CN1198565C - Volumizing hair care compositions containing siloxysilicates - Google Patents

Abstract

This invention relates to an improved formulation hair volumizers which comprise: (a) from 0.01-15 percent by weight (based on the total weight of the composition) of a selected liquid MQ resin having an M:Q ratio of 0.5-1.5 and a medium viscosity in the range of 1.0x103-1x106 centipoise; and (b) from 85-99.99 percent by weight (based on the total weight of the composition) of a hair care carrier (also called a vehicle). The compositions of this invention provide hair with increased volume without significant stiffness or stickiness and may be made in the form of a shampoo, conditioner, combination shampoo/conditioner, sprays, liquid rinses, gels or mousses.

Description

Volume-enhancing hair care composition containing siloxysilicate

field of invention

The present invention relates to an improved hair conditioning formulation. Specifically, the compositions of the present invention incorporate a selected class of siloxysilicate polymers useful as hair volumizers in hair conditioners. This case is related to a pending application filed on the same date (Attorney Docket No. IR 6232M) and both are owned by the same company (the U.S. patent application number for this case has not yet been given).

Background of the invention

Research to improve hair care products is ongoing. Because hair styles are different, the types of products used to treat different types of hair are different. One class of such products that people use to give their hair a fuller appearance is called hair lifters. Previous methods of increasing hair volume involved the use of fixative-based sprays, gels, or mousses to enhance hold and create volume. These products work by gluing the hair into a set hairstyle that adds volume. Such products generally have the disadvantage of making the hair stiff or excessively tacky and the user generally cannot restyle the hair without washing out and reapplying. The adhesive nature of these styling agents makes restyling difficult. Additionally, such fixative-based products may initially give volume, but continuous use of these products over time may lead to buildup on the hair causing loss of hair volume. The problem is exacerbated on those with fine hair, as this hair type is particularly sensitive to stress from hair product deposits.

Consumers want hair volumizing products that are not long-wear curlers or fixative-based hairsprays or styling gels. Consumers want volume products that add volume to flat or thinning hair while maintaining some restyleability. Thus, the hair relaxers used herein do not produce a long-lasting style, but rather re-style and volume the hair.

An example of a retention aid for hair styling is PCT Patent Application Publication No. WO 95/06057 by Torgerson et al. This document describes silicone-grafted thermoplastic elastomeric copolymers and hair and skin care compositions comprising such substances. These copolymers are useful in hairspray and mousse compositions. The copolymer described in this document is a water-soluble or alcohol-soluble or dispersible thermoplastic elastic copolymer, which has a backbone and two or more hydrophilic polymeric side chains and one or more polysilicone side chains, wherein The copolymers include:

(a) 20-89.9% monomer units copolymerizable with (b) and (c);

(b) 10-60% hydrophilic macromonomer units having one polymerized part and one part copolymerizable with (a) and (c);

(c) 0.1-20% polysilicone macromonomer units having one polymeric part and one part copolymerizable with (a) and (b).

US Patent 4,902,499 to Bolich et al. discloses hair conditioners that provide improved style retention and hair conditioning. The hair care composition includes 0.01-10% of a rigid silicone polymer and a volatile carrier. Suitable polymers include filler-reinforced dimethicone gums, cross-linked silicones, organo-substituted silicone gums, resin-reinforced silicones, and cross-linked silicone polymers.

US Patent 5,817,302 describes low viscosity MQ silicone resins and uses such MQ resins to prepare articles and personal care compositions.

WO 95/31173 describes the use of selected solid MQ resins (trimethylsiloxysilicate) in shampoos.

WO 94/08557 describes the use of selected solid MQ resins (polytrimethylsiloxysilicates) in shampoos.

European patent application EP 0 0240 350 B1 by Snyder et al. proposes a use patent for a composition having style retention and hair conditioning properties, wherein said composition comprises (a) a compound having a property of at least 1×10 ⁶ Pascal seconds (1× A rigid silicone polymer of complex viscosity of 10 ⁷ poise) selected from organosubstituted silicone gums, silicone elastomers, filler-reinforced dimethicone gums, resin-reinforced silicones and cross-linked silicones polymer; and (b) a volatile carrier selected from water, linear or branched C10-C16 volatile hydrocarbons and volatile silicones with a boiling point of 99-260°C, wherein if water is the only carrier, then Surfactants are also present at 0.05-50% by weight and wherein no silicone polymer is used in the production of the aqueous aerosol hair styling mousse composition, wherein said silicone polymer is in the form of an anionically stabilized hydroxyl group emulsion of polyorganosilicone.

Other attempts include forming hair thickeners. PCT Patent Application Publication No. WO 96/38120 to Grossman describes a hair thickening and conditioning gelatin composition for topical application to the hair. The disclosed formulations include an aqueous solution of gelatin, a water-soluble film-forming polymer, and an acid neutralizer to maintain the pH of the composition in the range of 6.0-9.5. Types of water-soluble film-forming polymers suitable for our composition include polyvinylpyrrolidone (PVP), polyvinyl acetate, partially hydrolyzed polyvinyl acetate, copolymers of pVP and vinyl acetate, polyvinyl alcohol , acrylate-acrylamide copolymer, acrylate-PVP copolymer, etc., wherein the polymer has a number average molecular weight of 5000-10000 Daltons.

Silicone resins comprising triorganosilicone units and silica units are known commercially available materials and are used in the formulation of a variety of products including adhesives, antifoams, and personal care products; however, the authors These compounds are not believed to have been used commercially in hair care products of the type described herein. Such resins are sometimes referred to as "MQ resins" because of the presence of monovalent (M) silicone units and tetravalent (Q) silica units.

Due to the reactivity of silyl hydride groups, it is sometimes desirable to include such groups in MQ type resins. Because of the high reactivity of the silyl hydride functional groups therein, silicone resins consisting of silica units and units of the general formula HR ¹ R ² SiO _1/2 , where each R ¹ and R ² can be the same or different, are often used and are each selected from hydrogen, monovalent hydrocarbons and monovalent halogenated hydrocarbons. This resin has been used as an organopolysilicone elastomer. As precursors to other synthetic silicones, it is generally required that these resins contain a limited number of silyl groups. US Patent 3772247 discloses organopolysilicone resins containing R ³ R ⁴ R ⁵ SiO _1/2 units, SiO ₂ units and HR ³ SiO and/or HSiO _3/2 type units, wherein R ³ , R ⁴ and R ⁵ are each independently selected from alkyl, aryl, alkaryl, alkenyl, cycloalkyl and cycloalkenyl. Although such resins possess silyl hydride groups, they also possess appreciable levels of divalent and trivalent organosiloxy groups.

U.S. Patent No. 4,774,310 to Butler discloses MQ resins consisting of R ³ R ⁴ R ⁵ SiO _1/2 units and SiO ₂ units, wherein R ³ , R ⁴ and R ⁵ are each independently selected from the group consisting of alkyl, aryl, alkane Aryl, alkenyl, cycloalkyl and cycloalkenyl. The MQ resin of this document uses an acidic catalyst to further react with disilone to form MQ type silicone resin, its M:Q ratio is 0.4:1 to 1:1, and the general formula H ^a R ⁿ _3-a SiO _1/2 The portion of units interrupted by hydrides is 0.1-30% of the total number of M units present, wherein R ⁿ is selected from groups as defined for R ³ , R ⁴ and R ⁵ .

British Patent 2,297,757 to Berthiaume et al. describes low viscosity organofunctional siloxysilicates of the "MQ" type and useful as cosmetic or personal care products. These functionalized MQ silicone resins have the general formula:

Wherein R ¹ and R ² are both phenyl or C ₁ -C ₁₂ alkyl, and M ¹ and M ² are independently selected from phenyl, phenethyl, polyether, hydrogen and C ₁ -C ₂₃ alkyl ( It may include a halogen-substituted hydrocarbon group), and wherein x, y, and z satisfy the following relationship: 0.5≦(x+y)/z≦4.0 and one of x and y may be 0.

U.S. Patent 5,585,094 to Villamarin discloses a method for semi-long-lasting hair conditioning in which a mixture of two silicones (one is hydroxyl-terminated dimethylpolysilicone and the other is methylhydrogenpolysilicone) Low viscosity oil-in-water emulsions are applied at acidic pH and unreacted. Preferably heat is used to crosslink the polymer.

US Patent 4,963,348 to Bolich et al. describes styling agents and compositions comprising a binder copolymer and a volatile diluent for providing hair style and hold.

However, there remains a need for compositions suitable as hair relaxers that do not make the hair stiff or unduly tacky.

Accordingly, it is an object of the present invention to provide volume-enhancing compositions that do not rely on binding the hair fibers together to achieve increased volume. In particular, an important object of the present invention is to provide a hair volume agent which imparts volume to the hair without binding the hair fibers. Another object of the present invention is to provide a volumizing agent which can re-groom and re-volumize the hair after shampooing. It is a further object of the present invention to provide compositions for use as hair volume agents which are suitable for adding a certain amount of hair volume. It is a further object of the present invention to provide compositions suitable as hair relaxers which use MQ resins and which make the hair resistant to the pressure of hair nets. These and other objects of the invention will be understood from the following description.

Brief description of the invention

The composition of the present invention is a hair relaxer comprising

(a) 0.01-15% by weight (based on the total weight of the composition) of a selected liquid MQ resin having an M:Q ratio of 0.5-1.5 and 1.0×10 ³ to 1×10 ⁶ centipoise ("cps " or "cP") of moderate viscosity (eg, 0.1-10% by weight, more preferably 0.1-7.0%, most preferably 0.1-4%); and

(b) 85-99.99% by weight (based on the total weight of the composition) of a hair care carrier (also known as a vehicle).

