CZ277394A3 - Adhesives containing grafted polysiloxane polymer and cosmetic mixtures prepared therefrom - Google Patents

Abstract

Polymeric adhesive agents are disclosed which comprise polysiloxane grafted polymers wherein: (a) the polymers are made by polymerization of polysiloxane-containing monomers and non-polysiloxane-containing monomers, typically by free radical polymerization; (b) the adhesive agent has a weight average molecular weight of at least about 20,000 and contains from about 1 % to about 50 %, by weight, of polysiloxane-containing monomer; and (c) the weight percentage of silicon present as unreacted polysiloxane-containing monomer and silicone-grafted polymer having a viscosity at 25 DEG C of below about 10,000,000 centistokes based on the total silicon present as unreacted silicon monomer and polysiloxane-grafted polymer is about 15 % or less. Also, the adhesive agent contains no more than about 4 %, by weight, of unreacted polysiloxane-containing monomer and polysiloxane-grafted polymer having a viscosity at 25 DEG C of below about 10,000,000 centistokes. Cosmetic compositions containing such adhesive agents are also disclosed.

Description

The present invention relates to adhesives comprising cross-linked polysiloxane polymers and compositions such as cosmetic compositions containing adhesives.

BACKGROUND OF THE INVENTION

The effort to keep the hair in the intended shape is widespread. Tazon conservation is usually achieved by one of the following methods: permanent chemical treatment or temporary treatment of the phason and hairstyle. A temporary treatment is one that can be removed with water or shampooing. Temporary treatment of the bean is usually done by applying the composition to wet hair after shampooing and / or conditioning before drying and / or bean treatment. Materials that exhibit the properties so useful are generally resins or gums and are generally applied in the form of foams, gels, hair lotions or sprays. However, this procedure has several significant drawbacks for the user. It requires a special step after the shampooing / conditioning, applying the treatment composition, and further, since the preservation of the bean is done using resin-setting materials on the hair, the hair may become sticky or stiff after application, and it is difficult to change the bean treatment without applying the composition. _: · ^ -. ·

Recently it has been discovered that hair protection compositions containing graft polysiloxane polymers show excellent results in terms of phason conservation and conditioning. The compositions may be incorporated into conventional formulations as set forth below, without being limited thereto, shampoos, conditioners, hair sprays, tonic, hair lotions, gels and foams. These compositions show an improvement in the properties of the treated hair without becoming stiff or sticky, as is the case with conventional hair conditioners.

Such types of adhesives, i.e. film-forming graft polysiloxone polymers, can also be used for other purposes such as, for example, topical skin applications in cosmetic applications or as drug delivery agents, and can also be used in a wide variety of applications adhesives, such as in the manufacture of adhesive papers or binding materials, and atdr ---- Polysiloxone graft polymers are described in EPO Application 90307528.1 published 16.1. 1991 as EPO Publication 0 408 311 A2, Hayama et al., U.S. Pat. No. 5,061,481, issued Oct. 29, 1991 to Suzuki et al. No. 5,106,609, Bolich et al., Issued Apr. 21, 1992; U.S. Patent 5,100,658, Boiich et al., Issued Mar. 31, 1992; No. 5,100,657, Ansher-Jackson et al., Issued Mar. 31, 1992; No. 5,104,646, Bolich et al., Issued Apr. 14, 1992; Seriál No. No. 07 / 758,319, Bolich et al., Issued Aug. 27, 1991; Seriál No. 07 / 758,320, Torgerson et al., Filed Aug. 27, 1991. Adhesive compositions comprising film-forming graft polysiloxone polymers are also described in U.S. Pat. No. 4,728,571, issued Mar. 1, 1988 to Clemens et al. No. 5,021,477, issued Jun. 4, 1991 to Garbe et al. No. 4,981,903, Mitra et al., Issued Jan. 1, 1991. Mitra et al.

By using these graft polysiloxane polymers, excellent appearance qualities can be achieved. In particular, for hair dressing compositions, it is desirable to achieve adhesion as well as a higher level of palpability at a given level of adhesion of compositions containing such adhesives. For example, it is particularly desirable to provide hair conditioning compositions with improved cohesiveness and / or softness for palpation for a given cohesiveness level. It is an object of the present invention to provide adhesives which provide an increase in the quality level.

These and some other improvements will become apparent in the detailed description that follows.

Unless otherwise indicated, all percentages are percent by weight and proportions are percentages by weight. The invention may include, consist of, or consist solely of the essential as well as optional ingredients and components described herein.

SUMMARY OF THE INVENTION

The present invention relates to polymeric adhesives and in particular to film-forming agents comprising a graft polysiloxane polymer prepared by polymerizing polymerizable polysiloxane-containing monomers with polymerizable monomers free of polysiloxane, wherein the adhesives have an average molecular weight of at least 20,000 and containing from 50% by weight polysiloxane-containing monomer. and the weight percent of silicone present as unreacted polysiloxane-containing monomers and grafted polysiloxane polymers have a viscosity of less than 1 x 10 ⁷ centistokes at 25 ° C based on the total silicone content present as unreacted polysiloxane-containing monomer and graft polysiloxane polymer is 15% or less. Adhesives should not contain more than 4% by weight of unreacted polysiloxane-containing monomer and graft polysiloxane polymer having a viscosity of less than 1 x 10 ⁷ at 25 ° C.

In another example, the present invention describes cosmetic compositions, and in particular hair care compositions such as hair care compositions - including such adhesives and a carrier suitable for application to the hair.

Description of the invention

In the description of the present invention, see below, essential as well as various optional components of the compositions are described.

Polymer Adhesives - - - .....—

Polymeric adhesives include a micro-grafting / polysiloxane polymer prepared by polymerizing polymerizable polysiloxane-containing monomers with polymerizable non-polysiloxane monomers, wherein the adhesives have an average molecular weight of at least 20,000 and contain from 1 to 50% by weight of the polysiloxane-containing monomer and and the graft polysiloxane polymers have a viscosity of less than 1 x 10 ⁷ centistokes at 25 ° C: to the total silicone content present as unreacted polysiloxane-containing monomer and the graft polysiloxane polymer is 15% or less.

The content of the polysiloxane-containing monomer in the adhesive comprises the monomer present in the adhesive both as an unreacted component and as a polymerized monomer. The adhesive should not contain more than 4% by weight of unreacted polysiloxane-containing monomer and graft polysiloxane polymer having a viscosity of less than 1x10 ⁷ at 25 ° C, preferably less than 3%, more preferably less than 2%, most preferably less than 1%. Furthermore, a certain limitation related to the adhesive is the maximum viscosity level as described above, which is preferably limited to 1x10 ⁶ , 1x10 ⁵ or 1x10 ⁴ and the like.

The cosmetic compositions of the present invention usually contain from 0.1% to 10% adhesive, preferably from 0.5% to 8% adhesive, although higher or lower amounts may be used for some applications. The adhesives described herein may advantageously be used for the manufacture of other cosmetic products such as make-up, mascara and eyeliner, nail polish, etc., as well as for skin topical products such as creams and lotions, including formulations for transport of drugs or other ingredients to the skin. Such an adhesive can also be used in other adhesive applications, e.g., in the manufacture of adhesive paper or wrapping paper, etc.

The adhesive should have an average molecular weight of at least 20,000. There is no upper limit for the molecular weight except where this would limit the applicability of the compositions of the present invention for practical reasons such as processing, aesthetic characteristics and formability, etc .. less than 1 χ 10 ⁷ generally less than 5x10 ⁶ and usually less than 3x 10 ⁶ . Preferably, the molecular weight is from 5x10 ⁴ to 2x10 ⁶ , more preferably from 7.5x10 ⁵ to 1x10 ⁶ and most preferably from 1x10 ⁵ to 7.5x10 ⁵ .

In particular, for cosmetic compositions, the dried adhesive forms have a Tg of at least -20 ° C, preferably at least 20 ° C, so that they are not sticky. As used herein, the designation * Tg "refers to the glass transition temperature of the non-silicone spine, and the designation Tm" refers to the melting point of the crystalline material of the non-silicone spine, if such conversion exists for the polymer. Preferably, the Tm (if any) is about -20 ° C, more preferably about 20 ° C.

