Polysiloxane block-copolymers in cosmetic compositions designated for topical applying in individual hygiene

FIELD: chemistry of polymers, hygiene.

SUBSTANCE: invention describes a method for preparing polysiloxane block-copolymer formed by links of the formula: [A][B] wherein A represents polymeric block formed of monomer polymerized by radical mechanism; B represents polysiloxane block. Method involves stage for formation of the polysiloxane macroinitiating agent as result of grafting radical initiating agent on polysiloxane by reaction of nucleophilic substitution occurring between groups of polysiloxane and radical initiating agent, respectively, and carrying out the radical polymerization reaction with transfer of atom between prepared by such manner the polysiloxane macroinitiating agent and monomers polymerizing by radical mechanism to obtain polysiloxane block-copolymer. Also, invention relates to cosmetic designated for individual hygiene. Method provides facility in preparing and economy.

EFFECT: improved preparing method.

6 cl, 3 tbl, 8 ex

The present invention relates to polysiloxane block copolymers suitable for use in cosmetic and intended for personal hygiene compositions, to receive them and to cosmetic and intended for the personal care compositions, such as compositions for hair styling containing polysiloxane block copolymers.

Cosmetic and intended for personal hygiene compositions, such as varnishes for styling hair sprays, mousses, gels and shampoos often contain tar, gum and adhesive polymers, enabling a wide range of beneficial properties, such as for example, film-forming ability, thickening, sensory properties and shaping of the hair and fixing them.

Polymers intended for use in such compositions include organic or containing linear siloxanes or grafted copolymers, which are formed of different monomers in alternating, statistical, block or homopolymer configurations.

Grafted copolymers known as film-forming polymers in compositions for hair care and other compositions intended for personal hygiene. Data grafted copolymers typically have a polymer main chain and one or more macromolecules grafted to the main chain, in this case,in order to create in General desirable polymer properties, the polymer main chain and macromonomers branches of the physical and chemical properties such as glass transition temperature and solubility in water, can be chosen independently from each other.

For example, WO 95/01383 and WO 95/01384 describe the use of soluble or dispersible in water or in alcohol graft copolymers in compositions for hair care and skin care, where the copolymer has a main chain and two or more polymer side chains, and the polymer is produced in the copolymerization statistically recurring Monomeric units a and B. the Monomer And choose so that it was inherent hydrophobic character, and macromonomer In contains a long hydrophilic part. EP 412704, EP 408313 and EP 412707 disclose the use for hair care acrylate copolymers with grafted siloxanes. US 4988506 describes the use of copolymers with grafted polysiloxane, not pressure-sensitive, in compositions for hair care.

Block copolymers have the advantage compared with the grafted copolymer, which is that the structure of the polymer can be controlled. This is particularly important when used for specific applications of polymer segments with different physical and chemical properties, for example, with alternating “hard” and “soft” segments in polymer clay is e, used in hair spray aerosol, to improve the fixation of the hair and sensations after it.

US 5468477 describes cosmetic and intended for personal hygiene compositions containing vinylsilane graft or block copolymer containing a segment of the siloxane polymer and a segment of the vinyl polymer. The block or graft copolymer is obtained by radical polymerization of the transfer agent siloxane chain with mercaptoquinoline and vinyl monomers. The copolymers obtained by this method, in General low molecular weight and low content of siloxane, which is explained by the premature breakage of the kinetic chain. In addition, the intermolecular crosslinking reaction leading to the formation of polymer in an uncontrolled manner and, consequently, to the formation of polydisperse systems with different length chains and molecular structures. In addition, the presence of mercaptopropyl is the lack of funds intended for personal hygiene, because groups tend to decay, and that creates problems associated with an unpleasant odor.

Another approach to the synthesis of block copolymers is to use organopolysiloxanes of macroinitiators that represent organopolysiloxane containing groups which form radicals. Data macroinitiator are described in US 5523365 and used in WO 98/48771, where for the synthesis of the block copolymer used polydimethylsiloxanes the macroinitiator with azo-groups. Problems lie in the costs and risks in relation to safety associated with the use of radical macroinitiator, which must be present in significant quantities, and otherwise in the final product, the content of the siloxane will be insufficient. In addition, the size polydimethylsiloxane macroinitiator suggests that the reaction is inefficient, and large quantities of unreacted siloxane must be removed in a time-consuming process of extraction, which is extremely difficult to make large-scale.

There is a need for convenient and cost-polysiloxane block copolymers, which could be used in cosmetic and intended for personal hygiene compositions.

