3. These grafted or vinyl silicone block copolymers are described in U.S. Patent No. 5,468,477, which is incorporated herein by reference. Preferred is a vinyl silicone copolymer sold by 3-M Company under the trademark VS-80, which also has the CTFA name Polysilicone-8 and the chemical name poly (dimethylsiloxane) -g-polyacrylates. Polysilicone 8 is soluble in water and miscible with most organic solvents, a colorless to slightly yellow liquid with a specific gravity of 1,013 at 25 ° C, a viscosity of about 20 centipoise at 25 ° C and the polymer has a weight molecular weight of approximately 26,000. Also suitable for use as graft copolymers or silicone blocks are the acrylic-silicone graft copolymers as described in US Patent No. ,061,481, which is incorporated herein by reference. These acrylsilicone copolymers can be prepared by radical polymerization of a dimethylpolysiloxane compound having a radical group polymerizable in one of the terminal molecular chains, and the radically polymerizable monomer consists mainly of an acrylate or methacrylate or both. The dimethylpolysiloxane having a radical group polymerizable in one of the terminal molecular chains is represented by the following general formula: wherein Ri is methyl or hydrogen, R is a linear or branched, divalent hydrocarbon group having from 1 to 10 carbon atoms and optionally containing one or two ether linkages therein, and one is 3-300. Examples of R2 include -CH2-, - (CH2) 3-, - (CH2) 5-, - (CJH2) 8-, - (CH2)? 0-, -CH2-CH (CH3) -CH2-, and so on Also suitable as graft copolymers or silicone blocks are those having a vinyl, methacrylic or acrylic backbone and pendant siloxane groups and pendant fluorochemical groups. These polymers preferably contain monomers A, C, D and optionally repeating B, wherein: A is at least one acrylic or methacrylic ester polymerizable by free radicals of a 1,1-dihydroperfluoroalkanol or analog thereof or ega-hydrofluoroalkanols, fluoroalkylsulfonamido alcohols, fluoroalkyl cyclic alcohols and fluoroether alcohols. B is at least one reinforcing monomer copolymerizable with A, C is a monomer having the general formula X (Y) nSi (R) 3-mZm wherein X is a vinyl group copolymerizable with the monomers A and B, and is a divalent linking group which is alkylene, arylene, alkarylene and aralkylene of 1 to 30 carbon atoms which may incorporate ester, amide, urethane or urea groups. n is zero or 1; m is an integer of 1 to 3, R is hydrogen, C 1-4 alkyl, aryl or alkoxy, Z is a monovalent siloxane polymer portion; and D is at least one acrylate or methacrylate copolymer polymerizable by free radicals. These polymers and their manufacture are described in U.S. Patent Nos. 5,209,924 and 4,972,037, which are incorporated herein by reference. It is preferred where the polymer is a combination of monomers A, C and D, wherein A is a polymerizable acrylic or methacrylic ester of an alcohol fluroalkylsulfonamido, and wherein D is a methacrylic acid ester of a straight chain alcohol or branched off from C? -i2 YC as already defined. A polymer with portions of the general formula is more preferred: wherein a, b and c are 1-100,000, and the terminal groups may be straight chain or branched alkyl, aryl, alkoxy and the like, of C? _2o- These polymers may be purchased from Minnesota Mining and Manufacturing Company under the trademarks polymers "Silicone plus". More preferred is poly (isobutyl methacrylate -co-methyl FOSEA) -g-poly (dimethylsiloxane) which is marketed under the trademark SA 70-5 IBMMF. Preferred compositions of the invention contain 0.1-10% of a silicone selected from cyclic volatile silicones, water-insoluble non-volatile silicones, linear and vinyl silicone copolymers, or mixtures thereof.