The polymers useful in the compositions of the present invention are graft polysiloxane polymers of polymerizable silicone-containing or polysiloxane-containing monomers and silicone-free monomers. The graft polysiloxane polymers should meet the following four

---- Criteria: - - - 1) After drying, the polymer phase is divided into a discontinuous phase comprising a silicone portion and a continuous phase comprising a non-silicone portion;

2) the silicone portion is covalently grafted to the non-silicone portion; and

3) the molecular weight of the silicone moiety is not less than 500 o

When using such compositions in cosmetic applications to hair or skin, the non-silicone portion should render the polymer soluble or dispersible in the vehicle of the composition to allow the polymer to deposit on the intended surface, eg, hair or skin.

The most preferred polymers include an organic backbone, usually of the carbon type, such as a polyvinyl backbone, and also preferably a polydimethylsioxane macromer having an average molecular weight of at least 500, preferably from 1000 to 100,000, more preferably from 2000 to 50,000, most preferably from 5,000 to 20,000. spine. The organic polymer backbones contemplated are derived from unsaturated polymerizable ethylene-type monomers which include vinyl monomers and other monomers for condensation, e.g., those which form polyamides and polyesters during polymerization and cycle opening monomers such as ethyloxazoline or caprolactone. The polymer is characterized in that, if included in the final blend, after drying, the polymer phase is separated as + i ιΑΙλ * VUIOIW / I II II lUVUtl H

ÍGZO,

Kieiu bie iii puiyun i itnyteiiuxui luva discontinuous phase, which includes polymer backbone. It is believed that this phase separation ability is related to the specific orientation of the polymer, which results in the desired feel and feel, film formation, or other adhesive properties. The phase separation capability of the polymer blends of the present invention is determined as described below.

O

The polymer is cast as a solid film using a suitable solvent (i.e., a solvent that dissolves both the polymer backbone and silicone). This film is cut and examined by transmission electron microgrophy. Microphase separation is demonstrated by observing inclusions in the continuous phase. These inclusions should have a suitable size corresponding to the size of the silicone chains (usually hundreds of nm or less) and a suitable density corresponding to the amount of silicone present.

These properties are well documented for polymers with this structure, see, e.g., SmithS. D., PhD Thesis, University of Virginia, 1987, and references cited therein.

The second way to determine the phase separation pattern is to detect an increase in the concentration of silicone on the surface of the polymer film compared to the concentration inside the polymer, since the silicone prefers low-energy air interface and orientates predominantly on the polymer surface. This creates a surface with silicone oriented towards the film's own surface. This phenomenon can be experimentally demonstrated by ESCA (electron spectroscopy for chemical analysis) on the surface of dried films. This procedure shows high silicone content and reduced polymer backbone content when analyzing the film surface. The surface in this case is an area of the strength of the first few tens of angstroms. By varying the angle of the test beam, the surface can be analyzed to different depths.

Examples of useful polymers and their preparation are described in detail in U.S. Pat. No. 4,593,935, Mazurek, issued September 15, 1987; No. 4,728,571, Clemens et al., Issued March 1, 1988, both of which are incorporated herein by reference. These polymers consist of: at least one free-radically polymerizable vinyl monomer or monomers (A); and optionally at least one copolymerizable monomer crosslinking agent which is more hydrophilic than A and is selected from the group consisting of hydrophilic monomers and macromers having a Tg or Tm of about -20 ° C (B). Polymers also contain polysiloxane-containing monomers. (C) Polymerizable macromers that can be used herein should be grouped collectively as polymerizable monomers as monomers'. Hydrophobic monomers are monomers that consist essentially of water-insoluble homopolymers. Hydrophilic monomers means monomers which do not form essentially water-insoluble homopolymers. Suitable polymers are also described in EPO Application 90307528.1, published as EPO Application 0 408 311 A2, 11.1. 1991, Hayama et al. No. 5,051,481, issued Oct. 29, 1991 to Suzuki et al. No. 5,105,509 to Bolich et al. 1992. U.S. Pat. Patent 5,100,658. Bolich et al., Issued 31.3. 1992, U.S. Pat. Patent 5,100,557. Ansher-Jackson et al., Issued Mar. 31, 1992; No. 5,104,646; Bolich et al., Issued Apr. 14, 1992; Seriál No. 07 / 758,319, Bolich et al., - “Registered” 27 Aug; 1991, U.S. Pat. Seriál No. 07 / 758,320, Torgenson et al., Registered Aug. 27, 1991 and references cited therein.

The grafted polysiloxane polymers described herein comprise from 1 to 50% by weight of C monomers, i.e., polysiloxine-containing monomers, and from 50 to 99% by weight of polysiloxane-free monomers, which may be selected from the group consisting of A and B monomers with mixtures thereof.

Examples of suitable hydrophobic A monomers are esters of acrylic or methacrylic acid and C1 to _C8 alcohols such as methanol, ethanol, methoxyethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol , 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol,

- 3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol,

t-butanol (2-methyl-2-propanol), cyclohexanol, neodecanol, 2-ethyl-1-butanol, * 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptanol, 2-ethyl-1 -hexanol,

3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-dodecanol, 1-hexadecanol, 1-octadecanol, dtp., C to C ₁₈ alcohols, preferably C up to C ₁₂ alcohols, styrene, polystyrene macromer, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl propionate, α-methylstyrene, t-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyltoluene and mixtures thereof. Preferred A monomers include n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate,

Ψ L · ^. · T) i i i-uuiyniienuKiyiui,

2-ethyl iexyl iit? OKI ylu i, meiyímeiOKryiai and mixtures thereof.

Most preferred A monomers include t-butyl acrylate, t-butyl methacrylate, and mixtures thereof:

Examples of suitable hydrophilic B monomers include acrylic acid, methacrylic acid, Ν, Ν-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternary dimethylaminoethyl methacrylate, methacrylamide,

N-butyl acrylamide, maleic acid and its monoesters, maleic anhydride, crotonic acid and itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, diallyldimethytammonium chloride, vinylpyrrolidone, vinyl ethers such as methylvinyl ether, polyvinyl sulfonate, other imides of maleic acid, other imides of maleic acid allyl alcohol, vinyl alcohol prepared by hydrolysis of vinyl acetate after polymerization, vinylcaprolactam and mixtures thereof. Preferred B monomers include acid

-acrylic, Ν, Ν-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinylpyrrolidone, the acid and amine salts described above and mixtures thereof.

Preferred polymerizable polysiloxane (C monomer) monomers can be represented by the general formula:

X (Y) _n Si (R) ₃ ; _m Z _m wherein X is a vinyl group copolymerizable with monomers A and B, Y is a bivalent spacer (spacer), R is H, OH, lower alkyl (e.g. C 1 to C ₄ ), aryl, alkylaryl, alkoxy or alkylamino, Z is a monovalent siloxane polymer group having an average molecular weight of at least 500 o which is substantially non-reactive under copolymerization conditions and is adjacent to the vinyl polymer backbone see above, n is 0 or 1 and m is a number from 1 to 3. C has an average molecular weight as described above. The preferred monomer O is represented by the general formula:

• •, ίί’ί

XC (= O) -O- (CH 2 O) _p -Si (R 1, where m is 1, 2, or 3 (preferably m = 1), p is 0 or 1, q is a number from 2 to 6, R ¹ is H, OH, lower alkyl, alkoxy- or alkylamino, aryl or alkylaryl (R ⁴ is preferably alkyl), X is R ² -CH = C- (R ³ ) -, R ² is H or COOH (R ² is preferably H ), R ³ is H, methyl or _-CH? COOH (preferably R ³ is m, ethyl), Z is R ⁴ - (- Si- (R ³⁾ - (R ^') O-)' ^4, R ⁵ and R ⁴ are independently lower alkyl, alkoxy or alkylamino, aryl, alkylaryl, H or OH (R ⁴ , R ⁵ and R ⁶ are preferably alkyl) and is a number of about 5 or greater, preferably from 10 to 1500 most preferably from 100 to 250. Most preferably, R ⁴ , R ⁵ and R ^{6 are} methyl, p = 0 and q = 3.

Typically, the amount of monomers A and B in the adhesive polymer is preferably from 50 to 99%, more preferably from 0 to 98%, most preferably from 75 to 95% by weight of the polymer in the adhesive. The content of monomers A ranges from 0 to 99%, the content of monomers B ranges from 0 to 99% and the content of monomers C ranges from 1 to 50%, preferably from 1 to 40%, more preferably from 2 to 25%. The composition of the composition of each particular polymer of the adhesive helps assure the formulation properties of the polymer. By suitably selecting and combining components A, B, and C, the adhesive polymer can be optimized for inclusion in a particular vehicle. polymers soluble in aqueous mixtures or other polar or hydrophilic solvents preferably contain from 0 to 85% (preferably from 5 to 70%) of monomer A, from 14 to 95% (preferably from 29 to 80%) of monomer B by from 1 to 40% (preferably from 2 to 25%) monomer C. The polymers dispersible in aqueous mixtures are preferably composed of: from Odo 70% (preferably from 5 to 70%) monomer A, from 20 to 80% (preferably from 20 to 60%) monomer B and from 1 to 40% (preferably from 2 to 25%) of monomer C. Polymers which are soluble or dispersible in low-polar or non-polar solvents such as cyclomethicone preferably contain from 5 to (preferably from 50 to 90%) monomer A, from 0 to 80% (preferably from 0 to 45%, most preferably from 0 to 20%) of monomer B and from 1 to 40% (preferably from 2 to 25%) of monomer C.

