HK1195877B - Hair care compositions - Google Patents

Description

Hair care composition

The application is a divisional application of Chinese patent application with application number 200980115313.9 (PCT/US 2009/038195), application date 3-25 of 2009 and invention name 'hair care composition'.

Technical Field

The present invention relates generally to compositions for use on hair. More particularly, the present invention relates to cosmetic compositions for improving the color retention of artificially colored hair and/or for applying films to lightening and feel-enhanced hair.

Background

Consumers have used a wide variety of cosmetic and personal care compositions to promote and/or modify the appearance of keratin fibers such as hair. One stylish change is to impart an artificial color to hair using chemical dyes. For example, hair may be treated with direct dyes or oxidative dyes, also known as "permanent" hair dyes, to achieve a desired color.

It is known in the art that artificial hair color, particularly red color tones, obtained by treatment with chemical dyes can quickly fade due to repeated shampooing and washing. Chemical dyes used to impart color to hair tend to increase the porosity of the hair keratin fibers. The increased porosity provides increased surface area and allows increased flow of fluid (e.g., water) through the hair fibers, thereby increasing the rate at which chemical dye molecules leach from the hair. Artificially colored hair can show significant fading after only a few washes. In particular, it has been demonstrated that more than 20% of the artificial hair color has disappeared during the first 5 washes.

Most hair care products currently available (e.g. hair conditioners, hair sprays) are specifically formulated as hydrophilic compositions. Such hair products are easily removed with water, with or without the addition of a shampoo, bringing the hair fibers into direct contact with the water and thereby allowing the chemical dye molecules to filter from the hairAnd (6) discharging. For example, US patent US6,706,674 describes a hair styling composition comprising a vinyl copolymer and a non-aqueous solvent. The nonaqueous solvent may contain a plurality of C₂-C₆An alcohol. It is stated that some embodiments of the hair styling composition may comprise triisostearyl trilinoleate as a viscosity control agent and/or fluoro C as a emollient_2-8Alkyl polydimethyl siloxane.

Recent advances in facilitating color retention and/or reducing color fading of artificially colored hair include the use of color protection agents. Typically, these color protection agents can be incorporated into hair care compositions by emulsifying, dissolving, or otherwise making them compatible with such hair care product compositions. The color protection agent may include mild surfactants, cationic conditioning agents, amino-functional silicones, uv absorbers, starch or sugar surfactants.

For example, US patent US5,922,310 describes a composition for preventing artificial hair dyes from fading and/or for slowing down the oxidation of hair comprising cationic antioxidant phenols.

US patents US6,129,909 and US6,180,091 describe hair treatment compositions comprising diesters or polyesters of naphthalene dicarboxylic acids for delivering gloss and/or color stability. It is stated that naphthalene dicarboxylic acids can be incorporated into the aqueous phase of hair treatment compositions to deliver improved light stability.

US patent US5,045,307 describes a method of treating dyed hair to reduce fading caused by exposure to solar uv light by applying an effective amount of a hair treating article comprising an effective amount of a water-insoluble benzophenone compound which is readily combined with a hair-durable carrier composition.

US patent US6,143,286 describes hair conditioning compositions comprising a cationic conditioning agent, a fatty alcohol, a non-ionic surfactant and a specific silicone polymer having difunctional and trifunctional units, the ratio of difunctional to each trifunctional unit being about 10: 80.

US patent publication No. US2005/0188481 describes compositions comprising at least one amylose-containing starch and their use for prolonging or improving the color durability and stability of artificially colored hair.

A number of hair dye manufacturers have incorporated color protection agents into "color-blocking" conditioners used after the first shampooing of newly artificially colored hair. However, the use of such conditioners does not provide enhanced color retention and/or reduced color fading during the first shampooing. During the first shampooing, newly artificially colored hair cannot be waterproofed or shampooed. Thus, a large number of chemical dye molecules can now leach out of the hair, resulting in a large amount of fading of the newly artificially colored hair before the color protectant is applied.

Despite advances in color protection agents, there remains a need in the art for enhanced color retention and/or reduced fading of artificially colored hair. It is therefore an object of the present invention to provide compositions and methods for imparting enhanced color retention and reduced color fading to artificially colored hair.

Disclosure of Invention

In accordance with the above and other objects, the present invention provides hair care compositions which impart improved color retention or reduced fading to artificially colored hair.

The present invention provides in a first aspect a hair care composition for improving colour retention in dyed hair comprising in a suitable vehicle at least two and preferably all three of the following ingredients: (i) silicone (silicone) polyurethane polymers; (ii) a film-forming ester; and (iii) a fluorosilicone. In various embodiments, the silicone polyurethane is a bis-hydroxypropyl dimethicone/SMDI copolymer; and/or the film forming ester is triisostearyl trioleate; and/or the fluorosilicone is perfluorononyl polydimethylsiloxane. The vehicle is preferably one in which the silicone polyurethane polymer, film-forming ester and fluorosilicone are dispersible but insoluble. An example of such a vehicle is an aqueous system comprising water and a thickener, for example a cationic thickener.

In another aspect, the present invention provides a method of improving color retention of artificially colored hair comprising applying to the colored hair any of the compositions of the present invention. These compositions can be applied to wet or dry hair, can be applied immediately after the hair is dyed, can be applied before the first wash (shampooing) or even after the first, second or third wash after the hair is dyed, while still providing measurable resistance to fading.