The present invention relates to an improved method for producing a polysiloxane block copolymers, in which the radical macroinitiator get from organopolysiloxanes using simple reactions of nucleophilic substitution. Thus obtained macroinitiator then can be used in radical polymerization atom transfer to the floor is to be placed polysiloxane block copolymers with controlled structure. Radical polymerization atom transfer outlines in Polymer Vol.39, No. 21, R-5170 (Nakagawa et al) and used in W98/51261 to graft copolymers.

In the first aspect of the present invention relates to a method for producing a polysiloxane block copolymer which is formed from units of the formula [A] [V], where a represents a polymer block formed from the polymerized by the radical mechanism of the monomer, and b is a polysiloxane block, and the method includes the stage of formation of polysiloxane macroinitiator by grafting a radical initiator to polysiloxan using reactions of nucleophilic substitution occurring between groups of polysiloxane and a radical initiator, respectively, and the reaction of the radical polymerization atom transfer between thus obtained the polysiloxane macroinitiator and the polymerized by a radical mechanism monomers with obtaining a polysiloxane the block copolymer.

In the second aspect of the invention relates to polysiloxane block copolymer which can be obtained by the method described above.

The invention also relates to a cosmetic intended for personal hygiene composition, such as a composition for hair styling, containing the above-described polysiloxane is a block copolymer.

Detailed description and preferred options for implementation

Way

The method of the present invention includes two stages of key reactions are:

The first reaction stage

The first reaction stage involves the formation of polysiloxane macroinitiator by grafting a radical initiator to polysiloxan using reactions of nucleophilic substitution between groups of polysiloxane and a radical initiator, respectively.

Usually the polysiloxane macroinitiator formed by the reaction of nucleophilic substitution between:

(i) a polysiloxane, as end groups of which has at least one group capable nucleophile to attack, using his atom is O, N or S,

and

(ii) a radical initiator containing at least one group-C(O)X, in which X represents tsepliaeva group that can be substituted by nucleophilic atom is O, N or S polysiloxane (i)and at least one group of organic halide capable of generating a radical in the presence containing a transition metal catalyst.

Polysiloxane (i) may be linear, branched or hyperbranched provided that as of end groups has at least one above-described group. The term “end group” it is meant that groups who occupies the end position in the polysiloxane or is close to the limit position.

Examples of preferred polysiloxanes described by the formula:

[Y(R³)_p-Si(R¹)(R²)-O-[Si(R¹) (R²)-O]_nSi(R¹)(R²)-(R⁴)_qZ]

where n is an integer in the range from 5 to 1000000;

R¹and R²independently from each other are selected from monovalent, possibly substituted, linear or branched hydrocarbon, C_1-18radicals;

R³and R⁴independently from each other selected from divalent, possibly substituted, linear or branched hydrocarbon, C_1-18radicals;

p and q represent integers whose value is 0 or 1, and

Y and Z independently of one another are selected from hydroxyl, -NH₂and-other⁵where R⁵represents a monovalent, possibly substituted, linear or branched hydrocarbon, C_1-18-radical. Any of Y and Z, but not both, may also be hydrogen or monovalent, possibly substituted, linear or branched hydrocarbon, C_1-18radicals, forming, thus, polysiloxan with one end group.

Examples of the unsubstituted monovalent radicals are alkyl radicals such as methyl, ethyl, n-sawn, ISO-propyl, n-boutigny, isobutylene, tert-boutigny, n-pentelenyi, isopentenyl, neopentylene and t is et-pentelenyi radical; CNS radicals, such as metaxylene, amoxilina, n-propoxyphenyl, isopropoxy, n-butoxyphenyl, isobutoxy, tert-butoxyphenyl, n-pentoxil, isopentenyl, neopentecostal and tert-pentoxil radical; hexylene radicals, such as n-sexily radical; alkeneamine radicals, such as vinyl, allyl, 5-exenergy, 4-vinylcyclohexane and 3-norbornanamine radical; cycloalkyl radicals, such as cyclopentyl, tsiklogeksilnogo, 4-ethylcyclohexyl and cycloheptyl radical; norbornylene radicals and methylcyclohexyl radicals; aryl radicals such as phenyl, biphenylyl, nattily, antilly and financilly radical; alkaline radicals, such as o-, m - and p-colliny radical, xylylene radicals and ailfenergy radical; and kalkilya radicals, such as benzyl, sterelny and phenylethylene radicals.