The compositions of the present invention provide increased hair volume without significant stiffness or excessive stickiness or loss of volume from the product on the hair. The compositions according to the invention can be prepared in the form of shampoos, conditioners, shampoo-conditioner combinations (so-called 2-in-1 products), sprays, liquid washes, gels or mousses.

Detailed Description of the Invention

Compositions of the present invention may be prepared with one or more selected liquid MQ resins having an M:Q ratio of 0.5-1.5 [also referred to as the x+y/z ratio (for Formula 1A) or x'/ z' ratio (if the x and y parts are the same, as in Equation 1B)] and 1.0 x ¹⁰³ to 1 x ¹⁰⁶ centipoise ("cps" or "cP") (or 1.0 to 1 x ¹⁰³ Pa-sec) Viscosity, preferably 1.5×10 ³ to 1×10 ⁶ centipoise, more preferably 1000-100,000 Cps, even more preferably 1000-50,000 cps, still more preferably 1000-20,000 cps such as 2,000-14,000 cps viscosity, a specific example 3,000-12,000 cps. While MQ resins with higher viscosities (eg, 50,000-100,000 cps) can be used, it is more convenient to use lower viscosities.

MQ resins suitable for use in the present invention can be represented by formula IA:

Formula LA

In the formula, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently selected from phenyl and C ₁ -C ₁₂ branched or unbranched hydrocarbons, preferably C ₁ -C ₁₂ branched or unbranched alkyl groups, more Preference is given to branched and unbranched C ₁ -C ₅ alkyl, especially methyl;

M ¹ and M ² are each independently selected from

(a) hydrogen,

(b) phenyl,

(c) phenethyl,

(d) polyethers of the following formula II:

-H ₂ C-(CH ₂ ) _n -(O-CH(R ¹⁰ )-CH ₂ ) _u -(OCH ₂ -CH ₂ ) _v -OR ¹¹ where n is a number from 1 to 20, -(CH ₂ )-chain may optionally contain an unsaturation of 1 or 2; u and v are each an integer independently selected from 0-20, provided that u+v≧1; R ¹⁰ is selected from C ₁ -C ₂₀ alkyl; R ¹¹ is selected from H, -CH ₃ and -C(O)CH ₃ ; and

(e) C ₁ -C ₂₄ branched or unbranched hydrocarbon optionally substituted by halogen substituted C ₁ -C ₃ hydrocarbyl, in particular C ₁ -C ₂₄ alkyl, especially methyl; and

where (x+y)/z is a number in the range of 0.5 to 1.5 and is preferably equal to 1; and

The values of R ⁴ , R ⁵ , R ⁶ , R ⁷ , x, y, z, M ¹ and M ² are selected such that the MQ resin has a viscosity of 1.0×10 ³ to 1×10 ⁶ centipoise, such as 1.5 x 10 ³ to 1 x 10 ⁶ centipoise viscosity liquid.

When x and y are the same, a particular type of MQ resin of formula IA can be represented by formula IB:

式IB

Formula IB

In the formula, R ¹ and R ³ are each independently selected from the same group as the definition of R ⁴ , R ⁵ , R ⁶ and R ⁷ in formula IA; R ² is selected from the same group as described in M ¹ and M ² ; preferably Each of R ¹ , R ² and R ³ is a methyl group; x'/z' is a value between 0.5 and 1.5, preferably x'/z' is 1.

One particular type of MQ resin useful in the present invention is a liquid trimethylsiloxysilicate polymer, specifically having a M:Q ratio of 1 (commercially available under the tradename ® , for example, from the General Electric Company, Waterford, New York) "MQ-A" resin).

The MQ resins useful in the present invention differ from other types of MQ resins that do not have all of the desirable properties of the present invention. As described in more detail below, it has been found that low viscosity liquid MQ resins with a M:Q ratio of 2 do not provide high volume and do not exhibit significant adhesive properties to hair; A solid MQ resin of 2 does not provide bulk and does not exhibit significant adhesive properties to hair; a solid MQ resin with a M:Q ratio of 0.7-1.0 provides volume but does not exhibit Shows outstanding adhesive properties to hair.

The vehicle in which the MQ resin resides is selected from sprays, rinses, shampoos, conditioners and "2 in 1" conditioning shampoos. In particular, these products can be used with volatile carriers (i.e. carriers with measurable vapor pressure) such as volatile silicones, _C2 - _C3 alcohols, isopropyl myristate and water, and mixtures of the foregoing, provided that If water is the sole carrier, eg, water-based shampoos, water-based conditioners, etc., then at least one surfactant is also used. A preferred class of carriers are volatile silicones having a boiling point of 99-260°C. The silicone may be a linear or a cyclic dimethicone, wherein the cyclic dimethicone contains from 3 to about 7 silicon atoms, most preferably 5 silicon atoms. These volatile silicones can be used alone or in combination with other volatile carriers. A specific volatile silicone is cyclomethicone (particularly D5 cyclomethicone).

If water is the sole carrier, a surfactant (selected from the group described below) is also present in an amount of from 0.1 to 50% by weight (based on the total weight of the composition).

Shampoo can be used as a carrier to which the selected MQ resin can be added. Suitable shampoos include conventional shampoos and conditioning shampoos. Particular shampoos include those formulated with surfactants, stabilizers, and liquid MQ resins selected as described above. As described below, other optional ingredients such as thickening agents, preservatives, fragrances, opacifying agents, foam regulators and the like can also be included in such formulations.

Suitable surfactants include:

(a) Anionic surfactants as described in U.S. Patent 4,902,499 to Bolich et al. and U.S. Patent 4,963,348 to Bolich et al. (both incorporated herein by reference), such as:

(i) Alkyl and alkyl ether sulfates of the formula R ²⁰ OSO ₃ M and R ²⁰ O(C ₂ H ₄ O) _w SO ₃ M, where R ²⁰ is an alkyl or chain of 10-20 carbon atoms Alkenyl, w is a number from 1 to 10, and M is a water-soluble cation such as ammonium, sodium, potassium and triethanolamine;

(ii) reaction products of fatty acids (such as those derived from coconut oil) esterified with isethionic acid and neutralized with sodium hydroxide;

(iii) Succinamic acid esters (salts), such as disodium N-octadecylsulfosuccinate, N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinamic acid tetra Sodium salt, dipentyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, and dioctyl sodium sulfosuccinate; and

(iv) Olefin sulfonates having 12 to 24 carbon atoms;

(b) amphoteric surfactants as described in U.S. Patent 4,902,499 to Bolich et al. (incorporated herein by reference), such as

(i) Derivatives of aliphatic secondary and tertiary amines, wherein the aliphatic group may be linear or branched and wherein one aliphatic substituent contains 8 to 18 carbon atoms and one contains an anionic water-solubilizing group group (such as carboxyl, sulfonate, sulfate, phosphate or phosphonate), examples of such compounds include sodium 3-dodecyl-alanine, sodium 3-dodecylaminopropanesulfonate, N- Alkyl taurine, N-higher alkyl aspartic acid (such as those sold under the trade name "MIRANOL" as described in US Patent No. 2,528,378);

(ii) Zwitterionic surfactants, examples of which are derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, wherein the aliphatic group may be linear or branched, and one of the aliphatic substituents contains 8 to 18 carbon atoms and one contains an anionic water solubilizing group (eg, carboxyl, sulfonate, sulfate, phosphate, or phosphonate);

(iii) Betaines, such as higher alkyl betaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylα-carboxyethylbetaine, cetyl Dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl - gamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl) alpha-carboxyethyl betaine and cocamidopropyl betaine.

(c) nonionic surfactants, including those nonionic surfactants selected from those described in Grote et al., U.S. Patent No. 4,741,855 (which is incorporated herein by reference), which are

(i) polyethylene oxide condensates of alkylphenols, wherein the alkyl moiety of the alkylphenol has 6-12 carbon atoms and may be linear or branched, and the ethylene oxide moiety is Alkylphenols are present in an amount of 10-60 moles of ethylene oxide;

(ii) a condensation product of ethylene oxide with a reaction product of propylene oxide and ethylenediamine, depending on the desired hydrophobic/hydrophilic balance (e.g., 40-80% by weight polyoxyethylene and having a molecular weight of 5,000-11,000 resulting from the reaction of an oxirane group with a hydrophobic base consisting of the reaction product of ethylenediamine and an excess of propylene oxide, wherein the base has a molecular weight of 2,500-3,000) ;

(iii) condensation products of C _8-18 linear or branched aliphatic alcohols and ethylene oxide (such as the coconut oil ethylene oxide condensate of 10-30 moles of ethylene oxide per mole of coconut oil alcohol, wherein The coconut oil moiety has 10-14 carbon atoms);

(iv) long-chain tertiary amine oxides of the formula (R ³⁰ )(R ³¹ )(R ³² )-N→O, wherein R ³⁰ is C _8-18 alkyl, alkenyl or monohydroxyalkyl; it has 0-10 vinyl moieties and 0-1 glyceryl moieties; R ³¹ and R ³² may be the same or different and each independently selected from C _1-3 alkyl and 0-1 hydroxyl. Arrows in structures are conventional representations of semipolar bonds. Examples of suitable long chain tertiary amine oxides include cocamidopropylamine oxide and laurylamine oxide.