The grafted polysiloxane polymers can be executed according to the procedure below. In general, polymers can be prepared by radical polymerization of silicone or polysiloxane-containing monomers. A film-forming cosmetic composition comprising this product is prepared essentially by removing unreacted polysiloxane-containing monomers and graft polysiloxane polymers having a viscosity of less than 10 ⁷ at 25 ° C, up to the content of silicone present as described above. The monomer or polymeric material that has been removed both have a relatively low molecular weight as compared to the smoky weight of the cosmetic composition.

It is not considered necessary to exclude from the present invention any graft polysiloxane polymer prepared by free-radical polymerization or by a method other than free-radical polymerization, unless such product substantially contains the abovementioned undesirable materials, either by subsequent purification after the polymerization reaction itself or another type of synthesis. It should be understood that block copolymerization products of alternating organic blocks and silicone blocks are not included as graft polysiloxane polymers. The general principles of radical polymerization methods are known and are described, for example, in the Principies of Polymerization. Odian. 2nd Edition, John Wiley & Sons, 1981, pp. 179-318. All the monomers used are introduced into the reactor together with a sufficient amount of a suitable solvent, resulting in a suitable viscosity ^- reaction mixture after completion of the reaction. Usual amounts of monomer used range from 20 to 50%. If necessary, unwanted polymerization terminators, especially oxygen, are removed. This is done by evacuating or purging with an inert gas such as argon or nitrogen. The polymerization initiator is added to the reaction and the temperature of the reaction mixture is adjusted to initiate the reaction, provided that thermal initiators are used. Redox or radiation initiators may also be used if desired. The polymerization is allowed to proceed until a high conversion level is reached, usually from a few hours to several days. The solvent is then usually removed by evaporating or precipitating the polymer by adding a solvent. If necessary, the polymer is subsequently purified.

As an example, Polymer 1, 2 and 3 described above and are prepared. _P as follows. There are many variations to these procedures that fall within the skill of the chemist skilled in the art (eg, choice of degassing and gas method, choice of initiator type, conversion range, amount and reactants, etc.). The choice of initiator and solvent is often determined by the requirements of certain monomers used, since different monomers have different solubilities and different reactivity to a particular initiator.

________Polymer 1: 20 parts of acrylic acid, 60 parts of t-butyl acrylate and 20 parts of monomer containing polysiloxane (molecular weight 10,000) were placed in a flask. Sufficient ethyl acetate or acetone (preferably acetone) was added as reaction solvent to give a final monomer of 40%. Then, the initiator, benzoyl peroxide, was added up to 0.5% by weight based on the amount of monomer. The vessel was evacuated, filled with nitrogen, then the mixture was heated to 60 ° C and this temperature was then maintained with stirring for 48 hours. Reaction η

The reaction mixture was transferred to a Teflon coated pan, placed in a vacuum oven, and the solvent was evaporated. A similar method can be used to prepare 80% / 120% t-butyl acrylate / polysiloxane containing monomer (10,000 molecular weight). Ethyl acetate is the preferred solvent for this synthesis.

- ^; Polymer 2: 20 parts of Ν, dim-dimethylacrylamide, 6 parts of isobutyl methacrylate and 20 parts of silicone macromer were placed in a reaction vessel with a temperature sensor, reflux condenser, inlet port and argon introduced. Sufficient toluene was added to achieve a final monomer concentration of 20% by weight. Argon was introduced for 1-2 hours while the mixture was heated to 62 ° C in a water bath. An initiator, azobisisobutyronitrile, up to 0.25% by weight of monomer present was added. The temperature was maintained at 62 ° C at a sufficient argon flow rate so; the solution was stirred. The reaction was monitored visually and it was ensured that there was no phase separation of the reactants during the polymerization. If turbidity is observed, it is necessary to add hot enough · degassed toluene to eliminate turbidity. The course of the reaction was monitored. Reaction # was complete after 4-6 hours and the mixture was purified as for Polymer 1.

Polymer 3: 10.5 parts were placed in a reaction vessel equipped with argon feed, a temperature sensor, a reflux condenser, and an inlet port.

Ν, dl-dimethylmethacrylamide, 5 parts of isobutyl methacrylate and 3.5 parts

Of 2-ethylhexyl methacrylate and 30 parts of a 10K PDMS macromer. Sufficient toluene or isopropanol was added to achieve a final monomer concentration of 20% by weight. The mixture was stirred for 1 hour and purged with argon. During the wash, the mixture was heated to 60 ° C in a water bath. Was added. initiator, azobisisobutvronitrile, up to 0.25% (if toluene is the solvent) or 0.125% (isopropanol is the solvent) by weight based on the weight of the monomer present. The mixture was stirred and purged with a slow stream of argon at 60 ° C for 6 hours. The reaction was then complete and the solvent was removed as in Polymer 2.

Removal of the undesired polysiloxane-containing monomer and / or graft polysiloxane polymeric material having a viscosity of less than 10 ⁷ at 25 ° C from the radical polymerization product can be accomplished by known methods. The materials to be removed generally have a lower molecular weight than the average molecular weight of the polymer material prior to extraction. These materials to be removed contain a relatively high proportion of polysiloxane relative to the organic compound (i.e. usually (but not necessarily) More than 50% polysiloxane.

Suitable techniques for removing unwanted polymeric material include a variety of standard procedures known in the art.

One useful method is supercritical fluid extraction, e.g. with supercritical carbon dioxide.

The supercritical fluid extraction is performed with a polymer that has been dried after removal from the reaction mixture to remove excess reaction solvent. The dried polymer is preferably crushed to form a fine powder whose enlarged surface helps to increase the extraction efficiency. The extraction can be performed with supercritical carbon dioxide at a temperature of at least 40 ° C and a pressure ranging from 400 to 500 atmospheres. The particular pressure and temperature values depend on known criteria, such as solvent, polymer batch size, fineness of the crushed material, and the desired extraction efficiency. Extraction occurs by washing the sample under pressure with supercritical carbon dioxide, usually for 1 to 4 hours. Unreacted polysiloxane-containing monomer and low molecular weight polysiloxane polymer are dissolved in carbon dioxide and conveniently transported from the remaining polymer by conventional procedures, e.g.

. Others in general. a useful method is membrane separation carried out according to known standard procedures.

A method that is particularly suitable for adhesives comprising graft polysiloxane polymers that are soluble in water, alcohol, or other polar solvents is non-polar solvent extraction. Suitable solvents include C ₃ -C ₆ hydrocarbons, preferably C ₆ -C ₆ hydrocarbons such as hexane. Prior to extraction, the polymerization reaction product is precipitated from the reaction solvent (e.g., by adding water) and dried. The solvent for extraction is preferably heated to a temperature near or slightly in excess of the Tg portion comprising the non-silicone backbone of the grafted polysiloxane polymer adhesive. The temperature is high enough to soften the polymer, but not high enough to solidify. The Tg of the polymer varies from species to species of polymer. The extraction solvent and the reaction product may be mixed before or after heating the solvent and should preferably be mixed in excess of solvent for a time that ensures effective removal of the soluble materials. The length of this time depends on the ^λ boiling point of the solvent. The Tg of the graft adhesive polysiloxane polymer, the temperature to which the solvent is currently heated, the desired degree of removal of unreacted monomer and the polysiloxane-containing polymer having a viscosity of less than 10 ⁷ at 25 ° C and the number of extraction cycles performed. Preferably, the extraction times are from 30 minutes to 2 hours, more preferably from 30 minutes to 1 hour. The solvent may be removed after each cycle by conventional means; eg by decantation by filtration, etc.: followed by drying or distillation to remove the remainder of the reaction solvent remaining in the product after the last extraction cycle.