Examples of substituted monovalent radicals are halogenated hydrocarbon radicals, such as CHLOROTHALONIL, 3-chloropropionyl, 3-bromopropionyl, 3,3,3-cryptosporidia and 5,5,5,4,4,3,3-getattachmentfilename radical and chloraniline, dichloraniline and triptoreline radical; mercaptopurine radicals, such as 2-mercaptoethyl and 3-mercaptopropyl radical; lanakila radicals, such as 2-tionately and 3-cyano who rapildy radical; aminoalkyl radicals, such as 3-aminopropyl, N-(2-amino-ethyl)-3-aminopropyl and N-(2-amino-ethyl)-3-amino-(2-methyl)through radical; aminoaryl radicals, such as AMINOPHENYL radical; aryloxyalkyl radicals, such as 3-Acrylonitrile and 3-methacryloxypropyl radical; hydroxyalkyl radicals, such as hydroxypropyl radical.

Preferred monovalent radicals independently from each other selected from unsubstituted or substituted alkyl (C₁-C₆radical or phenyl radical, in particular methyl, ethyl, sawn or phenyl radical.

Examples of divalent hydrocarbon radicals are linear or branched saturated alkylene radicals such as the methylene and ethylene radical, as well as propylene, butylene, Panteleeva, exelency, cyclohexyloxy and octadecenoyl radicals; alkoxy-alkylene radicals, such as methoxyethanol and ethoxyethanol radical; unsaturated alkylene or allenbyi radicals, such as hexadecanoic radical and phenylenebis radicals; alkalline radicals, such as methylphenylene and ethylenically radical, and alkoxy-allenbyi radicals, such as methoxyphenylacetyl, ethoxy-phenylenebis radical. The divalent hydrocarbon radicals, R^{3/sup> and R4can be attached via divalent radicals associated with the carbon atoms on both sides, such as-O-, -C(O)O-, -O(O)C-, -CONR6-, -NR6C(O)- and-C(O)-, where R6represents hydrogen or the above-described monovalent, possibly substituted, linear or branched hydrocarbon, C_1-18-radical.}

Particularly preferred polysiloxane corresponding to the above General formula are:

n = 5-1000000, preferably 5-500;

R¹and R²= methyl,

p and q = 0, and Y and Z = hydroxyl; or R and q = 1, R³and R⁴= (CH₂)₃and Y and Z = NH₂.

Radical initiator (ii) contains at least one group-C(O)X, in which X represents tsepliaeva group that can be substituted by nucleophilic atom is O, N or S polysiloxane (i)and at least one group of organic halide capable of generating a radical in the presence containing a transition metal catalyst.

Examples of preferred radical initiators are described by the formula:

R⁷-C(O)X,

where R⁷is a group of organic halide, and X is tsepliaeva group. Preferably X represents a halogen atom (F, Cl, Br or I). Under the “group of organic halide” refers to any linear, branched or cycle the definition (aromatic or other) carbon structure, either substituted or unsubstituted, which also contains a halogen atom (F, CL, Br or I).

Preferred radical initiators are described General formula:

C(R⁸)(R⁹)Hal'-(R¹⁰)_r-C(O)Hal,

where Hal' and Hal independently of one another denote halogen atoms, R⁸and R⁹independently from each other selected from hydrogen or the above-described monovalent, possibly substituted, linear or branched hydrocarbon, C_1-18radical, r is an integer whose value is 0 or 1, and R¹⁰selected from the above-described divalent, possibly substituted, linear or branched hydrocarbon, C_1-18-radicals.

Particularly preferred radical initiator corresponding to the above General formula is:

Hal and Hal' = Br, R⁸and R⁹= methyl, and r = 0.

The first reaction stage comprises a nucleophilic substitution reaction between (i) and (ii) commonly used in the reaction conditions. Nucleophilic atom is O, N or S polysiloxane (i) replaces tsepliaeva group X in radical initiator (ii), binding, thus (i) and (ii) with the formation of polysiloxane macroinitiator.

The second reaction stage

The second reaction stage comprises carrying out the reaction between the organic groups of the halide polysilk is anew macroinitiator, obtained in stage (i), and polymerized by the radical mechanism monomers in the presence of catalytic or stoichiometric amount of salt cu (I) or other transition metal compounds with the formation of polysiloxane block copolymer.

At this stage of the reaction groups of the organic halide act as initiators in the presence of the polymerized by the radical mechanism of the monomers and of the catalyst, resulting in a connection block of the polymerized by the radical mechanism of the monomers to the polysiloxane macroinitiator as a result of leaking radical polymerization atom transfer. This block of the polymerized by the radical mechanism of the monomers forming the polymer block (denoted as A) in the above-described polysiloxane block copolymer.