(v) long-chain tertiary phosphine oxides of formula R ²⁰ R ²¹ R ²² -P→O, wherein R ²⁰ is C _8-18 alkyl, alkenyl or monohydroxyalkyl; it has 0-10 epoxy Ethane moiety and 0-1 glyceryl moiety; R ²¹ and R ²² are each independently C _1-3 alkyl or monohydroxyl alkyl. Arrows in the formulas are conventional representations of semipolar bonds.

(vi) Long-chain dialkyl sulfoxides, which contain a short-chain alkyl or hydroxyalkyl group (especially methyl) of 1-3 carbon atoms and a _C8-20 alkyl, alkenyl, or hydroxyl group Long hydrophobic chains of alkyl or oxoalkyl groups with 0-10 oxirane moieties and 0-1 glyceryl moieties.

The stabilizer includes one or more of the ingredients listed below, and the amount of the stabilizer finally added is 0.1-7.0%:

(a) Long-chain fatty alcohols having more than 14 carbon atoms such as C _20-40 and mixtures of such long-chain fatty alcohols (such as a C>14 alcohol and ethylene homopolymer available from Petrolite Corporation, St.Louis, Missouri PETROLITE C-7138).

(b) acrylate/steareth-20 methacrylate copolymers (such as ACULYN® 22 available from Rohm & Haas, Philadelphia, Pennsylvania); and acrylate copolymers (such as ACULYN® ²² available from Rohm & Haas ⁾ . 33. ACUSOL® ^-445 , -810 and -830, ^ACRYSOL® ASE 75); and Acrylates/C _10-30 Alkyl Acrylate Crosspolymer (PEMULEN ^™ Polymerized Emulsion from BF Goodrich Company, Brecksville, Ohio agents, in particular the products named TR-1 and TR-2). For acrylate copolymer (ACUL YN® 33) products (having a pH in the range of 2.1-3.5), the neutralization step is performed using sodium phosphate (such as disodium phosphate), sodium hydroxide, or a cosmetically acceptable organic amine. Raise the pH to about 6.5.

(c) Reagents described in U.S. Patent No. 5,015,415 (incorporated herein by reference), particularly N,N-disubstituted anthramoylbenzoic acids and ammonium salts thereof of formula III:

Formula III

In the formula, R ²⁴ and R ²⁵ may be the same or different, and are each selected from C ₁₀ -C ₄₀ straight chain and branched chain alkyl and C ₁₀ -C ₄₀ straight chain and branched chain arylalkyl (for example, in the formula, R ²⁴ Same as R ²⁵ and each selected from stearyl and hydrogenated tallow such as STEPAN SAB-2 and STEPAN TAB® ^- 2 available from Stepan Company, Northfield, Illinois).

The stabilizer should be of a grade and purity acceptable for cosmetic use or as purified as necessary for cosmetic acceptance. Further discussion of these reagents can be found in US Patent 5,015,415 to Goze et al. and our co-pending patent application US Application No. 08/933521.

Shampoo carriers useful as vehicles for the above selected MQ resins can be formulated as solutions, suspensions or emulsions containing mild, aqueous, lathering and conditioning detergent compositions comprising (in total composition weight scale):

(a) 4.00-60.00% detersive surfactant selected from C ₈ -C ₁₈ alkyl sulfates, C ₈ -C ₁₈ alkyloxyethylene ethers containing 1-5 oxyethylene groups in the molecule Anionic detergents of sulfates, C ₁₀ -C ₁₈ acyl isethionates, C ₁₀ -C ₂₀ alkyl sulfonates, C ₁₀ -C ₂₀ alkenyl sulfonates, and mixtures thereof; and optionally one kind:

(i) 0.10-5.00% C ₁ -C ₃ alkylbenzene sulfonate or C ₅ -C ₆ alkyl sulfate of anionic hydrotrope;

(ii) 0.10-15.00% amphoteric surfactant selected from C ₈ -C ₁₈ alkyl betaines, C ₈ -C ₁₈ alkyl sultaines, C ₈ -C ₁₈ alkyl amido C ₂ -C ₃ Alkyl betaines, C ₈ -C ₁₈ alkyl amido C ₂ -C ₃ alkyl sultaines, C ₈ -C ₁₈ alkyl amphoacetates, C ₈ -C ₁₈ alkyl amphopropionates, Cocamidopropyl Betaine, and mixtures thereof; and

(iii) 0.1-4.0% non-ionic surfactants, especially selected from C ₈ -C ₂₂ monoethanolamides and mixtures thereof and C ₈ -C ₂₂ diethanolamides and mixtures thereof, especially coconut oil monoethanolamide and Coconut Diethanolamide;

with the proviso that the total amount of detersive surfactant does not exceed 60% by weight of the total weight of the composition, and preferably ranges from 6 to 30%;

(b) 0.10-7.0 (more preferably 0.10-5.00) % of stabilizers selected from the above, especially polyacrylic acid, derivatives of polyacrylic acid, acrylate copolymers, derivatives of acrylate copolymers and polymeric emulsifiers such as Acrylates/C10-30 alkyl acrylate crosslinked copolymers, specific products include those under the trade names ACULYN® 33, TAB®-2, SAB-2 and PEMULEN ^™ ; ACULYN® 22 acrylate/steareth- A mixture of 20 methacrylate copolymer and ACULYN® 33 product (such as about 50 to 50);

(c) an optional quaternized cellulose polymer (in particular at least one quaternized cellulose polymer, such as Polyquaternium-10);

(d) Other substances such as water or aqueous media.

For conditioning shampoos, a further ingredient (e) can optionally be added:

(e) 0.01-10.00% of a water-insoluble conditioning agent selected from:

(i) 0.10-6.00% of a water-insoluble silicone selected from polydimethyl silicones and silicones such as those described in U.S. Patent No. 4,741,855, which is incorporated herein by reference; these include polyalkylsilanes Ketones, polyaryl silicones, polyalkylaryl silicones, polyester silicone copolymers and mixtures of the foregoing in amounts of 0.1-10.00%, preferably about 0.5-5.0%, commercially available, for example, in the Viscasil series from General The Electric Company and polydimethylsilicone with a viscosity of 5-600,000 centistokes (eg, 60,000 centistokes) at 25°C available from Dow Corning in the Dow Corning 200 series; Methylphenyl silicones (such as SF 1075 methylphenyl fluid available from the General Electric Company and Dow Corning 556 cosmetic grade fluid available from Dow Corning); and dimethylpolyethylene oxide modified with polypropylene oxide Silicone and ethylene oxide or mixtures of EO and PO modified materials;

(ii) a mixture of at least one (d)(i) with 0.01-3.00% of a cationic polymer such as selected from quaternized cellulose polymers (especially at least one quaternized cellulose polymer Polyquaternium compounds such as Polyquaternium-10);

(iii) non-cellulosic quaternary ammonium compounds (eg Polyquaternium-7); and

(iv) a mixture of at least one of (d)(i) with 0.01-3.00% of a cationic polymer such as selected from at least one quaternized cellulosic polymer and non-cellulosic quaternary ammonium conditioning polymer of polyquaternary compounds.

Note that the use of certain silicones as described herein and in the patent literature may require the use of suspending or stabilizing agents.

Another specific type of shampoo can be prepared by mixing 0.1-15% of MQ resin, 4-60% of surfactant (such as synthetic surfactant), 0.5-7% of stabilizer (based on 100% active) and remaining items of water to prepare. Examples of suitable surfactants include ammonium lauryl sulfate, ammonium lauryl ether sulfate, triethylamine lauryl sulfate, triethylamine lauryl ether sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl ether sulfate, lauryl sulfate Monoethanolamine, monoethanolamine lauryl ether sulfate, diethanolamine lauryl sulfate, diethanolamine lauryl ether sulfate, sodium lauryl monoglyceride sulfate, sodium lauryl sulfate, sodium lauryl ether sulfate, potassium lauryl sulfate, lauryl ether sulfate Potassium, Lauryl Sarcosinate, Cocoyl Sarcosinate, Ammonium Cocoyl Sulfate, Ammonium Lauroyl Sulfate, Sodium Cocoyl Sulfate, Sodium Lauroyl Sulfate, Potassium Cocoyl Sulfate, Potassium Lauroyl Sulfate, Triethanolamine lauroyl sulfate, triethanolamine lauroyl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauroyl sulfate, sodium tridecylbenzene sulfonate, and sodium dodecylbenzene sulfonate and incorporated herein by reference Other materials described in columns 4-6 of US Patent No. 4,902,499 to Bolich et al.

Another specific example of a suitable vehicle for the delivery of formulations of the invention includes conditioning agents. Specific formulations are those prepared using lipid materials, cationic surfactants and water. Such formulations can be found in US Patent No. 5,120,531, which is incorporated herein by reference.

Lipid vehicle materials useful in the present invention are water-insoluble compounds possessing hydrophobic and hydrophilic moieties. Examples of suitable lipid materials are naturally or synthetically derived acids, acid derivatives, alcohols, esters, ethers, ketones, alcohol ethoxylates and amides, having 12-22 carbons, and preferably 12-18 and carbon chains of 16-18 carbons. Specific examples include esters such as cetyl palmitate and glyceryl monostearate; alcohols such as cetyl alcohol and stearyl alcohol. Specific lipid materials are (a) stearyl alcohol as a single lipid material and (b) a mixture of 55-65% cetyl alcohol and the balance stearyl alcohol. These lipid materials include fatty alcohols, fatty alcohol ethoxylates and fatty esters of natural or synthetically derived origin.