These and other aspects of the present invention will become apparent to those skilled in the art upon reading the following detailed description of the invention, including the exemplary embodiments and examples.

Detailed Description

In the following description of the present invention, it is to be understood that the terms used herein have their ordinary and customary meaning in the art, unless otherwise indicated. Unless otherwise stated, all weight percentages referred to herein are given in "% by weight" of the total composition.

The term "hair" means any hair of the body, including hair of the scalp, eyelashes, beard on the lips, beard, etc. In a preferred embodiment, the composition is applied to the hair of the scalp.

The present invention is based in part on the following findings: the film forming ester triisostearyl trioleate provides a stable water and surfactant resistant film, particularly when combined with silicone polyurethane polymers and/or fluorosilicones. The compositions of the present invention provide effective color retention and reduced color fading of artificially colored hair, particularly after repeated shampooing. In addition, such compositions impart desirable feel to the hair.

Preferred compositions generally comprise a combination of a silicone polyurethane polymer, a film-forming hydrophobic ester, and a fluorosilicone that is preferably both hydrophobic and oleophobic. It has been found that this novel composition has improved color retention and/or reduced fading on artificially colored hair.

Without wishing to be bound by any theory, it is believed that the combination of the present invention forms a water-repellent film on keratin fibres, thereby acting as a protective barrier against water and/or shampoo and improving the retention of dye molecules in artificially dyed hair. The waterproof membrane is not easily removed with water or shampoo alone and thus slows the rate of leaching of the chemical dye molecules from the hair.

The compositions of the present invention impart improved color retention and/or reduced fading to artificially colored hair using any range of relative proportions of silicone polyurethane polymer (a) to ester (b) to fluorosilicone (c), the ratio being expressed as a: b: c. Typically, a, b and c independently range from about 1 to about 50, more typically from about 1 to about 25, and usually from about 1 to about 10. Preferably, a, b and c independently range from about 1 to about 5, more preferably from about 1 to about 3, more preferably from about 1 to about 2, including a weight ratio of silicone polyurethane polymer to ester to fluorosilicone of from about 1:1:1 to about 10:1:10, more typically from about 1:1:1 to about 5:1:5, typically about 1:1: 1.

It is believed that the combination of the three major ingredients results in benefits not observed with each single ingredient or the same composition lacking the silicone polyurethane polymer, ester or fluorosilicone.

A first component of some embodiments of the compositions of the present invention is a silicone polyurethane polymer. There is essentially no limitation on the nature of the silicone polyurethane polymer, and any polymer comprising organosiloxane units and urethane linkages can be used in the practice of the present invention.

In one embodiment, the silicone polyurethane polymer is the reaction product of a hydroxy-functional polyorganosiloxane (preferably containing two or more hydroxy groups) and a diisocyanate moiety. Hydroxy-functional polyorganosiloxanes typically have the structure of formula I:

wherein R is independently at each occurrence selected from hydrogen, hydroxy and optionally substituted hydrocarbyl containing 1 to 10 carbon atoms, and in particular from optionally substituted alkyl, alkenyl, alkynyl, aryl, alkyl-aryl or aryl-alkyl; preferably R is selected from optionally substituted branched, straight or cyclic C_1-6Alkyl or alkenyl groups including, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclohexyl, vinyl, allyl, and the like, or C_1-8Aryl, alkyl-aryl or aryl-alkyl groups including, but not limited to, phenyl, benzyl, tolyl, xylyl, and the like;

wherein each of the aforementioned R groups may include optional substitution of one or more heteroatoms, including oxygen, nitrogen, phosphorus and halogens, particularly fluorine, with fluoroalkyl groups being typical (including perfluoroalkyl groups), such as mono-, di-and tri-fluoromethyl, perfluorophenyl, and the like, amino-substituted C_1-6Alkyl, including having the form- (CH)₂)_1-6-NR^N ₂And- (CH)₂)_1-6-NR^N-(CH₂)_1-6-NR^N ₂Wherein R is^NTypically hydrogen, but may be methyl, ethyl, propyl, and the like; polyether groups, including, but not limited to, the form- (CH)₂CH₂O)_nPolyethylene oxide group of (E), form- (CH)₃)CH₂O)_n-polyoxypropylene groups and combinations thereof; and amine oxide, phosphate, hydroxyl, ester and/or carboxylate functionalities, and the like; or wherein R may comprise an additional group-L-OH;

wherein L represents a bond or a linker; preferably L is a linker selected from divalent hydrocarbons having 1-10 carbon atoms, including divalent alkyl, alkenyl, alkynyl, aryl, alkyl-aryl or aryl-alkyl groups, and C_1-10Alkyl is typical and includes, but is not limited to, the form- (CH)₂)_1-10A divalent radical of (E), preferably- (CH)₂)_1-6-, more preferably L is-CH₂CH₂CH₂-；

And wherein n is an integer of 0 to 5,000, preferably 1 to 200, more preferably 10 to 100, more preferably 10 to 50. Preferably, R represents methyl in at least one or more occurrences, more preferably R represents methyl in all or substantially all occurrences, in the sense that R represents methyl in more than 90%, 95%, or 98% occurrences.