Analysis of polymer reaction product and extracted materials and ^? The purified film-forming agent can be performed by conventional analytical ³ techniques, such as nuclear magnetic resonance (NMR), infrared molecular spectroscopy, gel permeation chromatography, and atomic absorption or emission spectroscopy,

Carrier

The cosmetic compositions of the present invention include a carrier or carrier mixtures suitable for application to the skin or hair. The carriers are present in a content of from 0.5 to 99.5%, preferably from 5 to 99.5%, most preferably from 10 to 98% by weight of the composition. As indicated herein, "suitable for application to the hair" means that the carrier does not damage or it does not negatively affect the aesthetic properties of hair and does not cause skin irritation. The choice of a suitable solvent also depends on the type of polymer used and also when the product is intended to be left on the surface to which it has been applied (eg, hairspray, foam or tonic) or rinsed (eg, shampoo or conditioner) after use. .

Carriers used herein include solvents as well as other carriers or vehicles commonly used for hair care compositions. The selected solvent must dissolve or disperse the grafted polysiloxane polymer used. The grafted polysiloxane polymer can be designed using a suitable combination of polymers for mixtures with a variety of solvents. Suitable solvents for use in the present invention include, but are not limited to, water, lower alcohols (e.g., C ₁ to C ₆ monoalcohols such as ethanol and isopropanol), hydroalcoholic mixtures, hydrocarbons (such as isobutane, hexane, decane, acetone) halogenated hydrocarbons (such as Freon), linalool, hydrocarbon esters (such as ethyl acetate, dibutyl phthalate), volatile silicon derivatives, especially siloxanes (such as fenylpentametyldisiloxan, metoxypropylheptametylcyklotetrasiloxan, chlorpropylpentametyldisiloxan,. hydroxypropylpentametyldisiloxan, octamethylcyclotetrasiloxane, decamethyl-cyclopentasiloxane, cyclomethicone, and dimethicone having e.g. viscosity at 25 ° C (15 centipoise or less) and mixtures thereof.

When using cosmetic compositions as hair rinse conditioner compositions or as skin conditioners, the carrier may include gel vehicles which include two essential components: the lipid material of the vehicle and the cationic surfactant of the vehicle. Cationic surfactants are described in detail below. Gel type vehicles are generally described in the following documents, which are incorporated herein by reference: Barri, The Shelf Bodying Action of the Mixed Sodium Dodecyl Sulfate Emulsion Sulfate / Cetyl Alcohol, J. of

Colloid and Interface Science, 28: 82-91 (1968); Barri et al., The Self-Bodying ____

Action of Alkyltrimethylammonium Bromides / Cetostearyl Alcohol Mixed Emuisifiers; Influence of Quartemary Chain Length, J. of Colloid and Interface Science, 35, 689-708 (1971); Barri, et al., Rheology of Systems Containing Cetomacrogol 1000-Cetostearyl Alcohol, Shelf Bodying Action, J.of Cotloid and Interface Science, 38, 616-625 (1972).

The carrier may comprise one or more lipid vehicle materials which are substantially water insoluble and include hydrophobic and hydrophilic moieties. Lipid vehicle materials include natural or synthetic acids, acid derivatives, alcohols, esters, ethers, ketones and amides with hydrocarbon chains of 12 to 22 carbons, preferably from 16 to 18 carbons in the chain. Fatty alcohols and esters are preferred, fatty alcohols are particularly preferred.

Lipid vehicle materials useful in the present invention are described in Bailey's Industrial Oil and Fat Products (3rd edition, Swern).

D. ed) 1979, which is incorporated herein by reference. The fatty alcohols useful in the present invention are described in the following documents, which are incorporated herein by reference: US Patent 3,155,591, Hilfer, issued 3.11. 1964; US Patent 4,165,369, Watanabe et al., Issued Aug. 21, 2001. 1979; US Patent 4,269,824 to Villamarin et al. 1981; British Specification 1,532,585, published Nov. 15, 1978; Fukushima et al., The Effect of Cetostearyl Alcohol in Cosmetic Emulsions, Cosmetics & Toiletries, 98, 89-112 (1983). Fatty esters useful in the present invention are described in US Patent 3,341,465, Kaufman et al. 1976, incorporated herein by reference. If included in the compositions of the present invention, the lipid vehicle material is present at from about '0.1 to 10% of the composition, ^one cationic surfactant vehicle material is present at from 0.05 to 5.0% • ^s' mixture.

^'S Preferred esters for use herein include cetyl palmitate and glycerylmonosrearát. Cetyl alcohol and stearyl alcohol are preferred alcohols. A particularly preferred lipid vehicle material comprises a mixture of cetyl alcohol and stearyl alcohol ranging from 55 to 65% by weight of the cetyl alcohol mixture.

Preferred carriers for use in the present invention, particularly for hair rinse fluids, include:? combination of high-performance modi i cations. hvd roxyethylcell storage materials $ hardeners. (such as locust bean gua), certain surfactants, quaternary ammonium compounds (dialkyldimethylammonium chloride with vegetable fat alkyls), and / or chelating agents such as EDTA. These vehicles are described in detail in the following patents, which are incorporated herein by reference: U.S. Pat. No. 5,106,609, issued Apr. 21, 1992 to Bolich et al. No. 5,100,658, issued Mar. 31, 1992,

Bolich et al. U.S. Patent 5,104,646, issued April 14, 1992 to Bolich et al. No. 5,100,657, issued Mar. 31, 1992 to Ansher-Jackson et al. Carriers suitable for use in the present invention include, for example, those used for blends of tonics, foams, gels and hair sprays. Tonic, gels and non-aerosol hair sprays include a solvent such as water or alcohol, while foams and aerosol hair sprays also include a propellant such as trichlorofluoromethane, dichlorodifluoromethane, difluoroethane, dimethyl ether; propane, n-butane or isobutane. Low viscosity tonic or hair sprays may also include an emulsifier. Examples of suitable emulsifiers include nonionic, cationic, anionic surfactants or mixtures thereof. Particularly preferred are fluorosurfactants, preferably for hair spray compositions, and more preferably spray compositions having a relatively low content of volatile organic solvents such as alcohols and a relatively high water content (e.g., a 10% excess by weight of water). When such emulsifiers are used, their preferred content ranges from 0 to 7.5% of the composition. The propellant content can be adjusted, if desired, and generally ranges from 3 to 30% for the foam compositions and from 15 to 50% for the aerosol hair spray compositions.

Suitable spray cans are known and include conventional non-aerosol pump sprays (so-called "atomizer" spray cans) or propellant cans as described above, as well as pump aerosol cans using compressed air as a propellant. Pump aerosol containers are described, for example, in U.S. Pat. Patent 4,077,441,7.3. 1978, Olofsson; 4,850,577 25.7.

1989, TerStege, both of which are incorporated herein by reference, as well as U.S. Pat. Serial

No. 07/839, 648, Gosselin, Lund, Soika and Lefebvre, registered 21.2. 1992, ______Consumer Prpducj \ Pgckgge Incgrpqrating And Sprpy. Device Utilizing Lorge

Diameter Bubbles'. Pump spray aerosol sprays using a compressed air pump are also currently distributed by the Procter & Gamble Company under the Vidal Sassoon Airspray ® trademark.

Suitable ingredients

The cosmetic compositions of the present invention can be formulated into a wide variety of product types including foams, gels, water, tonic.

sprays, shampoos and conditioners. The added components required to formulate such products vary according to the type of product and may be routinely selected by a person skilled in the art of hair care. The following description lists some such additional components.

—Surtactants · ...... ^-; Surfactants are preferred adjunct ingredients in the compositions of the present invention, particularly in shampoos and conditioner compositions. If present, the composition comprises from 0.05 to 50% surfactant in the composition. In shampoos, the surfactant content is preferably from 10 to 30%, more preferably from 12 to 25% of the composition. In conditioners, the surfactant content is preferably from 0.2 to 3%.

Surtactants useful in the compositions of the present invention include anionic, nonionic, cationic, zwitterionic and amphoteric surfactants.

Useful synthetic anionic detergents include, in particular, shampoo mixtures, alkyl sulfates and alkyl ether sulfates. These materials are described by the general formula ROSO ₃ M and RO (C ₂ H _d O) _x SO ₃ M, wherein R is an alkyl or alkenyl having a carbon number of 10 to 20, x is a number from 1 to 10, M is a water-soluble cation such as is a cation of ammonium, sodium, potassium and triethanolammonium.