Cationic surfactants useful in forming such conditioners include the cationic surfactants described in US Patent No. 5,120,531 mentioned above and elsewhere. Specific examples include cationic surfactants having a positively charged amino or quaternary ammonium-containing hydrophilic moiety when dissolved in an aqueous composition, such as the general formula (R ¹⁰ )(R ¹¹ )(R ¹² )(R ¹³ )N ⁺¹ -A cationic surfactant of X, wherein R ¹⁰ is hydrogen, an aliphatic group with 1-22 carbon atoms, or an aromatic aryl or alkylaryl group with 12-22 carbon atoms; R ¹¹ is a group with An aliphatic group of 1-22 carbon atoms; R ¹² and R ¹³ are each independently selected from an alkyl group having 1-3 carbon atoms; X is selected from the group consisting of halogen, acetate, phosphate, nitrate and alkyl Anion of the sulfate group. In addition to carbon atoms and hydrogen atoms, the aliphatic group may contain ether linkages and other groups such as amide groups. Examples of quaternary ammonium salts include cetyltrimethylammonium chloride ("cetrimonium chloride"), lauryltrimethylammonium chloride ("laurtrimonium chloride"), tris(cetyl)methylammonium chloride ("tricetylmonium chloride"), octadecyldimethylbenzyl ammonium chloride ("stearalkonium chloride") and bis(partially hydrogenated tallow) dimethyl ammonium chloride, dioctadecyl dimethyl chloride ammonium chloride etc.

A particular class of conditioning agents is selected from the group consisting of quaternary ammonium compounds, especially di(cetyl)dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride and the cationic surfactants listed above. Other cationic substances in it.

An example of a conditioner to which the selected MQ resin may be added is a conditioner prepared with 0.1-10.0% lipid material, 0.05-5.0% cationic surfactant and water.

Rinse conditioners can be formulated by mixing MQ resins as described above (or mixtures thereof) with water (preferably distilled or deionized) or water/alcohol mixtures (e.g. in a ratio of 20:1 to 1:2) as part of the carrier. to prepare. It also includes 0.1-10% surfactant. The carrier is present in an amount of 75-99.5% by weight of the total composition, preferably about 85-99% and more preferably about 90-99%.

Sprays can be formulated by mixing 0.01-10% of MQ resin (or mixtures thereof) and one or more volatile substances such as water, ethanol, cyclomethicone (if significant amounts of water are included, comprising 0.1-10% of at least one surfactant) and one or more optional ingredients as described above.

Other specific examples of carriers (which may be in the form of shampoos, conditioners, conditioning shampoos, sprays, etc.) suitable for use as leavening agents of the present invention are familiar to those skilled in the art and are described, for example, in Kobot et al. Patent 3,577,517, US Patent 3,907,984 to Calvert et al., US Patent 4,012,501 to Farber, US Patent 4,223,009 to Chakrabarti et al., and US Patent 4,283,384 to Jacquet et al., all of which are incorporated herein by reference.

In addition to the above basic formulations for shampoos and conditioners, it may be desirable to add one or more of the following ingredients and mixtures thereof:

(a) Viscosity modifiers for shampoos-

Polyvinyl alcohol, ethanol, acrylic acid polymers and copolymers, cellulose ethers, diethanolamides or monoethanolamides of long-chain fatty acids (such as PEG 3 lauramide), block polymers of ethylene oxide and propylene oxide, Sodium chloride, sodium sulfate, water-soluble polymers (such as guar gum), especially thickeners such as hydroxypropyl cellulose, guar hydroxypropyltrimonium chloride, PEG-120 methyl glucose dioleate esters, pentaerythritol tetrastearate and xanthan gum.

(a1) Viscosity modifiers for conditioners -

Polyvinyl alcohol, ethyl alcohol, cellulose ethers, polyacrylamide, water-soluble polymers such as hydroxyethylcellulose, guar gum, and starch, especially a thickener such as hydroxyethylcellulose and guar hydroxypropyl trimethylammonium chloride.

(b) fragrances such as cosmetically acceptable fragrances used in hair care products;

(c) preservatives, such as antibacterial agents, especially methylchloromethylisothiazolinone and a mixture of methylisothiazolinone (sold under the trade name KATHON® CG by Rohm and Haas, Philadelphia, Pennsylvania), may also Includes benzyl alcohol, ethylparaben, propylparaben and imidazolidinyl urea, DMDM hydantoin, formalin, 2-bromo-2-nitropropane-1,3-diol ("Bronopol") and mixtures of the foregoing. Specific examples may also include synergists such as ethylenediaminetetraacetic acid (EDTA) or its sodium salt form (e.g. Bronopol and EDTA (such as 0.04% Bronopol and 0.1% EDTA); formalin, DMDM hydantoin and EDTA (such as 0.1% formalin, 0.45% DMDM hydantoin and 0.2% EDTA));

(d) Dyes or colorants, pearlizing agents (such as glycol distearate, sodium octyl sulfate, titanium dioxide or mica) and opacifying agents (such as glycol distearate, fatty ethoxylates, latex opacifiers, stearamide monoethanolamine (MEA) stearate, sodium cetyl stearate and lanolin derivatives);

(e) pH regulators such as citric acid, sodium carbonate, etc.;

(f) Chelating agents such as ethylenediaminetetraacetic acid and its sodium salt.

These additives may be included in a suitable amount such as about 0.01-60%, preferably about 0.5-40% by weight each based on the total weight of the composition.

Those skilled in the art will recognize that compositions formulated in accordance with the present invention can produce long-lasting volume over time so that the use of products prepared in accordance with the present invention can be varied from other types of commercial shampoos to obtain and maintain the desired volume. Effect. While hair volume gains vary from individual to individual, consistent use of the compositions of the present invention results in an overall volume gain of 10-40% as measured by the Mannequin Volume Test method as described below. In general, the effect will be more pronounced on thin, fine hair than on thick, long, coarse hair.

It should also be noted that the compositions of the present invention provide volume without actual hold properties (tack) and chemical bonding between the hair fibers. The hair can thus be restyled by re-combing or re-fluxing. This method is ineffective on fixative treated hair as it will lead to breakage of the fixative bond points between the hairs and thus loss of fixative hold. The lack of fixability in the compositions of the present invention can be assessed by the Curl Permanence Test, one of which is described below.

Examples of formulations that may be prepared according to the invention include:

Shampoo:

Formulation A - 0.1-7.5%, preferably 0.1-5% or 0.1-3.0% and more preferably 0.25-2.5% of selected liquid MQ resin, balance shampoo vehicle. For conditioning shampoos, 0.1-3.0%, especially 0.1-2.0%, of a conditioning agent may also be included.

Formula B-

10-18% of surfactants, especially selected from ammonium lauryl sulfate, ammonium lauryl ether sulfate, sodium lauryl ether sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, ammonium lauryl ether sulfate and mixtures of the foregoing;

0.25-2.5% of selected MQ resin;

0.10-5.00% stabilizer;

1-3% of ingredients acting as foam regulators and/or viscosity modifiers (for example at least one selected from the group consisting of cocamidodiethanolamine, cocamidomonoethanolamine and cocamidopropyl betaine); and

The remainder, water or other aqueous medium, may include effective amounts of preservatives and flavoring and coloring agents.

Formula C-

10-20% mixed surfactant system comprising at least one anionic surfactant and at least one amphoteric surfactant in a ratio of 60:40-40:60 As described above, examples of suitable amphoteric surfactants are cocamidopropyl betaine and cocamidopropylamine oxide); 0.25-2.5% of selected MQ resins;

0.10-5.00% stabilizer; and

The remainder is water or other aqueous medium which may include effective amounts of preservatives as well as flavoring and coloring agents.

Conditioner:

0.1-7.5%, preferably 0.1-5%, more preferably 0.2-2.5% of the selected liquid MQ resin and the rest as the carrier of the composition.

Formula D-

1-4% lipid material (eg stearyl alcohol and mixtures of stearyl and cetyl alcohol);

1-3% of quaternized compounds (for example bis(hexadecyl)dimethyl ammonium chloride; at least one of distearyl dimethyl ammonium chloride and cetyl trimethyl ammonium chloride species); and

The remainder is water or other aqueous medium which may include effective amounts of preservatives as well as flavoring and coloring agents.

Fluffy Spray:

0.01-7.5%, preferably 0.03-5.0%, more preferably 0.05-2.0% of selected MQ resin and volatile carrier such as ethanol.

Fluffy Hair Dye:

0.1-7.5%, preferably 0.1-5.0%, more preferably 0.2-2.5% of selected MQ resins and carriers such as water and suitable amounts of surfactants/stabilizers (such as Ceteth-20 and cetyltrimethylmethacrylate) to keep the emulsion stable ammonium chloride) (the amount of stabilizer depends on the amount of MQ resin used).

Hairspray with fixing additives:

0.01-7.5%, preferably 0.05-2.0%, of selected liquid MQ resins;

0.1-20%, preferably 0.5-15 volatile carrier;

72.5-99.89%, preferably 83-99.45%, of a fixative vehicle (which itself may contain a volatile carrier such as ethanol);

Its various components can be a single component or a mixture.

The compositions of the present invention can generally be prepared by conventional addition and mixing techniques. The MQ resin can be added in several ways. In the case of shampoo formulations, the MQ resin can be added separately as in the examples below, either alone or mixed with cyclomethicone or dimethicone. Alternatively the MQ resin can be added to the heated oil phase prior to any emulsion formation.