In one embodiment of the present invention, the hydroxy-functional polyorganosiloxane prepolymer comprises polymethylsiloxane and has the structure of formula Ia:

wherein L and n are as defined above. In a preferred embodiment of the present invention, the hydroxy-functional polyorganosiloxane is bis-hydroxypropyl polydimethylsiloxane comprising polymethylsiloxane and having the structure of formula Ib:

wherein n is as defined above.

The diisocyanate has the form O = C = N-R¹-N = C = O, wherein R¹Is a divalent hydrocarbon radical containing from 1 to 20 carbon atoms, including optional substitution with one or more heteroatoms, and in particular R¹Selected from optionally substituted branched, straight chain or cyclic alkyl, alkenyl, alkynyl, aryl, alkyl-aryl or aryl-alkyl; including, but not limited to:

a group of the form:

a group of the form:

a group of the form:

a group of the form:

and;

a group of the form:

and combinations thereof.

Suitable diisocyanates include, but are not limited to, dicyclohexylmethane-4, 4' -diisocyanate (SMDI); toluene diisocyanate; methylene diphenyl diisocyanate including 2,2' -MDI, 2,4' -MDI and 4,4' -MDI; 1, 6-hexamethylene diisocyanate; isophorone diisocyanate; methylene dicyclohexyl diisocyanate; xylene diisocyanate; cyclohexane diisocyanate; 3,3 '-dimethyl-4, 4' -diphenylmethane diisocyanate; p-phenylene diisocyanate; meta-phenylene diisocyanate; 4,4' -isopropylidene dicyclohexylisocyanate and the like. In a preferred embodiment, the diisocyanate comprises, consists essentially of, or consists of SMDI.

The polyorganosiloxane polyurethane polymer comprises repeating units derived from a hydroxy-functional polyorganosiloxane and a diisocyanate in the form of an AB alternating copolymer, wherein unit a has the structure of formula II:

wherein R, L and n are as defined above for formulas I, Ia and Ib, and wherein unit B has the structure of formula III:

wherein R is¹As defined above, and wherein units a and B are arranged in a linear, branched or cyclic configuration.

When the polymer is a cyclic polymer, it can be represented as:

wherein z is an integer value from 2 to 2,000. Wherein the polyorganosiloxane polyurethane polymer is cyclic and the propagation of the polymer is self-terminating. However, in the case of linear polymers, termination can be accomplished by: for example, the polymerization is carried out, the reaction is stopped with a monoalcohol or an amine such as a dialkylamine using a stoichiometric excess of the dihydroxy polyorganosiloxane of formula I relative to the diisocyanate, the monofunctional reactant, for example the mono-hydroxy polyorganosiloxane analogue of formula I and/or the monofunctional isocyanate reactant, is included quantitatively in the reaction mixture; or any other suitable method of terminating the urethane polymerization reaction. Thus, the polyorganosiloxane polymers may have different terminal groups including, but not limited to, hydroxyl groups including the group-L-OH, tri-alkylsilyl including trimethylsilyl, hydrocarbons such as linear, branched or cyclic alkyl or aryl groups, which may be amines, methanol, silanols, and the like.

The polymer may also comprise branching or grafting sites on the polyorganosiloxane, where one or more of the radicals R on formula I or II are, for example, the following radicals:

wherein R is as defined for formula I, R may represent a group-L-O-which further couples a side chain of unit B of formula III, whereby it may further couple with unit A of formula II, etc., or R may represent-L-OH, a group R as defined above, or a terminal group. When the polyorganosiloxanes contain branching or grafting points of this type, they may be present as T-type or Q-type branches or grafts, where T denotes that only one R group on the Si atom is a polyorganosiloxane chain as indicated above, and Q denotes that both twin R groups are of the polyorganosiloxane type. These types of polyorganosiloxane compounds are known as T-resins or Q-resins, branched or graft copolymers of polyorganosiloxane polyurethanes.

Polyorganosiloxane polyurethane polymers can also be prepared from functionalized isocyanate prepolymers. For example, the isocyanate prepolymer may be a difunctional or polyfunctional polyorganosiloxane isocyanate, such as a polyorganosiloxane diisocyanate of the formula IV:

r, R therein¹And L is as defined above, and wherein x is an integer from 0 to 5,000, preferably from 1 to 200, more preferably from 10 to 100, and more preferably from 10 to 50. The prepolymer may also be made multifunctional by introducing groups that also have isocyanate groups on one or more of the R groups. The isocyanate-functional polyorganosiloxane prepolymer is reacted with a hydroxy-functional polyorganosiloxane prepolymer, such as formula I or a polyfunctional analog thereof. The prepolymer of formula IV typically has a molecular weight of from about 4,000 to about 15,000 daltons. Prepolymers of formulas I, Ia and Ib typically have molecular weights of from about 250 to about 15,000 daltons.

In one presently preferred embodiment, the polyorganosiloxane polyurethane polymer used in the hair care compositions of the present invention is a copolymer comprising the reaction product of Ib and saturated methylene diphenyl diisocyanate (SMDI). A typical silicone polyurethane polymer is bis-hydroxypropyl dimethicone/SMDI copolymer (INCI).