OLEOUS CONDITIONING AGENTS The compositions of the invention may additionally contain 0.05-10%, preferably 0.1-8%, most preferably 1-7% of an oily conditioning agent which is an organic, non-volatile oil. The term "non-volatile" means that the oil does not have a measurable vapor pressure, that is, it has a vapor pressure less than about 2 mm of mercury at 20 ° C, preferably the non-volatile oil has a viscosity in the range from 10 to 1,000,000 centipoise at 25 ° C, preferably from 20 to 600,000 centipoise at 25 ° C. The oil may consist of esters of the formula RCO-OR 'wherein R or Rr each are independently an alkyl, alkenyl or alkoxycarbonyl alkyl or alkylcarbonyloxy straight or branched chain alkyl, of C? _25, preferably of C4-2o- Examples of these esters include isotridecyl isononanoate, PEG-4 diheptanoate, isostearyl neopentanoate, tridecyl neopentanoate, cetyl octanoate, cetyl palmitate, cetyl risinoleate, stearate cetyl, cetyl myristate, coco-bicaprylate / caprate, decyl isostearate, isodecyl oleate, isodecyl neopentanoate, isohexyl neopentanoate, octyl palmitate, dioctyl malate, tridecyl octanoate, myristyl myristate, octododecanol, and fatty alcohols as oleyl alcohol, isocetyl alcohol and the like, as well as the esters described on pages 24-26 of the CTFA Cosmetic Ingredient Handbook, first edition, 1988, which is incorporated herein by reference. The oil may consist of glyceryl esters of fatty acids or triglycerides such as castor oil, lanolin oil, triisocetyl citrate, triglycerides of C? O-? 8f caprylic / capric / triglycerides, coconut oil, corn oil, seed oil cotton, linseed oil, mink oil, olive oil, palm oil, illipe butter [sic], rape seed oil, soybean oil, sunflower seed oil, walnut oil, and the like . Also suitable as the oil are the glyceryl esters (excluding fats and oils which are glyceryl fatty acid esters) which are mainly mono-di- and triglycerides of fatty acids which are modified by reaction with other alcohols, for example, castor oil acetylated, glyceryl stearate, glyceryl dioleate, glyceryl distearate, glyceryl trioctanoate, glyceryl distearate, glyceryl linoleate, glyceryl myristate, glyceryl isostearate, PEG castor oils, glyceryl oleates PEG, glyceryl stearates PEG, cebacates glyceryl PEG, and others.

Also suitable as oil are non-volatile hydrocarbons such as isoparaffins, hydrogenated polyisobutene, mineral oil, squalene, petrolatum and others. Also suitable as the oil are lanolin derivatives such as acetylated lanolin, acetylated lanolin alcohol and others. Also suitable as the oil are different fluorinated oils such as fluoroesteres guerbet or perfluoro polyethers. Suitable perfluoro polyethers are described in U.S. Patent Nos. 5,183,589, 4,803,067, 5,183,588, all of which are incorporated herein by reference. These perfluoro polyethers are available commercially from Montefluos under the trademark Fomblin. Other suitable oils include sorbitan derivatives such as PEG sorbitan beeswax, PEG sorbitan isostearate, PEG sorbitan lanolate, PEG sorbitan laurate, PEG sorbitan oleate, PEG sorbitan palmitate, PEG sorbitan stearate, polysorbates, sorbitan trioleates, sorbitan sesquioleates. Sorbitan stearates, sorbitan tristearates, and others. The preferred non-volatile oils are the guerbet esters. The term "ester of guerbet" means an ester that is formed by the reaction of an alcohol, guerbet having the general formula: with a carboxylic acid of the general formula: R3COOH, or HOOC-R3-COOH wherein R1 and R2 are each independently a C4_2o alkyl and is a straight or branched chain saturated alkyl or alkenyl of C? so / - substituted or unsubstituted, or phenyl, wherein the substituents are halogen, hydroxyl, carboxyl and alkylcarbonylhydroxy. Preferably, the Guerbet ester is a fluoro-guerbet ester that is formed by the reaction of a Guerbet alcohol and carboxylic acid (as already defined), and a fluoroalcohol having the following general formula: CF3- (CH2) n-CH2- CH2-OH where n is from 3 to 40. The examples of the guerbet esters are as set forth in U.S. Patent No. 5,488,121 which is incorporated herein by reference. Suitable fluoro-guerbet esters are set forth in U.S. Patent 5,312,968 which is incorporated herein by reference. More preferred are the fluorosubstituted guerbet esters having the tentative CTFA name fluoro-octyldodecyl meadowfoamate. This ester is marketed by Siltech, Norcross Georgia as development ester L61125A, under the trademark Silube GME-F; or a cyclic fluoro-guerbet ester marketed under the trademark Fluorocxl ™ by Biosil, and with the chemical name dioctyldodecyl fluoroheptylcitrate. In addition, the composition may contain 0.001-5%, preferably 0.005-4% more preferably 0.01-3% by weight of humectant. The humectant is a hygroscopic ingredient that acts to wet the hair attracting water. Suitable humectants are polyhydric and dihydric alcohols such as propylene glycol, glucose, fructose, glycerin, maltitol and others. It is preferred where the conditioning composition of the invention contains 0.01-3% of a dihydric alcohol, in particular, propylene glycol. The invention will also be described in connection with the following examples which are set forth for the purpose of illustration only.