The catalyst for the second reaction stage is a transition metal salt, preferably a salt of Cu(I), such as a halide (Cl, F, Br, I) salts of Cu(I), and which is preferably present in the form of a complex with a ligand, which can be used to solubilize salts of Cu(I) in the reaction mixture. WO 98/51261 describes ligands, preferred for use in the solubilization of the salt Cu(I) in the reaction mixture (aprotic bidentate ligands, such as diphosphite, 2,2'-bipyridyl, substituted C_1-20the alkyl BP is ideal and combinations thereof, most preferably 2,2'-bipyridyl forming a complex with a halide salt of Cu(I), in particular with CuCl). WO 98/51262 also gives links to several articles in journals that describe examples of the method of polymerization (radical polymerization atom transfer), used in the second reaction stage in the method of the present invention. Additional examples of such descriptions can be found in Polymer Vol.39, No. 21, R-5170 (Nakagawa et al) and Macromolecules 1997, 30, 2190-2193 (Haddleton et al). Specialists in the relevant field will understand that they can be used and a variety of other ligands.

The method of polymerization in the second reaction stage can be implemented in bulk, solution, emulsion and suspension, as it is clear to experts in the respective field.

The polymerized by a radical mechanism monomers suitable for use in the second reaction stage in the method of the present invention, preferred are monomers with ethylene unsaturation type.

By “curable” refers to monomers which are polymerized in accordance with the second reaction stage in the method of the present invention when carrying out radical polymerization atom transfer, more preferably a living radical polymerization, atom transfer, where the length and structure of polymer chains is Ki can be determined by the stability of the radical, what, therefore, leads to improved monodispersity.

Under “having unsaturation of ethylene type” refers to monomers that contain at least one curable double bond carbon-carbon (which may be mono-, di-, tri - or Tetra-substituted). Can be used by any individual monomer or a combination of two or more monomers. In any case, the monomers are chosen so that they would meet physical and chemical requirements of the final polysiloxane block copolymer.

Suitable monomers with the unsaturation of ethylene type describes the following General formula:

H(R¹¹)C=C(R¹²) (C(O) (G)

where R¹¹and R¹²independently from each other selected from hydrogen, linear or branched C₁-C₁₀-alkyl, metaxylene, amoxilina, 2-hydroxyethoxyphenyl, 2-methoxyethanol and 2-ethoxyethylene groups;

G is selected from hydroxyl, -O(M)_2/v, -OR¹³, -NH₂-The other¹³and-N(R¹³) (R¹⁴);

where M represents a counterion with valency v is selected from ions of metals such as alkali metal ions and alkaline earth metal ions, ammonium ions and substituted ammonium ions, such as ions of mono-, di-, tri - and tetraalkylammonium, and each of R¹³and R¹⁴independently you Iraida from hydrogen, linear or branched C₁-C₈-alkyl, N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl and 2-ethoxyethyl. Representative non-limiting examples of monomers useful in the present invention include protected or unprotected acrylic acid and methacrylic acid and their salts, esters and amides.

Salts can be obtained for any counterions that represents any conventional non-toxic metal, ammonium or substituted ammonium. Esters can be derived from C_1-40-linear, With_3-40-or branched C_3-40-carbocyclic alcohols, polyhydric alcohols containing from about 2 to about 8 carbon atoms and from about 2 to about 8 hydroxyl groups (non-limiting examples of which include ethylene glycol, propylene glycol, butyleneglycol, hexyleneglycol, glycerol and 1,2,6-hexanetriol); aminoalcohols (non-limiting examples of which include aminoethanol, dimethylaminoethanol and Diethylaminoethanol and their quaternion derivatives); or ethers of alcohols (non-limiting examples of which include methoxyethanol and ethoxyethanol).

Amides can be unsubstituted, N-alkyl - or N-alkilaminometilen, or N,N-dialkyl - or N,N-dialkylaminomethyl, where the alkyl or alkylamino group mo the ut can be obtained from C _1-40-linear, With_3-40-or branched C_3-40-carbocyclic links. In addition, alkylamino-groups can be quaternity. Also useful as monomers are protected or unprotected acrylic and/or methacrylic acid, and their salts, esters and amides, where the substituents are in the second and third positions of the carbon atoms in acrylic and/or methacrylic acids, and they are independently from each other selected from C_1-4-alkyl, hydroxyl, halogen (-CL, -Br, -F, -I), -CN and-CO₂N, for example, methacrylic acid, metacrilato acid, alpha-chloroacrylate acid and 3-cyanacrylate acid. Salts, esters and amides data substituted acrylic and methacrylic acids can be defined as defined above salts, esters and amides of acrylic/methacrylic acids. Other useful monomers include vinyl and allyl esters With_1-40-linear, With_3-40-or branched C_3-40-carbocyclic carboxylic acids, vinyl - and allylchloride (for example, vinyl chloride, allylchloride), (for example, vinylpyridine, arilpirido); vinylidenechloride; and hydrocarbons having at least one unsaturated double bond carbon-carbon (for example, styrene, alpha-methylsterol, tert-butalbiral, butadiene, isoprene, cyclohexadiene, ethylene, n is cut 1-butene, 2-butene, isobutylene, n-methylsterol); and mixtures thereof.