A second ingredient of some embodiments of the hair compositions is a high molecular weight hydrophobic ester, which can form a water repellent hydrophobic film on the hair. The hydrophobic esters may be saturated or unsaturated and may include, but are not limited to, mono-esters of fatty acids, di-esters of dibasic acids, di-esters of tribasic acids, and tri-esters of tribasic acids. Monoesters include straight, branched or cyclic C₄-C₂₄Preferably C₈-C₂₄More preferably C₁₂-C₂₂Monocarboxylic acids and straight, branched or cyclic C₄-C₃₆Preferably C₈-C₂₄More preferably C₁₂-C₁₈Esterification products of alcohols. Diesters including straight, branched or cyclic C₄-C₄₈Dicarboxylic acids, typically C₈-C₄₄Dicarboxylic acids, more typically C₁₂-C₃₆Dicarboxylic acids with straight, branched or cyclic C₄-C₃₆Preferably C₈-C₂₄More preferably C₁₂-C₁₈Esterification products of alcohols. The dicarboxylic acid may be, for example, a dimer acid formed by dimerization of unsaturated fatty alcohols, such as linoleic acid. Diesters and triesters of tribasic acids including C₆-C₇₂Tricarboxylic acids, typically C₁₂-C₆₆Tricarboxylic acids with straight, branched or cyclic C₄-C₃₆Preferably C₈-C₂₄More preferably C₁₂-C₁₈Esterification products of alcohols. The tricarboxylic acid may be, for example, a trimer acid formed by trimerization of an unsaturated fatty alcohol, such as linoleic acid.

The esters are preferably high molecular weight esters, meaning that the molecular weight is at least 500. In some embodiments, the molecular weight of the ester is at least 750, at least 1000 or at least 1200. The esters are preferably hydrophobic. In a preferred embodiment of the invention, the ester is dispersible but insoluble in the vehicle.

One suitable hydrophobic ester is triisostearyl trilinoleate (INCI) (CAS Registry No.103213-22-5), available from Lubrizol Advanced Materials, Inc., under the trade name SCHERCEMOL^TMTIST Ester。

A third component of some embodiments of the compositions of the present invention is a fluorosilicone, which delivers excellent spreading characteristics. Fluorosilicones are preferably hydrophobic and oleophobic and are also preferably insoluble, but dispersible in the vehicle. There is essentially no restriction on the nature of the fluorosilicone. In one embodiment, the fluorosilicone comprises a fluorine substituted polyorganosiloxane. Fluorosilicones typically comprise the form- [ Si (R)₂)(R₃)-O]A repeating unit of (A) wherein R₂And/or R₃Independently is alkyl, aryl or alkylaryl (e.g. benzyl), wherein R₂And R₃Is substituted with one or more fluorine atoms. Preferably R₂Or R₃At least one of is C_1-30Alkyl, which contains one or more fluorine atoms and preferably contains perfluorinated segments, has the meaning of the form- (CF)₂)_xA segment of (a) wherein x is an integer from 1 to 29 and/or trifluoromethyl.

Preferred fluorosilicones have the general structure of formula V below:

wherein m is an integer of 1 to 5,000, preferably 1 to 200, more preferably 10 to 100, more preferably 10 to 50; wherein n is an integer from 0 to 4,999, preferably from 1 to 200, more preferably from 10 to 100, more preferably from 10 to 50; and wherein x is an integer from 0 to 12. One suitable fluorosilicone is under the trade name Phoenix Chemical, IncFSL-150、FSL-300. Perfluorononyl polydimethylsiloxanes sold under FSH-150, FSH-300, FSU-150 and FSU-300, all having the chemical Abstract number CAS 259725-95-6.

The hair care compositions of the present invention comprise a cosmetically acceptable vehicle. By "cosmetically acceptable" it is meant that the vehicle is safe when in contact with the external surface of the human body. It is useful to focus on any cosmetically acceptable vehicle known in the art. The vehicle may comprise water or a hydrophobic or hydrophilic organic solvent. Suitable hydrophilic solvents include, but are not limited to, alcohols (e.g., ethanol, isopropanol, benzyl alcohol, phenethyl alcohol, and the like), propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, octylene glycol, glycerol, carbitol, glycol ethers such as ethylene glycol monomethyl ether, monoethyl ether, and monobutyl ether, propylene glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol, and diethylene glycol alkyl ethers such as diethylene glycol monoethyl ether or monobutyl ether, and combinations of any thereof. Water is the preferred vehicle ingredient. Typically, the amount of water in the vehicle is from about 20% to about 99%, more typically from about 60% to about 95% by weight.

Suitable hydrophobic vehicles include hydrocarbon oils, which may be saturated or unsaturated, have aliphatic character and are straight or branched chain or contain alicyclic or aromatic rings. Essentially any oil is useful, however, highly hydrophobic oils are preferred. Suitable non-limiting examples include vegetable oils; esters such as octyl palmitate, isopropyl myristate and isopropyl palmitate; ethers such as dioctyl ether; fatty alcohols such as cetyl alcohol, stearyl alcohol and behenyl alcohol; isoparaffins such as isooctane, isododecane, and isohexadecane; silicone oils such as polydimethylsiloxane, cyclic siloxane and polysiloxane; hydrocarbon oils such as mineral oil, vaseline oil, isoeicosane and polyisobutylene; natural or synthetic waxes, and the like.