E TEMPLE 1 A hair conditioning composition was prepared according to the following formula: p / p% Water c.s Citric acid 0.15 M t ilparaben 0.20 Propilparaben 0.05 Panthenol 0.01 Cetearyl alcohol 2.00 Stearyl alcohol 1.20 Cetyl Alcohol 2.00 Propylene glycol 2.00 Ceteareth-20 0.50 Trimethylsilylamidomethicone 1.00 Perfume 0.50 Panthette 0.001 Behentrimonium Chloride 2.70 Dimethicone / dimethiconol 0.30 Dilinoleamidopropyl dimethylamine dimer dinoleate 1.40 Propylene glycol dicaprylate / dicaprate / PPGltrideceth-6 * 2.0 octyldodecyl fluoroheptyl citrate and cyclomethicone (40%) 1.0 0.50 ammonium / lactate / glycollate / isostearyl treatment * Policuaternium 37 ** Dermol ALFA, Alzo Inc. The above composition was prepared by mixing the ingredients in water and stirring well.

EXAMPLE 2 A hair conditioning composition was prepared according to the following formula: p / p% Perfume 0.80 Kathon CG (preservative) 0.04 Hydroxyethylcellulose 0.50 Cetyl alcohol 1.20 Stearamide propyldimethylamine 0.50 Ceramic alcohol / Ceteareth-20 - 2.0 Stearyl alcohol 1.0 Propylene glycol 2.0 Di (behenamidopropyl dimethyl LNA) dinoleate dimer 1.3 Methylparaben 0.2 Behentrimonium chloride 2.9 Propi lparaben 0.025 Citric acid 0.20 Polysilicone-8 * 0.50 Trimethylsilylamidodimethicone / octoxynol 40 isolauret- 2.0 6 / propylene glycol Sphingolipids 0.10 Citrate / glycolate / lactate / malate ** isostearyl 0.30 Dioctyldodecyldecyl-trimethylcitrate in cyclomethicone (40%) 1.00 * poly (dimethylsiloxane) -g-acrylates , marketed by 3- M Company with the brand VS-80. ** Dermol ALFA, marketed by Alzo, Inc.

EXAMPLE 3 A conditioning composition for hair was prepared according to the following formula: p / p% Water cs Citric acid 0.15 Methylparaben 0.20 Propylparaben 0.05 Panthenol 0.01 Cetearyl alcohol 2.00 Stearyl alcohol 1.20 Cetyl alcohol 1.00 Ceteareth-20 0.50 Trimethylsilylamidomethicone / bait chloride 2.00 trionium / nonoxynol-10 Perfume 0.50 Behentrimonium chloride 2.00 Dilinoleaiiiidopropyl dimethylamine dimer dinoleate 1.25 Malate / lactate / glycolate / citrate * isostearyl 0.30 Stearamide propyldimethylamine 0.75 Hydroxyethylcellulose 0.75 Cocamidopropylbetaine 2.00 Kathon CG 0.04 Dlmeticone copolyol eicosanate 0.01 Dermol ALFA, Alzo, Inc.