Preferred monomers useful in the present invention include monomers selected from protected and unprotected acrylic acid, methacrylic acid, metacrilato acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutylacetate, tert-butyl acrylate, 2-ethylhexyl acrylate, decidability, octylacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutylacetate, tert-butyl methacrylate, 2-ethylhexylacrylate, decylmethacrylate, methylethanamine, tilatequila, n-butylacrylate, isobutylacetate, tert-butylacrylate, 2-ethylhexylacrylate, decretariat, 2,3-dihydroxypropyl, 2,3-dihydroxyphenylalanine, 2-hydroxyethylacrylate, 2-hydroxypropylmethacrylate, hydroxypropylmethacrylate, glycerylmonostearate, glycerylmonostearate, glycidylmethacrylate, glycidylmethacrylate, acrylamide, methacrylamide, ethacrylate, N-methylacrylamide, N,N-dimethylacrylamide, N,N-dimethylacrylamide, N-ethylacetamide, N-isopropylacrylamide, N-butylacrylamide, N-tert-butylacrylamide, N,N-di-n-butylacrylamide, N,N-diethylacrylamide, N-octylacrylamide, N-octadecylamine, N,N-diethylacrylamide, N-phenylacetamide, N-methylmethacrylate, N-ethylmethylamine, N-dodecyldimethylamine, N N-dimethylaminoethylacrylate, quatern the series N,N-dimethylaminoethylacrylate, N,N-dimethylaminoethylmethacrylate, quaternionic N,N-dimethylaminoethylmethacrylate, N,N-dimethylaminoethylacrylate, N,N-dimethylaminoethylmethacrylate, quaternionic N,N-dimethylaminoethylacrylate, quaternionic N,N-dimethylaminoethylmethacrylate, 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate, 2-hydroxyethylacrylate, glycerolkinase, 2-ethoxyethylacetate, 2-ethoxyethylacetate, 2-ethoxyethylacetate, 2-ethoxyethylacetate, 2-ethoxyethylacetate, 2-ethoxyethylacetate, maleic acid, maleic anhydride and its complex monoufia, fumaric acid, basis of itaconic acid, taconova anhydride and its complex monoufia, crotonic acid, angelicajoj acid chloride of diallyldimethylammonium, vinylpyrrolidone, vinylimidazole, methylvinylether ether, methyl vinyl ketone are, maleimide, vinylpyridine, vinifera, styrelseledamot, allyl alcohol, alliterate, alliterate, vinyl acetate, vinyl alcohol, vinylcaprolactam and mixtures thereof.

The preferred monomers are monomers selected from methyl acrylate, methyl methacrylate, methylethanamine, ethyl acrylate, ethyl methacrylate, tilatequila, n-butyl acrylate, n-butyl methacrylate, n-butylacrylate, 2-ethylhexyl acrylate, 2-ethylhexylacrylate, 2-ethylhexylacrylate, N-octylacrylamide, 2-ethoxyethylacetate 2-hydroxyethylacrylate, N,N-dimethylaminoethylacrylate, N,N-dimethylaminoethylmethacrylate, acrylic acid, methacrylic acid, 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate and mixtures thereof.

The most preferred monomers are monomers selected from N,N-dimethylaminoethylacrylate, N,N-dimethylaminoethylmethacrylate, 2-ethylhexyl acrylate, hydroxyethylmethacrylate, N-octylacrylamide, 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate and mixtures thereof.

Polysiloxane block copolymers

Conventional polysiloxane block copolymer obtained by the method described above, formed from units of the General formula [A]L[B], where a represents a polymer block formed from the polymerized by the radical mechanism of monomer, b is a polysiloxane block, L is a divalent connecting group which connects the blocks a and b through links O-Si, N-Si and S-Si unit C. Preferably L is selected from:

-R¹⁵-C(O)-O-;

-R¹⁵-O-C(O)-O-;

-R¹⁵-C(O)-N(R¹⁶)-;

-R¹⁵-O-C(O)-N(R¹⁶), or

-R¹⁵-N(R¹⁶)-C(O)-N(R¹⁷)-,

where R¹⁵represents the above-described divalent, possibly substituted, linear or branched hydrocarbon, C_1-18radical, and

R¹⁶and R¹⁷independently from each other selected from the above Adewale is the shaft, possibly substituted, linear or branched hydrocarbon, C_1-18-radicals.