Suitable hydrophobic hydrocarbon oils may be saturated or unsaturated, have aliphatic character and are straight-chain or branched or contain alicyclic or aromatic rings. Hydrocarbon oils include those having from 6 to 20 carbon atoms, more preferably from 10 to 16 carbon atoms. Representative hydrocarbons include decane, dodecane,Tetradecane, tridecane and C_8-20An isoparaffin. Paraffinic hydrocarbons are available from Exxon under the ISOPARS trademark and Permethyl Corporation. Further, Permethyl Corporation, manufactured under the trade name Permethyl99A^TMC of (A)_8-20Paraffinic hydrocarbons such as C₁₂Isoparaffins (isododecane) are also suitable. Various commercial C₁₆Isoparaffins such as isohexadecane (having the trade name Permethyl R)^TM) Are also suitable. Examples of preferred volatile hydrocarbons include polydecanes such as isododecane and isodecane, including, for example, Permethyl-99A (Presperse Inc.) and C₇-C₈To C₁₂-C₁₅Isoparaffins such as Isopar Series available from Exxon Chemicals. A representative hydrocarbon solvent is isododecane.

The vehicle may comprise a silicone phase, which may include volatile silicone oils, non-volatile silicone oils, and combinations thereof. By volatile silicone oil is meant that the oil is susceptible to evaporation at ambient temperature. Typically, volatile silicone oils exhibit a vapor pressure of from about 1Pa to about 2kPa at 25 ℃; preferably having a viscosity of from about 0.1 to about 10 centistokes, preferably less than about 5 centistokes, preferably less than about 2 centistokes, at 25 ℃; and boils at about 35 c to about 250 c at atmospheric pressure.

Volatile silicones include cyclic and linear volatile dimethylsiloxane silicones. In one embodiment, the volatile silicones may include cyclomethicones, including tetrameric (D4), pentameric (D5), and hexamethomethicones (D6) cyclomethicones, or mixtures thereof. Particular mention may be made of the volatile cyclopolydimethylsiloxane hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethyl-cyclopentasiloxane. Suitable polydimethylsiloxane polymers are available from Dow Corning under the name Dow CorningFluid and has a viscosity of 0.65 to 600,000 centistokes or more. Suitable non-polar volatile liquid silicones are disclosed in U.S. Pat. No. 4,781,917, which is incorporated herein by reference in its entirety. Other volatile siloxane-based materials are describedIn Todd et al, "voltate Silicone fluids for Cosmetics", Cosmetics and Toiletries,91:27-32(1976), which is incorporated herein by reference in its entirety. Linear volatile silicones generally have viscosities of less than about 5 centistokes at 25 ℃, while cyclic silicones generally have viscosities of less than about 10 centistokes at 25 ℃. Examples of volatile silicones of different viscosities include Dow Corning200, Dow Corning244, Dow Corning245, Dow Corning344 and Dow Corning345(Dow Corning Corp.); SF-1204 and SF-1202Silicone Fluids (G.E. silicones), GE7207 and 7158(General Electric Co.); and SWS-03314(SWS Silicones Corp.), linear volatile Silicones including low molecular weight polydimethylsiloxane compounds such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and the like.

The non-volatile silicone oils typically include polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes or mixtures thereof. Polydimethylsiloxanes are preferred non-volatile silicone oils. Non-volatile silicone oils typically have a viscosity of from about 10 to about 60,000 centistokes at 25 ℃, preferably from about 10 to about 10,000 centistokes, more preferably from about 10 to about 500 centistokes; and a boiling point greater than 250 ℃ at atmospheric pressure. Non-limiting examples include dimethylpolysiloxane (polydimethylsiloxane), phenyl trimethicone, and diphenyl polydimethylsiloxane.

The vehicle may comprise a single phase, a biphasic system or an emulsion. Emulsions include oil-in-water, silicone-in-water, water-in-oil, water-in-silicone, and the like. When formulated as an emulsion, an emulsifier is typically included. If the product is designated as a spray, it is desirable to use a single phase vehicle or a dual phase vehicle comprising an aqueous phase and an oil phase, the oil phase comprising a silicone oil. Alternatively, the vehicle may be anhydrous. The anhydrous vehicle preferably comprises silicone oil. It is to be understood that the term "anhydrous" as used herein means that the composition comprises up to 5% water, more typically means that the composition comprises up to 1% water and typically the composition comprises an amount of water absorbed from ambient conditions.

In one embodiment, the combination of the silicone polyurethane polymer, film-forming ester, and fluorosilicone of the present invention is dispersible, but insoluble in the vehicle. It has been surprisingly found that the fading of hair color is significantly delayed when the combination is formulated with an incompatible vehicle than when the same vehicle is otherwise more compatible with the combination. Without wishing to be bound by any theory, it is believed that phase separation provides improved deposition of the inventive combination on hair keratin fibers and thereby improves the water resistant film covering formed by the protective barrier acting as a water resistant and/or shampoo.

In a preferred embodiment, the vehicle is a thickened aqueous system comprising water and a thickener. The thickener may be nonionic, cationic, anionic or zwitterionic. Preferably, the thickener is a cationic thickener including, but not limited to, cationic conditioning polymers. Suitable cationic polymers include, but are not limited to, cationized cellulose, cationized guar gum, diallyl quaternary ammonium salt/acrylamide copolymer, polyquaternium-37, and mixtures thereof. Among various cationic thickeners, a polyquaternium-37 (INCI) is particularly exemplified.