The compositions of the present invention make it easier for the hair to maintain a particular style or structure. Apparently, the use of this composition does not interfere with decoration and is not affected by the presence of conditioners. Furthermore, tests have demonstrated that the increase in volume does not decrease with repeated use, as may occur with fixatives that accumulate on the hair.

Another feature of the present invention is that it can be formulated as a hair rinsing composition. Thus, unlike anchor-based bulking agents which can be formulated as leave in products, it is not the case with the present invention that they can be formulated as either leave in products or rinse-off products.

The compositions of the invention can also be used in combination with fixatives without loss of volume. Tests have shown that the MQ resins described herein do not appear to interfere with fixatives.

Although the compositions of the present invention are described by the term "comprising", the compositions will also include the narrower range of combinations illustrated by the terms "consisting of" and "consisting essentially of" thing. Likewise, although the compositions of the present invention are described using "comprising", it is to be understood that the compositions also include those compositions made by combining the listed ingredients in the composition.

Example

The following examples are used to illustrate the present invention, but should not be regarded as limiting the present invention. Unless otherwise indicated, all percentages are by weight based on a 100% active level of all ingredients and all chemical and scientific terms have their usual and customary meanings. All temperatures are in degrees Celsius (°C). These conventions also apply to the rest of this patent application.

Embodiment 1-4 conditioner

Conditioners were prepared using the types and amounts of materials listed in Table 1. In a suitable vessel, disperse the hydroxyethylcellulose in distilled water at room temperature. The C9-11 alcohol ethoxylate (EO6:1) ("C9-11 Pareth-6") was then added with stirring, and the resulting solution was heated to 75°C. In a suitable vessel mix ceteth-20, steareth-20, stearyl alcohol, isostearamidopropyldimethylamine and bis(hexadecyl)dimethylammonium chloride and heat with stirring to 75°C. When both solutions were at 75°C, the water phase was added to the oil phase with stirring. The resulting emulsion was stirred at 75°C for 10 minutes and then cooled to 60°C. Liquid trimethylsiloxysilicate was dissolved in cyclomethicone and added to the emulsion at 62°C. The emulsion is then cooled to 38°C and the fragrance and preservatives are added at this temperature. Finally the formulation was cooled to room temperature. The MQ resin used was trimethylsiloxysilicate ("MQ-A") available from GE.

Table 1 Material Example 1% by weight Example 2% by weight Example 3% by weight Example 4% by weight distilled water 93.85% 93.85% 93.85% 93.85% Hydroxyethyl cellulose 0.50 1.00 1.0 1.0 C9-11 Pareth-6 0.20 0.20 0.20 0.20 Ceteth-20 0.50 0.50 0.50 0.50 Steareth-20 0.50 0.50 0.50 0.50 stearyl alcohol 2.00 2.00 2.00 2.00 Isostearamidopropyldimethylamine 0.80 0.80 0.80 0.80 Di(hexadecyl)dimethylammonium chloride 1.50 1.50 1.50 1.50 Liquid Trimethylsiloxysilicate 2.50 2.50 0.75 1.5 Cyclomethicone (D5) 2.50 2.50 2.50 2.50 spices 0.75 0.75 0.75 0.75 Methylchloromethylisothiazolinone and methylisothiazolinone 0.07 0.07 0.07 0.07

Embodiment 5 conditioner

A 300 g sample of conditioner was prepared with the following materials: 0.50% Hydroxyethylcellulose; 93.35% Distilled Water; 2.75% Cetearyl Alcohol; 0.50% Stearamidopropyl Dimethylamine; 0.15% Polyglyceryl-3 Diisostearate 0.25% citric acid; 0.20% methyldibromoglutaronitrile and phenoxyethanol (MERUARD® 1200 from Calgon Corporation, Pittsburgh, Pennsylvania); 0.15% glyceryl monostearate; 1.50% distearyl Dimethylammonium chloride; 0.25% MQ resin as described in Examples 1-4; 0.40% fragrance. In a suitable container, mix the hydroxyethylcellulose and distilled water with agitation. The solution was heated to 80°C. In a separate container mix cetearyl alcohol, distearyldimethylammonium chloride, stearamidopropyldimethylamine, glyceryl monostearate and polyglyceryl-3 diisostearate and mix in Heat to 80°C with stirring. When both mixtures were at 80°C, the water phase was added to the oil phase with stirring. The resulting emulsion was cooled to 60°C and the silicone MQ resin was added with stirring. Add fragrance and preservatives when the temperature reaches 38°C. The final formulation was then cooled to room temperature.

Embodiment 6-7 Shampoo preparation

Shampoo formulations were prepared using the types and amounts of materials described in Table II. In a suitable container, combine all of the water, tetrasodium EDTA, disodium phosphate (disodium phosphate), ammonium lauryl sulfate, sodium deceth-3 sulfate, cumyl Sodium Sulfonate, Cocamidopropyl Betaine Blend. The resulting solution was heated to 90°C with stirring. In a small container, combine the remaining 10% by weight of distilled water and Polyquaternium-10. While heating, add the contents of the small container on top of the solution being heated. In a suitable vessel mix and melt isosteareth-2, C _20-40 alcohol and distearyldimethyl ammonium chloride. Once melted, the mixture was added to the aqueous solution at 90°C with stirring. The resulting emulsion was then cooled to 60°C. Liquid trimethylsiloxysilicate (same MQ resin as described in Examples 1-4) was dissolved in cyclomethicone and added to the emulsion at 60°C with stirring. The resulting mixture is then cooled to 38° C. and flavor and preservatives are added at this temperature. The final formulation was then cooled to room temperature. Note that for Example 7 this procedure was used but without deceth-3 sodium sulfate, isosteareth-2, distearyldimethylammonium chloride or cyclomethicone.

Table II Material Example 6% (weight) Example 7% (weight) distilled water Appropriate amount Appropriate amount Tetrasodium EDTA 0.10 0.10 disodium phosphate 0.20 0.20 ammonium lauryl sulfate 3.36 8.26 Deceth-3 Sodium Sulfate 4.50 0 Sodium cumene sulfonate 2.80 0.66 Cocamidopropyl Betaine 9.00 9.00 Polyquaternium-10 0.90 0.55 Isosteareth-2 0.80 0.00 C20-40 Alcohol 4.00 2.00 Distearyl Dimethyl Ammonium Chloride 1.00 0.00 Liquid Trimethylsiloxysilicate 2.50 1.00 Cyclomethicone (D5) 2.50 0.00 spices 1.20 0.75 Methylchloromethylisothiazolinone and methylisothiazolinone 0.07 0.07

Examples 8-9 Shampoo formulations

Shampoo formulations were prepared using the types and amounts of materials listed in Table III. In a suitable container, except for 10% of the remaining distilled water, combine the remaining distilled water and sodium phosphate and mix for 10 minutes. Ammonium lauryl sulfate was added and mixed for 5 minutes. The resulting solution was heated to 50°C. The remaining portion of the water and Polyquaternium-10 were premixed for 1-2 minutes and added to the vessel and mixed for an additional 15 minutes. In a separate vessel, coconut diethanolamide ("cocamide DEA"), guar gum were mixed and heated to 50°C with constant stirring. When the two vessels reached 50°C, they were combined under stirring. Silicone MQ resin (same resin as in Examples 1-4) and Dimethicone (if included in the formulation) were added separately to the container and mixed for 15 minutes. Then let the container cool. Acrylate copolymer ("ACULYN(R) 33") and perfume are premixed and added to the emulsion. When the temperature of the mixture reached 38°C, the preservative was added. The final formulation was then cooled to room temperature.

Table III Material Example 8% (weight) Example 9% (weight) distilled water Appropriate amount Appropriate amount ammonium lauryl sulfate 16.80 16.80 Sodium dihydrogen phosphate 0.30 0.30 Polyquaternium-10 0.25 0.25 Coconut Diethanolamide 2.00 2.00 guar gum 0.22 0.22 Distearyl Dimethyl Ammonium Chloride 0.25 0.25 Dimethicone 0.00 1.00 MQ resin 2.50 2.50 Acrylate Copolymer 1.65 1.65 spices 0.75 0.75 Methylchloromethylisothiazolinone and methylisothiazolinone 0.07 0.07

Examples 10-11 Shampoo formulations

In a suitable container, combine all but 10% distilled water and sodium phosphate. Ammonium lauryl sulfate was added with stirring. The resulting solution was heated to 90°C. In a separate container the remaining distilled water and Polyquaternium-10 were premixed for 1 to 2 minutes and added to the solution and mixed for an additional 15 minutes. In a separate container, melt the Cocodiethanolamide, C20-40 Alcohol, and Distearyl Dimonium Chloride and add to the solution with stirring. The resulting emulsion is then allowed to cool. Silicone MQ resin (same resin as in Examples 1-4) and Dimethicone (if used in the formulation) were added separately to the 60°C solution under stirring. When the temperature of the emulsion reaches 38°C, the fragrance and preservative are added. The final formulation was then allowed to cool to room temperature.