Another suitable group of anionic surfactants are the water-soluble salts of the reaction of the organic residue and the sulfuric acid of the general formula R, SO ₃ M, where R 1 is a linear or branched, saturated aliphatic hydrocarbon chain of 8 to 24 carbon atoms, preferably 12 to 18 carbon atoms. atoms and M is a cation. Important examples are sulfonates of carbon chains formed by the reaction of hydrocarbons of a methane series including iso-, neo- and n-paraffins containing from 8 to 24 carbon atoms, preferably from 12 to 18 carbon atoms, and a sulfonating agent such as SO ₃ , JH _? SQ _A , pieum and which are printed according to known techniques, including discolouration and hydrolysis. Preferred are alkali metal salts, sulfonated C12-18 n-paraffins and their ammonium salts. Other examples of anionic synthetic surfactants falling within the scope of the present invention are the reaction products of fatty acids esterified with isothionic acid and neutralized with sodium hydroxide, where, for example, fatty acids are derived from coconut oil; sodium or potassium salts of methyltaurine amides and of bridge acids derived from coconut oil. Other onionic synthetic surfactants are described in US Patents 12,486,921; 2,486,922 and 2,396,278.

Other onionic synthetic surfactants include the group referred to as succinamates. This group includes surfactants such as disodium N-octadecylsulfosuccinamate,

Tetrasodium N- (1,2-dicarboxyethyl D-N-octadecylsulfosuccinamate), sodium sulfosuccinate diamyl ester, sodium sulfosuccinate dihexyl ester, sodium sulfosuccinate dioctyl ester.

Other suitable anionic surfactants are sulfonates of olefins having 12 to 24 carbon atoms in the chain. The term olefin sulfonates as used herein refers to compounds prepared by sulfonation of α-olefins using uncomplexed SO ₃ followed by neutralization of the acidic reaction mixture under conditions where the reaction products are hydrolyzed to give the corresponding hydroxyalkonsulfonates. The α-olefins used to prepare olefin sulfonates are derived from monoolefins having 12 to 24 carbon atoms in the chain, preferably having 14 to 16 carbon atoms in the chain. Another type of anionic organic surfactant is β-alkyloxyalkane sulfonates. These compounds have the general formula R 1, -CH (-OR ₂ ) -CH ₂ -SO ₅ M,. wherein R 1 is an unbranched alkyl chain of from 6 to 20, R ₂ is a lower alkyl chain of from 1 (preferably) to 3, and M is a water-soluble cation as described above.

Many other synthetic anionic surfactants are described in McCutcheon's Detergents and Emulsifiers, 1984 Annuai, issued by Allured Publishing Corporation (incorporated herein by reference). Patent 3,929,678. Laughlin et al., Issued Dec. 30, 1975, also discloses other types of surfactants and is therefore incorporated herein by reference.

Nonionic surfactants which are preferably used in combination with anionic, amphoteric or zwitterionic surfactants are broadly defined as compounds prepared by the condensation of alkylene oxide groups (naturally hydrophilic) with organic hydrophobic substances, which may be aliphatic or alkylaromatic in nature. Examples of preferred types of nonionic surfactants are:

2. Nonionic surfactants prepared by the condensation of ethylene oxide with the product formed by the reaction of propylene oxide with ethylenediamine.

3. Nonionic surfactants prepared by condensation of aliphatic alcohols of 8 to 18 carbon atoms in a branched or unbranched chain with ethylene oxide, such as condensates formed by the condensation of 10 to 30 moles of ethylene oxide with 1 mole of coconut-derived alcohol, using a fraction of alcohols from of coconut oil having 10 to 14 carbon atoms in the chain.

4. Long-chain tertiary amine oxides such as those corresponding to the general formula R, R ₂ R ₃ N -> O, wherein R 1 comprises alkyl, alkenyl or monohydroxyalkyl of 8 to 18 carbon atoms, from 0 to 10 ethylene oxide units and R ₂ and R ₃ comprises from 1 to 3 carbon atoms and from 0 to 1 hydroxy groups such as methyl, ethyl, propyl, hydroxyethyl or hydroxypropyl, and wherein the arrow in the formula indicates a semipolar bond.

5. Tertiary phosphine oxides corresponding to the general formula RR'RP-> O, wherein R comprises alkyl, alkenyl or monohydroxyalkyl of 8 to 18 carbon atoms, from 0 to 10 ethylene oxide units, from 0 to 1 giyceryl units and R 'and R are alkyl or monohydroxyalkyls comprise from 1 to 3 carbon atoms. The arrow in the formula indicates a semipolar bond.

6. Long chain dialkyl sulfoxides comprising one short chain containing from 1 to 3 carbon atoms (usually methyl) and a long hydrophobic chain comprising alkyl, alkenyl, hydroxyalkyl or ketoalkyl of 8 to 20 carbon atoms, from 0 to 10 ethylene oxide units and 0 to 1 giyceryl unit. Examples include: octadecylmethylsulphoxide, tert-dimethylsulfoxide, 3,9,9-tnoxaocadecyl-2-hydroxyethylsulphide, dpdecylmethylsulphoxide, oleyl-3-hydroxypropylsulphoxide, tetradecvimethylsulphoxide,

3-methoxytridecylmethylsulfoxide, 3-hydroxytridecyimethylsulfoxide,

3-hydroxy-4-dodecoxybutylmethylsulfoxide.

The cationic surfactants useful in the compositions of the present invention, in particular the conditioner compositions, include quaternary ammonium hydrophilic groups which are positively charged when dissolved in the aqueous compositions of the present invention. Such cationic surfactants are described in the following documents, which are incorporated herein by reference: M.C. Publishing Co., McCutcheon ' s, Detergents & Emulsifiers, North American edition 1979; Schwartz et al., Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; U.S. Pat. No. 3,155,591, Hilfer, issued Nov. 3, 2003. 1964; U.S. Pat. U.S. Patent 3,929,678 to Laughlin et al. 1975; U.S. Pat. No. 3,959,461 ... Bailey et al. 1976; U.S. Pat. No. 4,387,090, Bolich Jr., issued Jun. If cationic surfactants are present in the compositions, they are present in the range of from 0.05 to 5%.

Useful quaternary ammonium surfactants are described by the general formula:

^R 'in ^RT XRj Γ r, wherein R, to R ₄ are independently an aliphatic alkyl radical of carbon number 1 to 22 or an aromatic, alkoxy, polyoxyalkylene; alkyl amide, hydroxyalkyl, aryl or alkylaryl substituents of from 12 to 22 carbon atoms; and x is an anion such as a halogenide, acetate, phosphate, nitrate, alkyl sulfate. The aliphatic substituents may also contain ether moieties and linkers and other functional groups such as amino groups. Long aliphatic chains, from 12 carbons and above, can be saturated or unsaturated.

Other quaternary ammonium salts useful in the present invention include bis-quaternary ammonium salts such as propanediammonium dichloride with vegetable oil alkyl substitution. · · ——Tt— ·

Quaternary ammonium salts include dialkyldimethylammonium chlorides with alkyl groups containing from 12 to 22 carbon atoms and are derived from long-chain fatty acids such as hydrogenated fatty acids from vegetable fat (these fatty acids provide quaternary salts, where R and R ₂ include predominantly from 16 to 18 carbon atoms). Examples of such quaternary ammonium salts include dialkyldimethylammonium chlorides with alkyl groups of vegetable fat dialkyldimetylamoniummetylsulfát with alkyls vegetable fat dihexadecyldimetylomoniumchlorid, dialkyldimethylammonium chlorides with alkyl groups of a hydrogenated vegetable fat, dioctadecyl, dieikosyldimetylamdniumchlorid, didokosyldimetylamoniumchlorid, dialkyldimetylamoniumacetát with alkyls of hydrogenated vegetable fat, dihexadecyl dimethylammonium chloride, dihexadecyldimetylámoniumocetát, dialkyldipropylamoniumfosfát with vegetable fat alkyls, dialkyldimethylammonium nitrate with vegetable fat alkyls, dialkyldimethylammonium chloride with coconut alkyls, and stearyldimethylbenzylammonium chloride. Dialkyldimethylammonium chloride with vegetable fat alkyls, dicetyldimethylammonium chloride.

stearyldimethylbenzylammonium chloride and cetyltrimethylammonium chloride are preferred quaternary ammonium salts of the present invention. Dialkyldimethylammonium chloride with saturated or unsaturated vegetable fat alkyls is a particularly preferred quaternary ammonium salt.