The above composition was prepared by mixing the ingredients in water and stirring well. Although the invention has been described in connection with the preferred embodiment, it is not intended to limit the scope of the invention to the particular form established, but on the contrary, it is intended to cover these alternatives, modifications and equivalents as may be included within the spirit and scope of the invention as defined in the attached clauses.

Claims (19)

1. A conditioning composition for hair containing, by weight of the total composition: 0.1-20% cationic conditioning agent, 0.1-20% of one or more alpha or beta hydroxy acid esters, 0.1-30% fatty alcohol, 0.001- 10% nonionic surfactant, and 5-95% water.

2. The composition of claim 1, which contains one or more alpha hydroxy acid esters in addition to one or more beta hydroxy acid esters. The composition of claim 1, wherein the cationic conditioning agent is selected from the group consisting of: (a) a quaternary ammonium salt with the formula: wherein Rx is an aliphatic group of 1 to 22 carbon atoms, or aromatic, aryl or alkaryl group having from 12 to 22 carbon atoms; R2 and R3 each are independently an aliphatic group having 1-22 carbon atoms; and R 4 is an alkyl group of 1 to 3 carbon atoms, and X is an anion selected from halogen, acetate, phosphate, nitrate and methyl sulfate radicals. (b) a cationic silicone having the following formula: (R) aG3-a-Si- (-OSÍG2) n- (-0sÍGb (Rx) 2-b) m-0-SiG3-a (R1) a wherein G is H, phenyl, OH, C? -10 alkyl; a is 0 or an integer from 1 to 3; b is 0 or 1; the sum n + m is a number from 1 to 2,000; n is a number from 0 to 2,000; and m is an integer from 1 to 2,000; and Rx is a monovalent radical of the formula CqH2qL in which q is an integer from 2 to 8 and L is selected from the groups: -N (R2) CH2-CH2-N (R2) 2 -N (R2) 2 + -N (R2) 3A ~ + + -N (R2) CH2-CH2-NR3H2A ~ in which R2 is H, phenyl, benzyl, a saturated hydrocarbon radical and an alkyl radical containing from 1 to 20 carbon atoms is preferable; and A- is a halide ion; (c) an amide of the formula wherein R is a straight or branched chain alkyl, C? 2-22r n is an integer from 1 to 4 and X is lower alkyl, preferably methyl (c) an amidoamine salt; and (d) mixtures thereof. 4. The composition of claim 3, wherein the quaternary ammonium salt, Rx is a C2-22 alkyl, and R2 / - 3 and R4 are methyl. The composition of claim 5, wherein the quaternary ammonium salt is benetrimonium chloride [sic], cetrimonium chloride or mixtures thereof. The composition of claim 3, wherein the amide is di (behenamidopropyl dimethyl amine) dimer dilinoearate [sic], di (linoleamidopropyl dimethylamine) dimer linoleate, or mixtures thereof. The composition of claim 2, wherein the esters of the alpha hydroxy acids have the following general formula: wherein Ra and Rb are each independently H, F, Cl, I, Br, alkyl, aralkyl or straight or branched chain aryl or cyclic isomeric or nonisomeric, saturated or unsaturated form having 1-30 carbon atoms; and in addition Ra and Rb can carry OH, CHO, COOH, or alkoxy groups having from 1 to 10 carbon atoms; and Rc is a straight or branched chain, saturated or unsaturated alkyl having from 6 to 30 carbon atoms; and m and n are each independently integers from 0 to 2 with the proviso that n and m can not both be 0. The composition of claim 7, wherein Ra is selected from CH 2 CHOHCOOH, CHOHCH 3, and CH 20 H. 9. The composition of claim 8, wherein Rb is selected from 0 to CH2OH. 10. The composition of claim 9, wherein Rc is a branched chain C8 alkyl. The composition of claim 10, wherein the alpha and beta hydroxy acid esters are a mixture of isostearyl citrate, isostearyl lactate, isostearyl malate and isostearyl glycolate. The composition of claim 1, wherein the fatty alcohol has the formula RCH 2 OH, wherein R is a saturated or unsaturated alkyl, straight or branched chain having at least about 6 to 30 carbon atoms. The composition of claim 12, wherein the fatty alcohol is selected from the group consisting of cetyl alcohol, stearyl alcohol and mixtures thereof. 