Table IV Material Example 10% (weight) Example 11% (weight) distilled water Appropriate amount Appropriate amount ammonium lauryl sulfate 16.80 16.80 sodium phosphate 0.30 0.30 Polyquaternium-10 0.25 0.25 Coconut Diethanolamide 2.00 2.00 C20-40 Alcohol 2.00 2.00 Distearyl Dimethyl Ammonium Chloride 0.25 0.25 Dimethicone 0.00 1.00 MQ resin 2.50 2.50 spices 0.75 0.75 Methylchloromethylisothiazolinone and methylisothiazolinone 0.07 0.07

Examples 12-13 Shampoo formulations

In a suitable container, mix all but 10% by weight of distilled water and sodium dihydrogen phosphate with stirring. Ammonium lauryl sulfate was added with stirring. The resulting solution was heated to 60°C. In a small container, combine the remaining 10% by weight of distilled water and Polyquaternium-10. The contents of the small container were then added to the solution with heating and mixed for 15 minutes. In a separate container, combine the cocodiethanolamide, guar gum, and distearyldimonium chloride and melt. Once melted, the mixture was added to the 60°C aqueous solution with stirring. The Silicone MQ resin (same resin as in Examples 1-4) and Dimethicone (if included in the formulation) were added separately to the emulsion with stirring. Distearylphthalic acid amide (TAB-2) was melted in a separate vessel and added to the mixture cooled to 55°C. The resulting mixture is then cooled to 38° C. and flavor and preservatives are added at this temperature. The final formulation was cooled to room temperature.

Table V Material Example 12% (weight) Example 13% (weight) distilled water Appropriate amount Appropriate amount ammonium lauryl sulfate 16.80 16.80 sodium phosphate 0.30 0.30 Polyquaternium-10 0.25 0.25 Coconut Diethanolamide 2.00 2.00 guar gum 0.22 0.22 Distearyl Dimethyl Ammonium Chloride 0.25 0.25 Dimethicone 0.00 1.00 MQ resin 1.00 1.00 spices 0.75 0.75 Methylchloromethylisothiazolinone and methylisothiazolinone 0.07 0.07 Distearyl phthalic acid amide 2.00 2.00

Examples 14-15 Shampoo formulations

In a suitable container, all but 10% by weight of the distilled water was mixed with the C10-30 Alkyl Acrylates Crosspolymer (PEMULEN ^™ TR-1) under agitation. Ammonium lauryl sulfate was added with stirring, followed by sodium phosphate. In a small container, combine the remaining 10% by weight of distilled water and Polyquaternium-10. The contents of the small container were then added to the solution and mixed for an additional 15 minutes. In a separate container, combine the Cocodiethanolamide, Guar Gum, Fragrance, and Distearyl Dimonium Chloride and slowly add to the solution with good agitation. The Silicone MQ resin (same resin as in Examples 1-4) and Dimethicone (if included in the formulation) were added separately to the emulsion with continuous stirring. Preservatives are then added to obtain the final formulation. (Note that heating is used throughout this example in essentially the same manner as described in Examples 12-13). The final formulation was cooled to room temperature.

Table VI Material Example 14% (weight) Example 15% (weight) distilled water Appropriate amount Appropriate amount ammonium lauryl sulfate 55.00 55.00 sodium phosphate 0.30 0.30 Polyquaternium-10 0.20 0.20 Coconut Diethanolamide 2.00 2.00 guar gum 0.15 0.15 Distearyl Dimethyl Ammonium Chloride 0.25 0.25 Dimethicone 0.00 0.75 Silicone MQ resin 2.25 2.25 spices 0.75 0.75 Methylchloromethylisothiazolinone and methylisothiazolinone 0.07 0.07 Acrylates C10-30 Alkyl Acrylate Crosspolymer 0.30 0.30

Example 16 Spray

A spray was prepared with the following ingredients: 0.17% Dimethicone Copolyol; 0.2% Cyclomethicone (pentamer); 0.001% Octyl Salicylate; 0.001% Benzophenone-3; 0.001% Hydrolyzed Animal keratin; 0.35% fragrance; 1.0% MQ resin (the same type of resin used in Examples 1-4) and appropriate amount of ethanol (eg 95%). Combine SD Alcohol and Trimethylsiloxysilicate in a suitable container. Add dimethicone copolyol, cyclomethicone, octyl salicylate, benzophenone-3, hydrolyzed animal keratin and fragrance to the solution and place the resulting mixture in a in the bottle.

performance evaluation

Performance evaluations were performed for volume increase and adhesion performance as well as aesthetics. The following examples describe these evaluations.

Control Conditioner for Mannequin Testing: Example A

Control samples were prepared using the following ingredients: Part I: 4.50% Cetyl Alcohol; 2.50% Stearyl Alcohol; 2.40% Glyceryl Monostearate; 1.00% Cyclomethicone; 0.50% Polysorbate 80, Cetyl Acetate Mixture of wax esters and acetylated lanolin alcohol (SOLULAN 98 from Amerchol Corporation, Danbury, CT); 1.50% mineral oil; 2.50% white petrolatum; 0.50% propylene glycol; Lauryltrimethylammonium chloride in isopropanol (ARQUD(R) 12-50 from Akzo, Chicago, IL); Part III: 0.50% diazolidinyl urea; 0.75% fragrance. All first part materials were mixed with stirring and heated to 80°C. In a separate vessel all the second part materials were mixed with stirring and heated to 80°C. When both parts were at 80°C, the mixture of the first part was added to the second part mixture with stirring and stirred at 80°C for 10 minutes and then cooled to 40°C. When the combined mixture is at 40°C, add the third portion of ingredients and mix the entire mixture until homogeneous. The resulting mixture was cooled to room temperature.

Manikin volumetric determination

There is a definite need to assess volume using a reliable test that more closely approximates real life results on the user's hair. Manikin volumetric methods fill this need.

Hair volume is related to the volume of the total assembly of hair fibers on the head rather than the volume of individual fibers. Depending on the hair style and length, individual fibers of the hair contact and help support other fibers, thereby maintaining the structure of the hair as a whole. For example, fine hair is less able to support its own weight or the weight of other hair. As a result, the entire hair combination lies flat on the head and thus takes up less volume. Insofar as hair volume is related to the structure of hair as a whole, any hair volume test performed in order to predict the volume of actual hair on the head must use a model of combinations of hair fibers whose configuration resembles that of actual hair on the head . Most existing methods do not use this standard, as many rely on volumetric measurements of single fibers, non-fixed combinations of fibers, or tresses. Because in a braid all the fibers are held together at one end rather than individually at thousands of points throughout the hair, the hair fibers in a braid cannot be viewed as a space-filled structure like actual hair, each Hair supports each other to create volume. Therefore volume measurements on tresses cannot be expected to truly predict actual hair volume changes.

British Patent 2,297,757 describes a modified Robbins and Crawford method in which measurements of tresses provide data for analysis. Because the hair fibers in the tresses have no real opportunity to create space to fill the fiber combination or style on the hair, results related to the consumer's actual hair condition cannot be expected to be obtained with this method.

For laboratory work on the compositions of the present invention, volume measurements have been performed on mannequin heads with numerous points of attachment of actual hair throughout the head. It can therefore be assumed that this hair is the same type of space-filling structure that forms on the human head. Half-head testing in beauty salons and related venues, including testing on women, demonstrates that mannequin volume testing is very good at predicting actual volume changes on the consumer's head.

The mannequin volume test utilizes the traditional beauty parlor half-head test method and image analysis technology to quantify the change in volume. In this test, volume measurements are taken on the hair sections on each side of the head prior to treatment to eliminate possible bias due to unequal amounts of hair in the two hair sections. The head is then processed and dried. All formulations of the invention were tested against a light conditioner as a control. A conditioner formulation is needed as a control to eliminate volume gains from friction damage that can occur when grooming on mannequin heads. Detanglement or roughening of the hair surface is a widely accepted method of adding volume to hair. The technique of detangling hair has been used for decades to achieve a large increase in hair volume. It is noted in the results below that the control conditioner did not negatively affect hair volume. All volume changes measured from the control treatments were positive, indicating that the post-treatment volume was never lower than the pre-treatment volume. (Note that pre-treatment volume is that of clean hair).

To demonstrate that the conditioner control (Example A) did not reduce volume, a series of experiments were performed to validate the use of a light conditioner as a control. For the conditioner, a composition prepared according to Example 1 without MQ resin was tested against a light conditioner prepared in Example A. The results were not significantly different (-4.8% difference and p-value 0.27). For shampoos, the same logic was used; a composition prepared according to Example A was tested against a formulation prepared according to Example 8 but without the MQ resin. The measured volumes provided by the two formulations were not significantly different (3% difference, p-value equal to 0.73), confirming that the conditioner control did not cause a reduction in hair volume.

The mannequin head used in the volumetric experiments was the "Sarah" head purchased from Pivot Point International, Chicago, Illinois. Before the experimental treatments, the mannequin heads were cleaned with a detergent solution containing 20% SLES 2EO, 5% cocamidopropyl betaine and 0.8% sodium cumene sulfonate. To reduce tangles, work detergent into hair with a vent brush. Rinse the head with running water at 38°C (100°F) until the rinse water is clear and clear. The mannequin head was washed twice, each time with 5 ml of detergent solution followed by 2.5 ml of solution. After washing, the mannequin hair was detangled with a brush and then straightened. Then let the hair dry overnight. The hair of the washed mannequin must be combed as flat as possible so that the measured intrinsic volume is minimally affected by the hairstyle. In volumetric experiments, treat both sides of the mannequin head separately. Each side was first wetted with 38°C (100°F) water and then treated with 3ml of control formulation or fluffy formulation. The side of the fluff formulation was alternately applied to each new test head. After application of the formulation, the test formulation was rubbed into the hair for 30 seconds, followed by rinsing with 38°C (100°F) water until the rinse water was clear and clear for at least 60 seconds. For experiments with more than one application of the fluffy formulation and rinse, all applications were done consecutively on one side rather than alternated on both sides of the head. For conditioners containing MQ resin (Examples 1-5), volume measurements were taken after one application. For shampoos containing MQ resin (Examples 7-15), the shampoo was washed 3 times before volume measurements were taken. For Example 6, only one wash was performed. Expression changes on the mannequin head were measured using a Zeiss Kontron image analyzer connected to a Sony XC-77CE compact video camera with 60mm Nikon AFMicro-Nikkor lens. An image of the mannequin is captured by a camera, digitized and the area on each side is measured using a program written for this purpose. Evaluate the apparent change in volume by measuring the cleaned mannequin head, processing the mannequin head, and re-measuring. The percent volume change per side is calculated using the following formula:

Volume change (V _side )=100×[V _side (back)-V _side (front)]/V _side (front) where the V _side is the apparent volume measured on the specific side of the head, Whereas, pre and post refer to values measured before and after treatment. The volume change of a specific treatment is represented by the formula ΔV=ΔV _treatment -ΔV _control . In determining the volume change for a specific treatment, measurements were performed on at least 5 heads per experiment. Data on the control and treated sides were then evaluated using a Paired t-test. Results may also include "p" values that are acceptable in statistical practice; a p-value greater than 0.05 indicates that the data are not statistically significant at the 95% confidence level.