Suitable cationic surfactants are also long-chain primary, secondary and tertiary amide salts whose alkyl substituents preferably contain from 12 to 22 carbon atoms and may be substituted or unsubstituted. Such amines include stearamidopropyldimethylamine, diethylaminoethyl stearamide, dimethyl stearylamine, alkyldimethylamine with soybean alkyl, alkylamine with soybean alkyl, myristylamine, tridecylamine, ethylstearyl amine, N-alkylstearyl amine, ethoxylated stearyl amine, ethoxylate (E). Suitable amine salts include an anion such as a halide, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate. Such salts are stearylamine hydrochloride, alkylamine chloride with soybean alkyl, n-alkylsilylphosphine, N-alkyl propylene dibasic anhydride, rosin amine, and stearamidine propyldimethylaminate. Cationic amine surfactants useful in the present invention are described in U.S. Pat. No. 4,275,055, Nachtigal et al. 1981, which is. listed here as a reference.

Zwitterionic surfactants useful for shampoos and conditioners are i

documented by those generally described as derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds with branched or unbranched aliphatic alkyl, and wherein one of the aliphatic substituents comprises from 8 to 18 carbon atoms and one of the aliphatic substituents comprises an anionic group to solubilize in water, e.g., a carboxyl, sulfonate, sulfate, phosphate or phosphonate group. The general formula of these substances is:

(r ₃ ) x

R ₂ -Y ( ₊ ) -CH ₂ -R ₄ -Z (-) wherein R ₂ is an alkyl, alkenyl or hydroxyalkyl group containing from 8 to 18 carbon atoms, from 0 to 1G ethylene oxide units and from 0 to 1 glyceryl unit; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R ₃ is an alkyl or monohydroxyalkyl group containing from 1 to 3 carbon atoms; if Y is a sulfur atom, then X is one; if Y is a nitrogen or phosphorus atom, then X is 2; R ₄ is an alkylene or hydroxyalkylene group having from 1 to 4 carbon atoms; Z is a carboxylate, sulfonate, sulfate, phosphonate or phosphate group.

4? Other zwitterions, such as betaines, are also useful in the present invention, and examples thereof include higher alkyl alkyl betaines, coconut alkyl alkyldimethylcarboxymethyl betaine, lauryldimethylcarboxymethyl betaine, lauryldimethyl-α-carboxyethyl betaine (cetyldimethylcarboxymethyl betaine), lauryldimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine stearyl-bis- (2-hydroxypropyl) carboxymethylbetaine, oleyldimethyl-T-krboxypropylbetaine, and N = - (4-hydroxypropyl) - (2-hydroxypropyl) -sulfobetaine may be represented by alkyldimethylsulfopropylbetaine with coconut stearyl dipetyl alkyl, lauryl-bis- (2-hydroxyethyl) sulfopropyibetaine, etc .; amidobetaines and amidosulfobetaines wherein the RCONH (CH ₂ ) ₃ group is attached to the nitrogen atom of the betaine are also useful in the present invention.

Examples of amphoteric surfactants useful in the present invention are generally described as derivatives of aliphatic, secondary and tertiary amines with a branched or unbranched alkyl group and wherein one of the aliphatic substituents comprises from 8 to 18 carbon atoms and one substituent comprises an anionic group to solubilize in water such as - - carboxylate sulphonate, sulphate, phosphonate or phosphate group. Examples of such compounds include sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropanesulfonate, N-alkyltaurines such as that prepared by reacting dodecylamine with sodium isothionate as described in U.S. Pat. U.S. Patent 2,658,072, a higher alkyl N-alkylsulfonic acid such as that prepared as described in U.S. Pat. No. 2,438,091 and the product sold under the trade name Miranol as described in U.S. Pat. Patent 2,528,378.

Fluorosurfactants The compositions of the present invention may include a fluorosurfactant,

- which may be cationic, anionic, amphoteric, zwifterionic, non-ionic, or

- which may be a mixture of these types of fluorosurfactants.

Fluorosurfactants include perfluorinated materials such as those within the scope of the present invention

- the general formula: CF ₃ (CF ₂ ) _X - (CH ₂ ) _Y -Z, where Z is an organic or inorganic moiety providing solubilization, X is a number from 2 to 17, and in particular from 7 to Π, and Y is a number from 0 to 4, and these may be cationic, anionic, amphoteric, zwitterionic in nature, depending on the nature of the group or groups designated as Z, which may include carboxy, sulfate, sulfonate, quaternary ammonium, phosphate or phosphonate groups, and combinations thereof. The foamedoyl compounds are well known in the art and are described in the following documents, which are incorporated herein by reference: U.S. Patent 4,176,176, Cella et al. 1979, US Patent 3,993,745 to Cella et al. 1976 and US Patent 3,993,744, Cella et al., Issued Nov. 23, 1976.

Cationic fluorosurfactants include fluorinated alkyl quaternary ammonium salts with a wide range of anions such as iodide, chloride, methylsulfate, phosphate and nitrate, preferably iodide; and those _fluoro- surfactants falling within the general formula Rf CH ₂ CH ₂ SCH ₂ CH ₂ N * (CH ₃ ) ₃ (CH ₃ SO ₄ ) ·, where R _F is F (CF ₂ CF ₂ ) 4, such as Zonyl FSC® , supplied by DuPont. Preferred fluorinated alkyl quaternary ammonium iodides are sold under the tradename Fluorad FC-135®, available from 3M.

Anionic fluorosurfactants include mono- and bis-perfluoraikylfosfáty such as ZONYL FSC supplied by DuPont under the general formula "~~ <R _F CH ₂ CH ₂ O) P (O) (ONH _{4) 2} (R _F CH ₂ CH ₂ O ₁₂ P (O) (ONH ₄ ), where R _F is F (CF ₂ CF ₂ ) ₃ . ₈ ; mono- and bis-fluoroalkylphosphates with a range of cations such as ammonium, sodium, potassium, triethanolammonium and diethanolammonium. preferably ammonium salts, complexed with non-fluorinated quats, preferably aliphatic quaternary methyl sulfates such as Zonyl FSJ®, supplied by DuPont; perfluoralylsulfonic acids with a wide range of cations such as ammonium, sodium, potassium, triethanolammonium and diethanolammonium, preferably ammonium salts such as Zonyl TBS®, supplied by DuPont, according to the general formula R _F CH ₂ CH ₂ SO ₃ X, where R _F is F (CF ₂ CF ₂ ) ₃ -, and X is H or NH ₄ ; telomeric phosphates with a wide range of cations such as ammonium, sodium, potassium, triethanolammonium and diethanolammonium, preferably diethanolammonium salts such as Zonyl RP® supplied by DuPont; perfluoroalkylamine sulfonates such as Fluorad FC-99® supplied by 3M; perfluorool ammonium sulfonates such as Fluorad FC-93®, Fluorad FC-120®,

L-12402®, supplied by 3M; potassium perfluoroalkyl sulfonates such as Fluorad FC-95® and Fluorad FC-98®, supplied by 3M; potassium fluorinated carboxylates such as Fluorad FC-129® supplied by 3M; perfluorinated '~ ammonium carboxylate such as Fluorad FC-143® supplied by 3M and fluorosurfactants according to the general formula R _F CH ₂ CH ₂ SCH ₂ CH ₂ CO ₂ Li, wherein R _F is F (CF ₂ CF _{2) 3-n} such as ZONYL FSA®, available from DuPont.

Amphoteric fluorosurfactants include fluorinated alkyl amphoteric detergents such as Fluorad FC-100® supplied by 3M.

Zwitterionic fluorosurfactants preferred for use in the compositions of the present invention are the fluorosurfactants of the general formula R _F CH ₂ CH (OCOCH ₃ ) CH ₂ NJCH ₃ ) ₂ CH ₂ CO ₂ , wherein R _F is F (CF ₂ CF ₂ ) ₃ ? Zonyl FSK®, supplied by DuPont.

The fluorosurfactants may be used alone or in combination in the hair spray compositions of the present invention.

When fluorosurfactants are used, their content ranges from 0.01 to 2%, preferably from 0.01 to 1.5% by weight of the composition.

The above surfactants may be used alone or in combination in the compositions of the present invention. Cosmetic compositions contain a wide range of suitable components to achieve cosmetically or aesthetically more acceptable compositions or to achieve other beneficial properties in use. Such conventional suitable ingredients are well known to those skilled in the art and are, for example, agents imparting a pearl appearance to the compositions such as ethylene glycol distearate; preservatives such as benzyl alcohol, methylparaben, propylparaben and imidazolidinylurea; viscosity enhancers and modifiers such as long chain fatty acid diethanolamide (e.g., PEG 3 and lauryldiethanolamide), coconut alkylmonoethanolamide, dimethicone copolyols, guar gum, methylcellulose, starches and derivatives thereof; fatty alcohols such as cetostearyl alcohol; sodium chloride; sodium sulfate; polyvinyl alcohol; ethanol; pH adjusting agents such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide.

sodium carbonate; generally salts such as potassium acetate and sodium chloride; a coloring agent such as any of FD&C or D&C dyes; hair oxidizing (bleaching) agents such as hydrogen peroxide, persulfate or perborate salts; hair reducing agents such as thioglycoiates; perfumes; masking agents such as disodium ethylenediaminetetraacetate; and polymer-plasticizing agents such as glycerin, diisobutyl adipate, butyl stearate and propylene glycol. Such suitable ingredients are used individually in the contents of o and QJ. yýno.9.CL®. 99_0,05 and 5% by weight of the mixture.