Other suitable thickeners may include, for example, homopolymers of acrylic acid (under the trade nameSold by Lubrizol Corp.), acrylates/C_10-30Alkyl acrylate Cross-Linked Polymer (available under the trade name1342 and 1382; and from BFGoodrichTR-1 and TR-2), acrylate/Steareth-20 itaconate copolymer (trade name from National Starch)2001) acrylate/Ceteth-20 itaconate copolymers (available from nature)Trade name of nal Starch3001) Bentonite, PVM/MA decadiene crosspolymer which is a crosspolymer of crosslinked methyl vinyl ether/maleic anhydride copolymers of 1, 9-decadiene (commercially available under the trade name from International Specialties Products)QM), acrylate/steareth-20 methacrylate copolymer (under the trade name ACRYSOL)^TMSold under ICS-1 by Rohm and Haas Co.), acrylamide/sodium acrylate copolymer (under the trade nameSold by hoechst AG under the name PN 73), acrylate copolymers (sold by Goldschmidt under the name anti l 208), acrylic acid/acrylyl nitrogen copolymers (sold under the name acrylic acid/acrylyl nitrogen copolymersSA-100H, supplied by Lipo under SR-150H), acrylic acid/acrylate copolymer (under the trade name5514. 515, 525, XL-19X2, X1-28, XL-40, 526, sold by BF Goodrich), ammonium acrylate/acrylyl nitrogen copolymer (sold under the trade name "Xl")Sold by Lipo under SS-201), quaternary ammonium salt-18 bentonite which is a sodium salt of crosslinked poly (acrylic acid) (sold by 3V under the trade names PNC430, PNC410, PNC 400), selectrium chloride hectorite (sold under the trade name PNC430, PNC410, PNC 400), and the likeSold by Southern Clay Products, infra), the quaternary ammonium salt-18 hectorite (Bentone38), the selelammonium chloride hectorite (Bentone27), the poly (acrylic acid) (sold under the trade name "poly (acrylic acid)")Sold by BF and under the trade name of BF at 400Sold by Alco, infra), trihydroxystearin (commercially available under the trade name Rheox)And the Southern Clay Products under the trade name FLOWTONE^TM) Dimethylaminoethyl methacrylate and acrylamide copolymers (from Ciba Specialties)SC63), acrylic polymer anionic or cationic thickeners (under the trade name SYNTHALEN)^TMSold by 3V below), polyacrylate-1 crosslinked polymer (INCI) (trade nameSold by Lubrizol Corp. under Aqua CC), sodium acrylate copolymer (under the trade name ofSold by Ciba under ADM) and polyacrylamidomethylpropanesulfonic acid (sold by Cognis Care Chemicals under the trade name Cosmedia HSP-1180).

The thickener preferably comprises from about 0.001% to about 25%, more preferably from about 0.1% to about 15%, more preferably from about 0.5% to about 5% by weight of the vehicle.

The silicone polyurethane polymer, film-forming ester, and fluorosilicone collectively comprise from about 1% to about 50% by weight of the total composition, including the vehicle. More typically, the silicone polyurethane polymer, film-forming ester, and fluorosilicone collectively comprise from about 1% to about 25% or from about 1% to about 10% by weight of the total composition, including the vehicle.

The compositions of the present invention may optionally contain other active and inactive ingredients typically associated with hair care products. The nature of these other ingredients and the amounts used should preferably be suitable for formulating stable hair care products which form a hydrophobic film on the keratin fibres. Preferably these further ingredients include at least one bioactive ingredient for improving keratin fibres. Other active and/or inactive ingredients for hair care products may be selected within the purview of one skilled in the art. Suitable additional ingredients include, but are not limited to, amino acids, antioxidants, chelating agents, colorants, emollients, emulsifiers, excipients, fillers, fragrances, gelling agents, humectants, minerals, moisturizers, light stabilizers (e.g., UV absorbers), preservatives, stabilizers, colorants, surfactants, viscosity and/or rheology modifiers, vitamins, waxes, and mixtures thereof. It is contemplated that the hair care products of the present invention may also include anti-dandruff, deodorant, sunscreen and/or antiperspirant ingredients.

These compositions may be in any suitable form including, but not limited to, gels, creams, liquids, emulsions, sprays, and the like.

The present invention provides a method for improving the color retention and/or reducing the fading of artificially colored hair comprising applying to the keratin fibers a hair care composition having a combination of a silicone polyurethane polymer, a film forming ester and a fluorosilicone in a suitable vehicle. However, the invention is not limited to application to artificially colored hair. These methods and compositions may be applied to any hair (whether dyed or undyed) to impart a water-repellent film on keratin fibers.

The hair care compositions of the present invention can be applied to wet or dry hair at any time after the hair is artificially colored using chemical dyes. The hair care composition is preferably applied to the hair after the artificial dyeing, but before the first wash. More preferably, the hair care composition is applied to the hair immediately after the hair is artificially dyed with the chemical dye. However, although the compositions are applied to the hair after the first shampoo or even after the second or third shampoo, significant benefits are still obtained. In addition, the hair care composition can be reapplied at any time according to the needs of the consumer. In one embodiment, the hair care composition may be reapplied to the hair prior to each wash.

Although the presently preferred embodiment of the formulation of the present invention contains all three ingredients (silicone polyurethanes, esters, and fluorosilicones), the present invention is not so limited. In some embodiments, the compositions of the present invention comprise two of these three ingredients. Accordingly, the following combinations are considered to be within the scope of the present invention: silicone polyurethanes and hydrophobic esters; silicone polyurethanes and fluorosilicones; and hydrophobic esters and fluorosilicones. These compositions may comprise two ingredients in a weight ratio of about 10:1 to about 1:10 or about 5:1 to about 1:5 or about 2:1 to about 1:2 or about 1: 1. In some embodiments, it is believed that the two-component combination will deliver at least additive color-retention improvement and preferably synergistic improvement.