The General molecular structure of the siloxane block copolymers according to this invention can be described by the formula A-L-B, A-L-B-L-A -(A-L-B)_n-where n is an integer equal to 2 or more, or [A-L-][A-L-]B[-L -] [L-A], where A-L-B is a double structure, A-L-B-L-A is a three-block structure -(A-L-B)_n- is a multiblock structure, a [A-L-][A-L]B[L-A][-L-A] represents a dendritic structure.

Cosmetic and intended for personal hygiene composition

Polysiloxane block copolymers of the present invention is preferably administered in a composition for hair care, in particular in compositions for hair lacquers in aerosol cans, but they can also be entered in a wide range of other types of products, including mousses, gels, lotions, tonics, drugs, sprays, shampoos, conditioners, conditioners, hand lotions and body care products, face moisturizers, sunscreens, anti-acne, pain relievers for local use, mascara and so on. Media and additional components required for obtaining the compositions of these products will vary from one type is redakcii to another, and they can be a specialist in the relevant field of the selected routine. The following is a description of some of these carriers and additional components.

Media

Compositions for hair care in accordance with the present invention may contain a carrier or a mixture of these media are suitable for use for hair care. Carriers are present in amounts of from about 0.5% to about 99.5%pure, preferably from about 5.0 percent to about 99.5%pure, more preferably from about 10.0% to about 98,0% of the composition. As stated in the description, the phrase “suitable for use for hair care” means that the carrier does not spoil the aesthetic parameters hair or not has a negative impact or not cause irritation on the skin. Carriers suitable for use in compositions for hair care in accordance with the present invention include, for example, the media used in the preparation of the compositions of paints for hair sprays, mousses, tonics, gels, shampoos, conditioners and rinses. Choosing the right media will also depend on the particular copolymer used, and whether implied that make up the composition of the product will stay on the surface the STI, on which it has been applied (e.g., hair spray, aerosol, mousse, tonic or gel), or it will be washed off after use (e.g., shampoo, conditioner, mouthwash).

The media used in the present invention, can include a wide range of components typically used in compositions for hair care. The carriers can contain a solvent for dissolving or dispersing the copolymer, preferably water, C1-C6-alcohols, (lower alkyl) acetate and mixtures thereof. The media can also contain a wide range of additional compounds, such as acetone, hydrocarbons (such as isobutane, hexane, decane), halogenated hydrocarbons (such as freons), and volatile derivatives, siloxanes, such as cyclomethicone. If the composition for hair care is hair spray aerosol, tonic, gel or mousse, the preferred solvents include water, ethanol, volatile derivatives, siloxanes, and mixtures thereof. The solvents used in such mixtures may be miscible or immiscible with each other. Mousses and hair sprays aerosol can also use any of the commonly used propellants to deliver material in the form of foam (in the case of Moussa) or in the form of a fine-grained homogeneous aerosol(in the case of hairspray aerosol). Examples of suitable propellants include compounds such as Trichlorofluoromethane, DICHLORODIFLUOROMETHANE, defloratin, dimethyl ether, propane, n-butane or isobutane. Products such as tonic or hair spray aerosol with a low viscosity, can also be used emulsifier. Examples of suitable emulsifiers include nonionic, cationic, anionic surfactant, or a mixture thereof. If such an emulsifier is used, it preferably will be present in a content ranging from approximately 0.01% to approximately 7.5% of the composition. The amount of propellant can be increased to a desirable, but in General it is in the range from approximately 3% to approximately 30% of the mousse compositions and from about 15% to about 50% of the songs hairspray aerosol.

Suitable containers for aerosol well-known state of the art and they include a normal non-aerosol spray guns, that is, “atomizers”, aerosol containers or tanks containing the above-described propellant, as well as sprinklers, creating an aerosol, using as propellant compressed air.

If the compositions for hair care will conditioners and rinses, then the media can in order to include a large variety of compounds with conditioning effect. If the compositions for hair care products are the shampoos, the media may include, for example, surfactants, suspendresume additives and thickeners.

The media may be present in the form of a wide range of forms. For example, in the present invention are useful carriers in the form of emulsions, including emulsions relating to the types of “oil in water”, “water in oil”, “water in oil in water” and “oil-in-water in the siloxane”. The viscosity of these emulsions can be in a wide range of viscosities, for example, from about 100 centipoise to about 200,000 centipoise. These emulsions can also be submitted in the form of aerosols using either mechanical sprinklers or Isobaric aerosol packaging, using conventional propellants. These carriers can also be submitted in the form of a mousse. Other suitable carriers for topical application include anhydrous liquid solvents, such as oils, alcohols, siloxanes (e.g., mineral oil, ethanol, isopropanol, Dimethicone, cyclomethicone and the like); a single-phase liquid solvents water-based (such as water-alcohol solvents); and thickened options data anhydrous solvents and single-phase solvents water-based (for example, when the viscosity of the solvent by the addition of suitable gums, resins, vos is s, polymers, salts and the like has been increased to obtain the consistency of a solid or semi-solid body).