Volume data were obtained from the formulations described in Examples 1-15. The data are listed in Table VII. Note that the data reflect the average of at least 5 evaluations.

Table VII Example % volume increase p-value 1 24.4 0.039 2 21.9 0.032 3 - - 4 20.7 0.008 5 26.1 0.014 6 37.3 0.058 7 21.8 0.025 8 20.0 0.044 9 20.7 0.003 10 16.7 0.045 11 - - 12 20.1 0.017 13 - - 14 29.2 0.007 15 21.1 0.020

The volume increases reported in Table VII were almost all statistically significant (p<0.05). The magnitude of the volume increase ranged from 16.6% to 37.3%, showing that the composition of the present invention is very effective in providing a significant increase in hair volume.

Evidence for the observed volume increase from MQ resin, MQ-A and not from the vehicle is provided by comparing the experimental results of mannequin volume testing of the conditioner of Example 1 with the same formulation without MQ resin. Comparing the conditioner minus the MQ treated side, a 25% increase in volume was observed for the side treated with the MQ containing formulation, confirming that the volume came from the resin and not the vehicle.

human test

Further supporting evidence for the bulking efficacy of the formulations of the invention can be provided by human subjects. In a separate test, female subjects were provided with test samples of the volumizing conditioner of Example 1 or the volumizing shampoo of Example 9. Subjects were instructed to use the sample product for 5 days in the case of the conditioner and 10 days in the case of the shampoo.

Subjects recorded their evaluation of the effect of the test product on hair volume compared to their normal hair volume. The evaluation uses a scale of 1 to 5, with 1 being significantly less volume and 5 being significantly more volume. Data were collected and then analyzed using the Wilcoxon SignedRank Test as described in Practical Nonparametric Statistics, 2nded, W. J. Conover, John Wiley and Sons, 1980. The results indicated that both the conditioner and shampoo test products provided a significant increase in hair volume (95% confidence level).

Curl Persistence

Three locks of clean European hair (3.5 g each) were prepared for each experimental treatment. The uncurled length (L _u ) of each tress was determined before treatment. The hair was then dampened with water, combed out and excess water squeezed out with the thumb and forefinger of gloved hands. Next, the hair was hung from the roots and curled with a standard 2.22 cm (7/8 inch) plastic curling iron, secured with the plastic clip provided with the curling iron and allowed to dry for at least 16 hours. After drying, the plastic curling irons were carefully removed from the hair and treated with a 2.5% solution of the test MQ resin in toluene. This solvent was used because it forms a solution with the MQ resin tested. The test solution was sprayed onto the hair using a Seaquist P 22/290 pump with approximately 0.25 g per actuation. To ensure even application, spray hair 15cm (6 inches) from hair. Each tress was sprayed four times on the front and four times on the back for a total application of 2 grams of solution. Place freshly sprayed hair on a wire rack and allow to dry for 1 hour. Next, they were hung in a humid chamber at 21°C and 80% relative humidity. Length measurements were recorded at 0, 0.25, 0.5, 1, 2, 3, 4 and 24 hours. Curl persistence was calculated for each reading using the following formula:

Curl Persistence (%)=[L _u -L(t)]/[L _u -L(0)]

where L _u is the length of uncurled hair, L(t) is the length of hair at time t, and L(0) is the length of hair at time 0. Its data are listed in Table VIII. The listed value is "Percent Curl Persistence". All MQ resins used were purchased from General Electric Company.

Table VIII MQ resin 15 minutes 1 hour 4 hours 24 hours 50% solids solution of trimethylsiloxysilicate in cyclomethicone (MQ-B) ^{a, d} 43.3 ^* 39.8 ^* 35.0 ^* 34.1 ^* Trimethylsiloxysilicate (MQ-A) ^a 2.2 -6.1 -5.5 -5.1 Tetradecyldimethylsiloxysilicate (MQ-D) ^{a, b} 2.4 2.5 3.6 4.1 Octadecyldimethylsiloxysilicate (MQ-E) ^{a, b} 24.3 ^* 3.0 3.4 4.5 (C16-18)Alkyldimethylsiloxysilicate (MQ-G)a,b,e 11.6 8.3 4.3 4.2 C20-24 Dimethylsilyl silicate (MQ-F) ^{a, b} 9.7 2.1 2.0 3.1 Poly(oxyethylene)dimethylsiloxysilicate (MQ-H) ^a,c,e 15.9 ^* 16.3 ^* 9.7 7.8

a = Purchased from General Electric Company

b = each M unit of the polymer is substituted with a long chain alkyl group

c = each M unit of the polymer is substituted with polyoxyethylene groups of 12-13 oxyethylene units per group

d = Items purchased from General Electric

e = described in US Patent 5,684,112

All curl retention values have been subtracted from the toluene control. Statistically significant tabulated values are marked with an asterisk.

Of the MQ resins listed in Table VIII, only "MQ-B" exhibited significant curl retention after the full 24 hours of the experiment. This indicates that the resin has remarkable adhesive properties. Therefore, the immobilization mechanism can contribute to the increase in volume of this resin listed in Table IX.

Liquid MQ "MQ-A", on the other hand, did not exhibit significant curl permanence and thus no significant adhesive properties. Despite the lack of cohesiveness, it can be seen from the examples in Table VII that liquid MQ still clearly provides high volume.

Summary Example

By way of summary of the examples, Table IX lists the volume measurements obtained on the MQ resins described in Table VIII, where each MQ resin was formulated into the shampoo formulation of Example 8 and the conditioner formulation of Example 1 or both. Among those. The level of MQ resin added in these formulations was 2.5% active.

The data in the column labeled "Deposition" in Table IX are actually relative deposition values and were obtained on wool samples (7cm x 11cm) wetted in running tap water at 38°C with 1ml of the test product (including test MQ resin (shampoo or conditioner containing test MQ resin) treatment and rinse under running tap water at 38°C for 1 minute. MQ resin deposition was then measured using ESCA (Electron Spectroscopy for Chemical Analysis), familiar to those skilled in the art. ESCA is used to quantitatively and qualitatively determine the elemental composition of solid surfaces. The surface of the product tested was wool. Wool is often used as a substitute for human hair because it is chemically and morphologically similar to human hair, and because it is much easier to measure than human hair. As is familiar to those skilled in the art, ESCA uses the photoelectric effect to obtain information about the chemical composition of solid surfaces. The sample surface is irradiated with X-ray photons which interact with the atoms of the material surface. If the photon has sufficient energy, an electron is emitted from the orbital of the surface atom. The kinetic energy of these emitted photoelectrons is measured by an electron spectrometer. The relationship describing this process is BE=X-ray energy-KE, where KE and BE are the measured kinetic energy and calculated binding energy of the emitted photoelectron, respectively. The electron binding energy is characteristic of the element and the electron subshell that emits electrons and is used to identify different elements at solid surfaces. The characteristic peaks of the MQ resin were first determined using the pure material. The peak areas appearing on the sample are used to determine the relative concentration of elements on the sample surface. For MQ resin deposition, the Si peak shows a unique shape that helps to distinguish MQ resin from other silicones such as dimethicone. The area under the silicon peak allows the calculation of the percent silicon present. For each sample tested, 3 replicate wool samples were prepared. Of the three samples, two were initially analyzed. If there is a large discrepancy between the 2 determinations, a third sample is tested for confirmation. The method was carried out with the examples listed in Table IX. The value in the Deposition column is calculated by dividing the measured deposition of the specific MQ resin on the wool sample by the deposition of the trimethylsiloxysilicate resin (MQ-A) on the wool. These values are therefore relative laydowns of the various resins relative to the MQ-A resin.