The pH of the compositions of the present invention is generally from 3 to 9, preferably from 4 to 8.

As with all compositions, the compositions of the present invention should not contain components that undesirably interfere with the effect of these compositions.

The cosmetic compositions of the present invention may be prepared by conventional formulation techniques of mixing. Methods for preparing various types of cosmetic compositions are described more specifically in the following examples.

DETAILED DESCRIPTION OF THE INVENTION

The cosmetic compositions of the present invention are used in a conventional manner for conditioning / conditioning / strengthening / film forming / providing adhesive properties and other beneficial effects of the present invention. The method of use depends on the type of composition used, but generally involves applying an effective amount of the product to the hair or skin, which can then be rinsed (in the case of shampoos and some conditioners) or left on the hair (in the case of sprays, mousses, gels, lotions). , film-forming lotions with drugs and tonic). By effective amount is meant an amount sufficient to provide the desired film-forming effect. Preferably, hair rinse materials, dressings, foams and gels are applied to wet or damp hair prior to drying and bean treatment, after application of these mixtures the hair is dried and treated in a conventional manner by the user. Hair sprays are usually applied to dry hair after they have been dried and their bean treated. Cosmetics and lotions are applied to the face, skin or eye area by conventional methods of handling such products.

In another aspect, adhesives comprising graft polysiloxane polymers such as those described in U.S. Pat. Patent

No. 4,693,935, Mazurek, issued 15.9. 1987 and U.S. Pat. Patent 4,728,571. Clemens et al., Issued March 1, 1988, to prepare adhesive products such as adhesive tapes and packaging materials. The adhesives described herein may include pressure-sensitive or non-pressure-sensitive film-forming polymers.

The following experiments and examples further illustrate preferred cases falling within the scope of the present invention only and are presented ^- for the purpose of illustration and does not limit the present invention since it is possible to find many possible variations of the invention without these fall within the frame of the present invention.

Experiment A

60% / 20% / 20% t-butyl acrylate / acrylate / polyimethylsiloxane (PDMS) vinyl polymer (MW 10,000) was prepared by radical polymerization in an acetone reaction medium as described for the Polymer Ί above. Percentages are by weight of the total amount of monomers added to the reaction.

The reaction product was precipitated from acetone by addition of water and dried, extracted with hexane by adding excess hexane and heating to boiling, i.e. at about 70 ° C. The Tg of the non-silicone portion of the adhesive polymer is 63 ° C. The mixture was kept at this temperature for 30 minutes and cooled to room temperature, the hexane was removed by suction under vacuum. Two additional hexane extraction cycles were performed in the same manner as described above. After the third cycle, the residual hexane retained in the product was removed by distillation and vacuum drying. · /

Experiment 6

Polymer 80% / 20% t-butyl acrylate / PDMS (MW 10,000) would be prepared according to the same procedure as Polymer 1 above, except that the polymerized monomers are 80% t-butyl acrylate and 20% PDMS-containing vinyl polymer . Ethyl acetate was used as the reaction medium.

The reaction product was precipitated from the reaction solvent by the addition of water, dried, and ground to a fine powder for supercritical fluid oxide extraction.

C W + ZZN I z z ^

LAIIUI \ CS was caused by the layman

ΧΟΛ - ^ 4 .-. X—. - uuu uiinubiei,

The extraction vessel was continuously washed under pressure with supercritical carbon dioxide for 1 hour.

The low molecular weight polymer and the polysiloxane-containing monomer were solubilized by supercritical carbon dioxide for 1 hour and discharged from the remaining polymer through a pressure line maintained at the same pressure as the extraction vessel in which the extracted materials were kept and dried and extracted after extraction and depressurisation. from the extraction vessel.

Examples 1-3

The following hair sprays are exemplary of the compositions of the present invention.

- Component · - - - Example number (% by weight) 3 1 2 Graft polysiloxane polymer (Exp. A) 4,5 4,5 4,5 Ethanol 79.0 79.0 79.0 Diisobutyl adipate 0.7 - - KOH solution (45%) 1.0 1.0 1.0 Perfume 0.2 0.2 0.2 FC-120 Fluorosurfactant (3M Co) (25% activ.) - - 0.14 Water 100% replenishment

This product was prepared by dissolving the silicone polymer in ethanol and stirring for several hours until all the polymer had dissolved. A plasticizer was then added, if appropriate. Subsequently, a potassium hydroxide solution, water or a water-surfactant solution was added, if appropriate, and the perfume was last added.

Example 4

The following composition is a hair conditioning tonic of the present invention.

% Weight component

Graft polysiloxane polymer (Exp. A) 0.70

Perfume 0.10

Ethanol supplement to 100%

The mixture is prepared by mixing the above ingredients in a conventional manner.

Example 5 ’

The following composition is a shampoo according to the present invention.

Component

Ammonium lauryl sulfate

Coconut Alkyamidopropyl Betaine Graft Polysiloxane Polymer (Exp. A) Ethanol

PEG 10Distearate

NaOH

Glydant ”

Perfume

DRO water% weight 7,00. -6.00-2.00 10.00 2.00 0.15 0.38 1.00 100% supplement ¹⁵ is a preservative commercially available from Glyco, Inc.

The shampoo was prepared by mixing ammonium lauryl sulfate (usually supplied as a 28% aqueous solution) with a silicone copolymer, heating the mixture to 70 ° C for 30 minutes with stirring. The remaining ingredients were added and the mixture was stirred for an additional 30 minutes, cooled to room temperature and the pH of the mixture was adjusted by addition of citric acid or NaOH, if necessary.

Example 6

The following mixture is a permanent cold waving according to the present invention.

Thioglycolic acid

Monoethanolamine

Graft polysiloxane polymer (Exp. A) PEG 10 monostearate DRO water% weight 5.00 6.00 1.50 0.50 replenishment to 100%

The mixture was prepared by all ingredients, heating the mixture to 60 ° C for 30 minutes and allowed to cool to room temperature.

Example 7

The following composition is a bean treatment gel according to the present invention.

Component

Graft polysiloxane polymer (Exp. A)

Carbopol940 ⁿ

Triethanolamine

Dye solution

Perfume

Laureth-23

DRO water% by weight

2.00

0.75

1.00

0.05

0.10

0.10 supplement to 100% ¹⁵ is crosslinked polyacrylic acid, available commercially from BF Goodrich

The mixture was prepared by mixing the ingredients in a conventional manner. .

Example 8

The following composition is the hair conditioning foam of the present invention.

Component— - - -% by weight

Graft polysiloxane polymer (Exp. A) 3.00

Ethanol__15,00

Coconut amine oxide

DC 190 ^υ 0.20

Coconut oil amide DEA 0.30

Perfume 0.10

Izobutan 7,00

DRO Water Refill at 100% ¹⁵ is a dimethicone copolyol available commercially from Dow Corning

The mixture is prepared by mixing all the above ingredients except isobutane at room temperature. Aluminum aerosol cans were filled with 95 parts of the blends and sealed with a valve that was pressed into place and then filled with 5 parts of isobutane.

- Examples9-10 - - - -. -. . -------...... --- - - ---- The following composition is water for conditioning the hair and conditioner of the present invention.

Component Example 9 10 Citric acid 0.02 0.02 Sodium citrate 0.09 0.09 Cetyl alcohol 0.12 0.012 Stearyl alcohol 0.08 0.08 Natrosol Plus CS Grade D-67 ^υ 1.05 1.10 Xanthan gum ²⁵ 0.25 0.25 Premix of polymer for treatment of phason Graft polysiloxane polymer (Exp. B) 1.75 1.75 Octamethylcyclotetrasiloxane 5.98 5.98 Decamethylcyclopentasiloxane 2.56 2.56 Butylastearate 0.15 0.15 Kathon CG 0.03 0.03 Perfume 0.33 0.33

Premlx Conditioner

DROvoda 12,18 11,88

Adogen 442-100 ^ 0.75 0.75 nuuyci 1 * 4/1 - 0.60 _SteaMrlmetylamoniumc Silicone rubber premix 0.30 - Decamethylcyclopentasiloxane 1.42 1/32 Polydimethyl Siloxane Gum ³⁵ 0.25 0.25 Amodimethlcone Dow Corning Q2-8220 - 0.10 DRO water added to 100%

¹⁵ is a hydrophobically modified hydroxyethylcellulose from Aqualon Corp.