Additional components

In cosmetic and intended for the personal care compositions of the present invention may be used in a wide range of additional components. Examples include:

- sun protection factors, such as 2-ethylhexyl-p-methoxycinnamate, 2-ethylhexyl-N,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2-phenylbenzimidazol-5-sulfonic acid, octocrylene, oxybenzone, homogentisate, octisalate, 4,4'-methoxy-tert-butylbenzoyl, 4-isopropyl-dibenzoylmethane, 3-benzylidene, 3-(4-methylbenzylidene) camphor, titanium dioxide, zinc oxide, silicon dioxide, iron oxide and mixtures thereof.

- anti-dandruff, such as zinc pyrithione, pyroceramic, selenium disulfide, sulfur, coal tar, and the like.

components with conditioning effect for the compositions for hair care, such as hydrocarbons, silicone fluids and cationic compounds. The hydrocarbons may be either linear or branched and can contain from about 10 to about 16, preferably from about 12 to about 16 carbon atoms. Examples of suitable carbohydrate is childbirth are the Dean, dodecan, tetradecane, tridecane and mixtures thereof. Examples of suitable siloxane components with conditioning effect, useful in the present invention, can include either cyclic or linear polydimethylsiloxane, phenyl - and alkylperoxy and elexandria polyalcohol copolymer. Cationic components with conditioning effect, useful in the present invention, may include a Quaternary ammonium salt or salts of fatty amines.

- surfactants for the compositions in the form of a shampoo and conditioner for hair. For shampoo, the content is preferably in the range from about 10% to about 30%, preferably from about 12% to about 25% of the composition. For air conditioners preferred levels of surfactant is in the range from about 0.2% to about 3%. Surfactants useful in the compositions of the present invention include anionic, nonionic, cationic, zwitterionic and amphoteric surfactants.

- containing groups, carboxylic acid polymer thickeners. Data crosslinked polymers contain monomer units of one or more types derived from acrylic acid, substituted acrylic acids and salts and esters of data acrylic sour and substituted acrylic acids, where the stapler contains two or more double carbon-carbon, and the binder is derived from a polyhydric alcohol. Examples of the group containing carboxylic acid polymer thickeners useful in the present invention are those selected from the group consisting of carbomer, acrylates/mesh-based polymers C10-C30-alkylacrylate and mixtures thereof. Compositions of the present invention may contain from about 0.025% of up to about 1%, more preferably from about 0.05% to about 0.75 percent, and most preferably from about 0.10% up to about 0.50% of the group containing carboxylic acid polymer thickeners.

- emulsifiers to emulsify various carrier components in the compositions of the present invention. Suitable types of emulsifying agents include polyethylene glycol 20-sorbitanoleat (Polysorbate 20), polyethylene glycol 5 soya Sterol, stearyl simple ether-20, methylthiazolyl simple ether-20, PPG-2-methylglutaronitrile, simple cetyl ether-10, Polysorbate 80, cetilistat, cetilistat potassium, diethanolamines, Polysorbate 60, literallayout, PEG-100 stearate, and mixtures thereof. The emulsifiers can be used individually or as a mixture of two or more, and they can range from about 0.1% to about 10%, more p is edocfile from about 1% to about 7%, and most preferably from about 1% to about 5% of the composition of the present invention.

- vitamins and their derivatives (for example, ascorbic acid, vitamin E, tocopherylacetate, retinoic acid, retinol, retinoids, and the like).

cationic polymers (for example, cationic derivatives of the guar gums, such as chloride guar-hydroxypropyltrimonium and chloride hydroxypropyl-guar-hydroxypropyltrimonium available in the form of a series Jaguar With the company Rhone - Poulenc).

- stabilizers, antioxidants, chelating agents and additives intended for extraction of other compounds; and components, giving aesthetic characteristics, such as flavouring agents, dyes, nutrients for hair and essential oils.

Hereinafter the invention will be illustrated in the following non-limiting examples:

EXAMPLES

Examples 1-8

Three-block copolymers AVA described by the following General formula:

Three-block copolymers AVA PDMAEMA-PDMS-PDMAEMA were obtained by radical polymerization atom transfer (ATRP). To obtain an ATRP initiator commercially available polydimethylsiloxane (PDMS) with end aminopropylene group was introduced halide functionality. Achieved asked molecular weight with ultrasound the second polydispersity.