Table IX illustrate form M:Q ratio viscosity Result (volume change) p-value (volume change) Sedimentation Trimethylsiloxysilicate (MQ-A) liquid 1:1 4500-12000cP Shampoo + 20% Conditioner + 24.4% 0.0440.039 11 50% solids solution of trimethylsiloxysilicate in cyclomethicone (MQ-B) solid dissolved in cyclomethicone 0.7:1 solid Shampoo + 31.1% Conditioner + 21.4% 0.0020.066 0.800.70 Tetradecyldimethylsiloxysilicate (MQ-D) liquid 2:1 50cP Shampoo - 2.8% 0.52 1.57 Octadecyldimethylsiloxysilicate (MQ-E) solid (waxy) 2:1 solid Shampoo + 2.1% Conditioner + 8% 0.670.37 1.710.68 (C20-C24)Alkyldimethylsiloxysilicate (MQ-F) solid (waxy) 2:1 solid Shampoo + 6.4% Conditioner - 8.9% 0.300.57 2.401.32 (C16-C18)Alkyldimethylsiloxysilicate (MQ-G) liquid 2:1 50cP Shampoo +4.3% 0.33 2.15 Poly(oxyethylene)dimethylsiloxysilicate (MQ-H) liquid 2:1 340cP Conditioners - 12.7% 0.22 0.50

Note that the resin designated "MQ-A" in Table IX provided increased bulk without appreciable adhesive properties. Compared to this performance, no MQ resins with a M:Q ratio of 2 were observed to provide large volumes; although these resins had comparable (relative) or greater Amounts of methylsiloxysilicate (MQ-A) were deposited, but they had little or no adhesion properties (Table VIII) and provided no volume. The MQ-B resin provides significant bulk, but exhibits adhesive properties (unlike the MQ-A resin). Because of the adhesive properties of MQ-B resins, it is predicted that MQ-B resins will suffer from the same defects as conventional anchoring polymers.

Examples 16 and 17

Samples of Examples 16 and 17 were prepared using the following ingredients: 16.80% Ammonium Lauryl Sulfate; 0.30% Monosodium Phosphate; 0.25% Polyquaternium-10; 2.00% Cocodiethanolamide; 0.22% Guar Gum; 0.50% Distearyl Phthalamide; 1.76% Sodium Cumene Sulfonate; 0.75% Perfume; 0.07% Preservative (KATHONCG), and the ingredients listed in Table X. Use an appropriate amount of distilled water to bring the total to 100%. Note that the MQ-A is the same as the MQ-A described in the previous embodiments.

Table X Element Example 16 Example 17 MQ resin (MQ-A) 0.75 0.60 Dimethicone 1.00 2.00 ACULYN 22 0.90 0.90 ACULYN 33 0.84 0.84 distilled water Appropriate amount Appropriate amount

With the exception of 10% distilled water remaining, all remaining water and sodium phosphate were combined in a suitable vessel, mixed for 10 minutes and heated to 50°C. ACULYN(R) 22 Acrylate Material, ACULYN(R) 33 Acrylate Copolymer, and Ammonium Lauryl Sulfate were added to the vessel, the pH was raised to 7.0 using 50% sodium hydroxide and the ingredients were mixed for 10 minutes. Add sodium cumene sulfonate and mix until homogeneous. The pH was then lowered to 6.0-6.5 using 50% citric acid. Premix remaining distilled water and Polyquaternium-10 for 1-2 minutes and add to container. In a separate vessel the coconut diethanolamide, guar gum and distearyldimethylammonium chloride were combined and heated to 50°C with stirring. Add this to the main container with stirring. Distearylphthalic acid amide was melted at a temperature of 45-50°C in a separate vessel and added to said vessel with stirring. Add the silicone MQ resin to the container and mix for 15 minutes. Add the dimethicone to the container and mix for 15 minutes. Then let the container begin to cool. When the temperature of the mixture reaches 40°C, the fragrance is added. After continuing to cool, add the preservative at a temperature below 38°C. The final formulation was cooled to room temperature.

Claims (28)

1, a kind of fluffy Haircare composition of hair that makes comprises the MQ resin of the formula IA of effective dose:

Formula IA

In the formula:

M ¹And M ²Respectively be independently selected from

(a) hydrogen,

(b) phenyl,

(c) phenethyl,

(d) polyethers of Formula Il:

-H ₂C-(CH ₂) _n-(O-CH (R ¹⁰)-CH ₂) _u-(OCH ₂-CH ₂) _v-OR ¹¹N is the number of 1-20 in the formula II formula ,-(CH ₂)-chain can be chosen wantonly and comprise 1 or 2 degree of unsaturation; U and v respectively are independently selected from the integer of 0-20, and condition is u+v 〉=1; R ⁴, R ⁵, R ⁶And R ⁷Respectively be independently selected from phenyl and C _1-12Branch and unbranched hydrocarbon; R ¹⁰Be selected from C ₁-C ₂₀Alkyl; R ¹¹Be selected from H ,-CH ₃With-C (O) CH ₃With

(e) C that is replaced by halogen ₁-C ₃The optional C that replaces of alkyl ₁-C ₂₄Branch or unbranched hydrocarbon; With

(x+y)/z is the number of 0.5 to 1.5 scope in the formula; And R ⁴, R ⁵, R ⁶, R ⁷, x, y, z, M ¹And M ²Value be selected from and make described MQ resin for having 1.0 * 10 ³To 1 * 10 ⁶The value of the liquid of the viscosity of centipoise.

2, according to the compositions of claim 1, wherein said compositions is a kind of water base shampoo.

3, according to the compositions of claim 1, wherein said compositions is water base conditioner.

4, according to the compositions of claim 1, wherein said compositions is a kind of spray.

5, according to the compositions of claim 1, wherein said compositions is a kind of hair dye.

6, according to the compositions of claim 1, comprise

(a) based on the MQ resin of the formula IA of described composition total weight 0.01-15% weight; With

(b) based on the hair care carrier that is selected from shampoo, conditioner, spray and hair dye of described composition total weight 85-99.99% weight.

7, according to the compositions of claim 1, the viscosity of wherein said MQ resin is 1.5 * 10 ³To 1 * 10 ⁶The scope of centipoise.

8, according to the compositions of claim 1, the viscosity of wherein said MQ resin is at 1000-100, the scope of 000 centipoise.

9, according to the compositions of claim 1, the viscosity of wherein said MQ resin is 1,000-50, the scope of 000 centipoise.

10, according to the compositions of claim 1, wherein said MQ resin has formula IB:

Formula IB

R in the formula ²Be selected from and M ¹Identical group; R ¹And R ³Respectively be independently selected from and R ⁴Defined identical group; X '/z ' is 0.5 to 1.5 a number.

11, according to the compositions of claim 1, M wherein ¹And M ²Respectively be independently selected from C ₁-C ₂₄Branch and unbranched alkyl.

12, according to the compositions of claim 11, M wherein ¹, M ², R ⁴, R ⁵, R ⁶And R ⁷It respectively is methyl.

13, according to the compositions of claim 10, R wherein ²Be selected from C ₁-C ₂₄Branch and unbranched alkyl.

14, according to the compositions of claim 13, R wherein ¹, R ²And R ³It respectively is methyl.

15, according to the compositions of claim 1, (x+y)/z=1 wherein.

16, according to the compositions of claim 10, x '/z '=1 wherein.

17, according to the compositions of claim 14, x '/z '=1 wherein.

18, according to the compositions of claim 1, also comprise fixative.

19,, comprise the MQ resin of 0.1-7.5% according to the compositions of claim 2.

20,, comprise the MQ resin of 0.1-5.0% according to the compositions of claim 19.

21,, comprise the MQ resin of 0.1-3.0% according to the compositions of claim 19.

22,, comprise the MQ resin of 0.2-2.5% according to the compositions of claim 19.

23,, also comprise the conditioner of 0.1-2.0% according to the compositions of claim 18.

24, according to the compositions of claim 2, also comprise the detersive surfactant of 4.00-60.00%, be selected from C ₈-C ₁₈Alkyl sulfate, in molecule, contain the C of 1-5 oxyethylene group ₈-C ₁₈Alkyl oxyethylene group ether sulfate, C ₁₀-C ₁₈Acyl isethinate, C ₁₀-C ₂₀Alkylsulfonate, C ₁₀-C ₂₀At least a anionic detergent of olefin sulfonate or its mixture; Or at least a:

(i) C of the water-soluble growth regulator of 0.10-5.00% anion ₁-C ₃Alkylbenzenesulfonate or C ₅-C ₆Alkyl sulfate;

(ii) the 0.10-15.00% amphoteric surfactant is selected from C ₈-C ₁₈Alkyl betaine, C ₈-C ₁₈Alkyl sulfobetaines, C ₈-C ₁₈Alkylamidoalkyl C ₂-C ₃Alkyl betaine, C ₈-C ₁₈Alkylamidoalkyl C ₂-C ₃Alkyl sulfobetaines, C ₈-C ₁₈Alkyl both sexes acetate, C ₈-C ₁₈Alkyl both sexes propionate, cocamidopropyl betaine or its mixture; With

(iii) 0.1-4.0% non-ionic surface active agent,

Condition is 60% weight that the total amount of detersive surfactant is no more than described composition total weight.

25,, also comprise the stabilizing agent of 0.10-5.00% according to the compositions of claim 2.

26,, also comprise matrix material and at least a cationic surfactant according to the compositions of claim 3.

27, according to the compositions of claim 26, wherein said at least a cationic surfactant is selected from the cationic surfactant that contains amino or quaternary ammonium hydrophilic segment.

28, according to the compositions of claim 27, wherein said at least a cationic surfactant is selected from formula (R ¹⁰) (R ¹¹) (R ¹²) (R ¹³) N ^{+ 1}The component of-X, R in the formula ¹⁰For the aliphatic group of hydrogen, a 1-22 carbon atom or have the aromatics aryl or the alkylaryl of 12-22 carbon atom; R ¹¹For having the aliphatic group of 1-22 carbon atom; R ¹²And R ¹³Respectively be independently selected from alkyl with 1-3 carbon atom; X is the anion that is selected from halogen, acetate, phosphate radical, nitrate anion and alkyl sulfate group.