²⁾ is easily dispersing xantham gum ³⁾ is SE-76 gum from General Electric ⁴⁾ is dialkyldimethylammonium chloride with vegetable oil alkyls from Sherex Chemical Co., Dublin. Ohio, USA ⁵⁾ is an alkyltrimethyldmonium chloride with vegetable oil alkyls from Sherex Chemical Corporation. The premix of the tazone treatment polymer was prepared by mixing the polymer, octamethyltetrasiloxane and decamethylpentasiloxane and butyl stearate.

The silicone gum premix was prepared by mixing and mixing (in a separate container) silicone gum and decamethylcyclopentasiloxane until the mixture became homogeneous.

Conditioner premix was prepared by mixing and mixing (in a separate container) DRO water, primary and secondary hardener (pre-melted if homogeneous if necessary) at 82 ° C, silicone rubber premix and amodiomethicone at 71 ° C until the mixture did not become homogeneous.

In another vessel, the DRO water was heated to 71 ° C, then citric acid, sodium citrate, cetyl alcohol, stearyl alcohol and Natrosol Plus CS grade, D-67 were added and mixed until homogeneous. Thereafter, a premix polymer for the treatment of the phonon, Kathon CG and the perfume was added and the mixture was stirred until it became homogeneous. The mixture was then dispersed in a homogenizer such as a Tekmar homogenizer and cooled to 38 ° C, added to the final vessel, stirred until it became homogeneous to produce a material for hair rinsing and bean treatment.

After applying the blend of Examples 9 or 10 in a conventional manner to the hair, they provide effective conditioning, the ability to adjust the bean and firming without. made the hair sticky.

They did

The following composition is a hair spray according to the present invention and was prepared as follows:

Component

Graft polysiloxane polymer (Exp. A)

Water

Ethanol

KOH (45% solution)% by weight

4.00

11.00

63.50

0.90

Izobutan ~ ™ .. ... . - -15,00

Difluoroethane

6.00

All ingredients except propellants were stirred at room temperature until the polymer had dissolved, the mixture was placed in an aerosol canister equipped with a conventional aerosol spray valve which was pressed into place in vacuo. The vessel was filled with propellants through the valve and the vessel was fitted with a conventional aerosol spray activator.

Industrial applicability

The present invention describes the preparation and use of graft polysiloxane polymers and adhesives prepared therefrom, which can be used in the industrial production of cosmetics.

Claims (11)

PATENT CLAIMS An adhesive comprising a graft polysiloxane polymer and cosmetic compositions thereof, characterized in that they are prepared by polymerizing polysiloxane-containing monomers with polysiloxane-free monomers, wherein the adhesive has an average molecular weight of at least 20,000 and comprises from 1 to 50% by weight of polysiloxane-containing monomers; the adhesive is characterized by the percentage by weight of silicone present as unreacted polysiloxane-containing monomer and of grafted polysiloxane polymer having a viscosity at 25 ° C of less than 10 ⁷ centistokes based on the total silicone content present as unreacted polysiloxane-containing monomer or less and containing not more than 4% by weight of unreacted polysiloxane-containing monomer and graft polysiloxane polymer with a viscosity at 25 ° C of less than 10 ⁷ centistokes. / Second adhesive of claim !, vyznačujícísetím, Z e _r weight percentage of unreacted polysiloxane-containing monomer and polysiloxane-grafted polymer having a viscosity at 25 * C of less than 10 ⁷ centistokes based on the total silicon present as unreacted polysiloxane-containing monomer and polysiloxane-grafted % of the polymer T0 or less, preferably 5% and less, and the adhesive does not contain more than 3% by weight, preferably more than 1% of unreacted monomer-containing monomer. polysiloxane g grafted. polysiloxane polymer having a viscosity at 25 ° C of less than 10 ⁷ centistokes. Adhesive according to claims 1 and 2, characterized in that it has an average molecular weight of at least 75,000, preferably of at least 100,000, more preferably of from 100,000 to 750,000. Adhesive according to claim 1, 2 or 2, characterized in that the polymer comprises from 50 to 99% by weight of an adhesive of polymerizable, unsaturated polymerizable ethylene-type monomers and from 1 to 50%, preferably from 2 to 25% of polysiloxane-containing monomers having a molecular weight. At least 1000 and the structure according to the general formula: ~ X (Y) _n Si (R) j _rr (Z) _RT ,, wherein X is a vinyl group copolymerizable with the A and monomeryA - - BvYje divalent linking group, R is hydrogen, hydroxy, lower alkyl, aryl, alkylaryi, alkylamino, or Z is a monovalent polymeric siloxane group having an average molecular weight of at least 500, which is non-reactive under polymerization conditions and adheres to the vinyl polymer backbone after polymerization, n is 0 or 1, and is a number from 1 to 3. Adhesive according to claim 4, characterized in that the polysiloxane-free monomer is a free-radically polymerizable vinyl monomer. Adhesive according to claims 4 and 5, characterized in that the polysiloxane-free monomer is selected from the group consisting of hydrophobic monomers selected from the group consisting of esters of acrylic acid and C 1 to C ₁₈ alcohols, methacrylic acid esters and C 1 to C , ₈ alcohols, styrene, F of polystyrene macromer, vinyl acetate, vinyl chloride, vinyl propionate, vinylidene chloride, α-methylstyrene, t-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, yinyltoluene, acrylic acid, methacrylic acid, Ν, dim-dimethylacrylamide, dimethylaminoethyl acrylate, dimethylaminoethyl acrylate butylacrylamide, maleic acid and its monoesters, maleic anhydrides and its esters, crotonic acids, and itaconic acid, acrylamides, acrylate alcohols, hydroxyethyl methacrylate, diallyldimethylammonium chloride, vinylpyrrolidone, allyl amide, vinylethereside, vinylethereside, vinylethereside, vinylethereside, vinylethereside, vinylethereside, vinylethereside, , vinyl alcohol, vinylcaprolactam and mixtures thereof and hydrophilic monomers selected from the group consisting of acrylic acid, methacrylic acid, Ν, dim-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, methacrylamide, Nt-butyl acrylamide, maleic acid, maleic anhydride of its monoesters, crotonic and itaconic acids, ocrylamide, acrylate alcohols, hydroxyethyl methacrylate, diallyldimethylammonium chloride, vinylpyrrolidone. vinyl ethers, maleic acid imides, vinylpyridine, vinylimidazole and other polar vinyl-substituted heterocycles, styrene sulfonate, allyl alcohol, vinyl alcohol, vinylcaprolactam, salts of said acids and amines, and mixtures thereof. Adhesive according to claim 6, characterized in that the hydrophobic monomers are selected from the group consisting of t-butyl acrylate, t-butyl methacrylate and mixtures thereof. Adhesive according to claim 6 or 7, characterized in that the hydrophobic monomers are selected from the group consisting of acrylic acid, Ν, Ν-dimethylacrylamide, dimethylaminoethyl methacrylate, quarremized dimethylaminoethyl methacrylate, vinylpyrrolidone, salts of said acids and amines and mixtures thereof. j Adhesive according to claim 6, 7 or 8, characterized in that - it comprises from 0 to 95% of hydrophobic monomers, from 14 to 95% of hydrophilic monomers and from 1 to 40% of polysiloxane-containing monomers, preferably from 5 to 70% of hydrophobic monomers from 29 to 80% of hydrophilic monomers and from 2 to 25% of polysiloxane-containing monomers. _ Adhesive according to claim 6, 7 or 8, characterized in that it comprises from 0 to 70% of hydrophobic monomers, from 20 to 80% of hydrophilic monomers and from 1 to 40% of polysiloxane-containing monomers, preferably from 5 to 70% % hydrophobic monomers, from 20 to 60% hydrophilic monomers, and from 2 da.25% polysiloxane-containing monomers; 11. A hair care and bean treatment composition comprising an adhesive according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 for a carrier suitable for application to the hair. 12. A hair care composition which is in the form of a liquid suitable for application to the hair as a spray, wherein the carrier comprises water. to C ₆ monoalcohol or mixtures thereof.