14. The composition of claim 1, wherein the nonionic surfactant is an alkoxylated alcohols [sic] formed by the reaction of an alcohol with an alkylene oxide. 15. The composition of claim 14, wherein the acylated alcohol is formed by the reaction of ethylene oxide and a fatty alcohol having from 6 to 30 carbon atoms. The composition of claim 14, wherein the nonionic surfactant is formed with the reaction of ethylene oxide and a mixture of cetyl and stearyl alcohol. The composition of claim 16, wherein the non-ionic surfactant is Ceteareth-20. 18. The composition of claim 1 further contains 0.01-20% of a silicone conditioning agent. The composition of claim 18, wherein the silicone conditioning agent is selected from the group consisting of: (a) cyclic volatile silicones having the general formula: where n = 3-7; (b) linear volatile silicones having the general formula: (CH3) 3 Si-0- [Si (CH3) 2-0] n-Si (CH3) 3 where n = 0-7, preferably 0-5; (c) non-volatile silicone fluids insoluble in water having the general formula: wherein R and R 'are each independently alkyl or aryl, and x and y are each independently 0-100,000 with the proviso that there is at least x or y, and A is a siloxy capacete unit. (d) trialkylsiloxysilicate polymers having the general formula: [< RR'R ») 3Si01 / 2]? [S¡o2jy wherein R, R 'and R "are each independently a straight or branched chain alkyl of C? _? o or phenyl, and y and are such that the ratio of the units (RR'R") 3SYO / 2 to the units SIOO2 is 0.5 wing l.5 a l. (e) vinyl silicone copolymers having the general formula: where: Gs is a monovalent portion which can independently be the same as different [sic] selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and ZSA; A is an essential vinyl polymeric segment [sic] of a polymerized monomer polymerizable by free radicals, Z is a divalent linking group which is alkylene of C-ioalkylarylene and alkoxyalkylene, G6 is a monovalent portion which can be independently same or different, and is alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and -ZSA, G2 is A, G4 is A, Rx is a monovalent portion that is independently the same or different, and is selected from alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen and hydroxyl, R2 can be independently the same or different, and is a divalent linking group such as: C? _? al, arylene, alkarylene and alkoxyalkylene, R3 is a monovalent portion which can be independently the same or different and is alkyl, aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen or hydroxyl, R4 can independently be the same or different and are divalent linking groups including alkylene, arylene, alkarylene and alkylene-alkylene of C? _? o, x is an integer of 0-3, and is an integer of 5 or greater, and q is an integer of 0-

3. (f) acrylic-silicone graft copolymers prepared by the radical polymerization of a dimethylpolysiloxane compound having a radical group polymerizable in one of the terminal molecular chains, having the following general formula: wherein R x is methyl or hydrogen, R 2 is a linear or branched, divalent hydrocarbon having 1-10 carbon atoms and optionally containing one or two ether linkages therein, and 1 is 3-300; with an acrylate or methacrylate or both; and (f) acrylic-silicone copolymers having a methacrylic or acrylic backbone and pendant siloxane groups and pendant fluorochemical groups; (g) hydroxy-substituted polydimethylsiloxanes, and (h) mixtures thereof.