Detailed description of the preferred embodiments

Example I

Compositions comprising a silicone polyurethane polymer, a high molecular weight ester and a fluorosilicone in a 1:1:1 weight ratio were prepared according to table 1, wherein the vehicle was (i) and an oil-in-water emulsion system or (ii) and an aqueous system comprising water thickened with polyquaternium-37.

Table 1.

Color retention of artificially colored hair treated with the hair care composition containing each vehicle. A hair sample is treated with a chemical dye having a red hue to impart artificial hair color and then treated with the composition of the present invention. Then used in the ADVANCED TECHNIQUES^TMA commercial shampoo product sold under the name (Avon Products, Inc.) was washed and rinsed with water. The treatment, wash and rinse cycle was repeated fifteen (15) times. Combinations in aqueous bases thickened with cationsThe substance treated hair samples were significantly better than the oil-in-water emulsion in terms of color retention.

Example II

The effect of adding triisostearyl trioleate (INCI), a high molecular weight hydrophobic ester and silicone polyurethane and/or fluorosilicone to hair care compositions was investigated with respect to color retention of hair dyes treated with hair care compositions. Compositions were prepared according to table 2, wherein the vehicle was (i) a common hair conditioner composition (vehicle a); (ii) (ii) an aqueous system comprising water thickened with a cationic compound (vehicle B) or (iii) a biphasic system comprising water and silicone oil (vehicle C).

Vehicles for hair care compositions were prepared according to table 3 below.

Table 3.

The following test protocol was used to examine the color retention of artificially colored hair treated with the hair care composition containing each vehicle.

Color retention test method

Using CLAIROL HYDRIENCE as a commodity chemical dye^TM,Ruby Twilight3RR(Procter&Gamble) or L ' OREAL PREFERENCE Medium Brown (L ' OREAL), the hair samples were treated according to the manufacturer's instructions. Each hair sample was rinsed in running warm water for 5 minutes. Each hair sample was dry rubbed gently with a towel to remove most of the residual moisture. 0.5mL of the hair care composition was applied to the hair sample using a pipette and manually distributed through by repeated downward movements. The hair samples were kept at room temperature until air-dried for 72 hours. Each hair sample was then washed, rinsed, treated, and dried for a total of fifteen (15) minutes.

Each time using flowing warm water at 100-^oThe hair sample was rinsed for 30 seconds at temperature F. Excess water was manually removed from the hair sample by squeezing the hair sample between the middle and index fingers.

To wash each hair sample, 0.5mL of commercial shampoo was applied to the hair sample using a pipette. The shampoo was manually distributed throughout by applying repeated downward movements for 30 seconds. The shampoo washed hair samples were placed in running warm water at 100-. Excess water was manually removed from the hair sample by squeezing the hair sample between the middle and index fingers. 0.5mL of the hair care composition was applied to the hair sample using a pipette and the shampoo was manually distributed through by applying repeated downward movements.

The hair samples treated with the hair care composition were kept in an oven at an elevated temperature oF 120 ° f until air dried until all residual moisture in the hair samples evaporated. Once the hair sample is dried, the hair sample is repeatedly subjected to the rinsing, washing, treating, and drying steps for an additional fourteen (14) times.

The color retention of each hair sample was evaluated visually by comparison with a control hair sample, which was a hair sample that was artificially colored with the same chemical dye according to the manufacturer's instructions, was not treated with any other hair care composition, and was not repeatedly washed and dried. The results are shown in table 4 below. Hair samples treated with hair care compositions which clearly provided hair color retention are indicated by two asterisks (") in table 4, while hair samples treated with hair care compositions which provided some color retention are indicated by one asterisk (")

Table 4.

	Medium A	Medium B	Medium C
				Shampoo only
Media		*
				Sample 1
Sample 2
				Sample 3
Sample No. 4			**
				Sample No. 5	**	**	**
Sample No. 6		**	**
				Sample 7	**		*
Sample 8		**	*
				Sample 9	**	**
Sample 10	**	**

The results show that triisostearyl trilinoleate in combination with fluorosilicones, especially perfluorononyl dimethicone, in conventional hair conditioner compositions acts in a synergistic manner to improve color retention of hair colors treated with the hair conditioner compositions. As shown in table 4, a combination of triisostearyl trilinoleate and perfluorononyl dimethicone at 2% by weight in vehicle a (e.g., sample 9) provided color retention superior to the addition, absence of triisostearyl trilinoleate, absence of fluorosilicone and addition of perfluorononyl dimethicone, absence of high molecular weight hydrophobic esters. As can be observed from table 4, the addition of up to 5% by weight of triisostearyl trilinoleate to vehicle a, but the absence of fluorosilicone (samples 1 and 4) did not provide any visible improvement in artificial hair color retention. Similarly, the addition of up to 5% by weight of perfluorononyl polydimethylsiloxane to vehicle a, but the absence of the high molecular weight hydrophobic ester (samples 3 and 6) did not provide any visible improvement in artificial hair color retention.

When triisostearyl trilinoleate and fluorosilicones are used in combination with an aqueous system comprising water thickened with a cationic compound, a lower threshold amount of triisostearyl trilinoleate may be desired. The results show that the addition of triisostearyl trilinoleate with perfluorononyl polydimethylsiloxane as low as 1% by weight in an aqueous system (vehicle B) containing water thickened with a cationic compound (samples 8 and 9) provides a visible improvement in the color retention of the artificial hair color. In contrast, the addition of up to 5% by weight of triisostearyl trilinoleate to vehicle B in the absence of fluorosilicone (samples 1 and 4) did not provide any visible improvement in the retention of artificial hair color. When the amount of perfluorononyl polydimethylsiloxane was increased to 5%, the addition of perfluorononyl polydimethylsiloxane to vehicle B in the absence of the high molecular weight hydrophobic ester provided only a visible improvement in color retention. Thus, the results show that the combination of triisostearyl trilinoleate and fluorosilicone in vehicle B is at least additive, if not synergistic, and requires a low threshold amount of triisostearyl trilinoleate for visible color retention effects.

Claims (17)

1. A method for improving the color retention of artificially colored hair, said method comprising applying to said hair a composition comprising:

(i) a silicone polyurethane polymer comprising a bis-hydroxypropyl dimethicone/SMDI copolymer, wherein the nomenclature is according to the international nomenclature for cosmetic raw materials;

(ii) a film-forming ester, wherein the film-forming ester comprises C₁₂-C₆₆Tricarboxylic acids and branched C₁₂-C₁₈Triesters of alcohols;

(iii) a fluorosilicone, wherein the fluorosilicone has the following structure:

wherein m is an integer of 10 to 50,

n is an integer of 10 to 50, and

x is an integer from 0 to 12; and

(iv) a vehicle;

wherein the silicone polyurethane polymer, the film-forming ester, and the fluorosilicone are dispersible but insoluble in the vehicle; and the composition comprises 1-5 parts of the silicone polyurethane polymer, 1-5 parts of the film-forming ester, and 1-5 parts of the fluorosilicone, on a weight basis.

2. The method of claim 1, wherein the weight ratio of silicone polyurethane polymer to film-forming ester to fluorosilicone is 1:1: 1.

3. The method of claim 1, wherein the film-forming ester has a molecular weight greater than 1000.

4. The method of claim 3, wherein the film forming ester is triisostearyl trilinoleate, wherein the nomenclature is according to International cosmetic raw materials nomenclature.

5. The method of claim 1, wherein the fluorosilicone comprises perfluorononyl polydimethylsiloxane, wherein nomenclature is according to International nomenclature for cosmetic raw materials.

6. The method of claim 1, wherein the vehicle comprises water and a thickener.

7. The method of claim 6, wherein the thickener is a cationic thickener.

8. The method of claim 7, wherein the cationic thickener is polyquaternium-37, wherein the nomenclature is according to the International nomenclature of cosmetic raw materials.

9. The method of claim 1 wherein said silicone polyurethane polymer, said film-forming ester and said fluorosilicone together comprise from 1% to 20% by weight of the composition.

10. The method of claim 1 wherein said silicone polyurethane polymer, said film-forming ester and said fluorosilicone together comprise from 1% to 10% by weight of the composition.

11. The method of claim 1, wherein the composition is applied to the hair prior to the first shampooing.

12. The method of claim 1, wherein the composition is applied to the hair after the first shampoo but before the second shampoo.

13. A composition for improving the color retention of artificially colored hair, the composition comprising:

(i) bis-hydroxypropyl dimethicone/SMDI copolymer;

(ii) triisostearyl trilinoleate;

(iii) perfluorononyl polydimethylsiloxane; and

(iv) a vehicle comprising water and a cationic thickener;

wherein the bis-hydroxypropyl dimethicone/SMDI copolymer, the triisostearyl trilinoleate, and the perfluorononyl dimethicone together comprise from 1% to 20% by weight of the composition.

14. A method for improving the color retention of artificially colored hair, said method comprising applying to said hair a composition comprising:

(i) silicone polyurethane polymers, including bis-hydroxypropyl dimethicone/SMDI copolymer, wherein the nomenclature is according to the international nomenclature for cosmetic raw materials;

(ii) film-forming esters of C₁₂-C₆₆Tricarboxylic acids and C₁₂-C₁₈Triesters of alcohols; it has a molecular weight of at least 500 and is hydrophobic;

(iii) a hydrophobic and oleophobic fluorosilicone, wherein the fluorosilicone has the following structure:

wherein m is an integer of 10 to 50,

n is an integer of 10 to 50, and

x is an integer from 0 to 12; and

(iv) a vehicle;

wherein the silicone polyurethane polymer, the film-forming ester, and the fluorosilicone are dispersible but insoluble in the vehicle;

wherein the composition comprises 1-5 parts of the silicone polyurethane polymer, 1-5 parts of the film-forming ester, and 1-5 parts of the fluorosilicone, on a weight basis.

15. The method of claim 14, wherein the weight ratio of silicone polyurethane polymer to film-forming ester to fluorosilicone is 1:1: 1.

16. The method of claim 14, wherein the film-forming ester has a molecular weight greater than 1000.

17. The method of claim 14, wherein the film forming ester is triisostearyl trilinoleate, wherein the nomenclature is according to international cosmetic raw material nomenclature.