The way to obtain

Cu^IBr (0,2732 g, 1,905 mmol) together with a magnetic stir bar were placed in a dry flask Slanka, which then was evacuated and three times was purged with nitrogen. Using a degassed syringe into the flask Slanka was added 2-dimethylaminoethylmethacrylate (3.9 ml, is 0.023 mol), toluene (7.2 ml) and PDMS-initiator (1) (2 g, 0,952 mmol). *After the solution was removed oxygen in the three cycles of freeze-pumping-thawing. Finally, as in the flask had reached the desired reaction temperature 90°C, under stirring was added ligand n-propyl-2-pyridylmethylamine (2) (0.54 ml, 3,809 mmol). After addition of the ligand the reaction mixture immediately became dark brown in color.

*Target molecular weight DMAEMA = 4000, molecular weight initiator = 2000 (total = 6000). The ratio of [monomer]:[initiator] determines the molecular weight of the final polymer. In the described ATRP desired ratio of [monomer]:[initiator]=25:1. Ratios for other reagents listed as follows: [Cu^IBr]:[initiator]=1:2, [ligand]:[Cu^IBr]=2:1 and the volume of solvent:the amount of monomer =2:1.

The monomer was purified, passing it through a column of basic alumina prior to use, and blew the nitrogen is m for at least one hour. This method was also degirolami and toluene, which was used as solvent for all polymerizate. Cu^IBr was purified before use in accordance with the published method.¹

1) Keller, R.N.; Wycoff, H.D. Inorganic Synthesis, 1947, 2, 1.

Cleaning polymer

The resulting dark brown solution was passed through a column of aluminum oxide several times using commonly used solvent, such as dichloromethane or tetrahydrofuran. When the solution became colorless, the solvent was removed under vacuum to obtain a pale yellow solid phase.

Results

Film formation

Preparing a solution of ethanol/water (55%:45%). In solution (10 ml) was added a small sample of the polymer (0.5 g). For some of the samples required dilution, but other dissolved immediately. A small amount of solution (1 ml) were placed in a plastic Cup and left to dry for 3 hours.

Analysis of adhesion

The parameters for the Diastron MTT600: % elongation = 100

Speed (mm/min) = 10

The maximum is the amount of force (g) = 200

The force measuring

device (gram-force) = 2

5%-aqueous solution of alcohol (55% ethanol/water): 1 μl, put the eyedropper on the connection.

Temperature = 20°

Humidity = 50%

Sensory properties

The polymer obtained in example 1 was used to obtain 55%of the composition, when sprayed to the evaporator watercooling circuit (VOC), (4,2% polymer, 55% ethanol and 40.8% water). The composition was sprayed onto a piece of hair and the results were compared with results for a commercial product composition for spraying Suave ® Extra Hold (4,2% AMPHOMER ®).

The composition containing the polymer of example 1 had significant benefits in terms of softness and fewer deposits (both before and after brushing).

1. A method of obtaining a polysiloxane block copolymer which is formed from units of the formula [A][V], where a represents a polymer block formed from a polymer clay is isoimage on the radical mechanism of the monomer, and is a polysiloxane block, and the method includes the stage of formation of polysiloxane macroinitiator in the vaccination of a radical initiator to polysiloxan using reactions of nucleophilic substitution occurring between groups of polysiloxane and a radical initiator, respectively, and the reaction of the radical polymerization atom transfer between thus obtained the polysiloxane macroinitiator and the polymerized by a radical mechanism monomers with getting polysiloxane block copolymer.

2. The method according to claim 1, characterized in that it includes the stages of (a) education polysiloxane macroinitiator in the reaction of nucleophilic substitution between (i) a polysiloxane, as end groups of which has at least one group capable nucleophile to attack, using his atom is O, N or S, and (ii) a radical initiator containing at least one group-C(O)X, in which X represents tsepliaeva group that can be substituted by nucleophilic atom is O, N or S polysiloxane (i)and at least one a group of organic halide capable of generating a radical in the presence containing a transition metal catalyst, followed by (b) conducting the reaction between the organic groups of the halide Policia Sanogo macroinitiator, obtained in stage a)and the polymerized by a radical mechanism monomers in the presence of catalytic amounts of salt cu (I) with the formation of polysiloxane block copolymer.

3. Polysiloxane block copolymer obtained by the method according to claim 1 or 2.

4. Polysiloxane block copolymer according to claim 3, which is formed from units of the General formula [A]L[B], where a represents a polymer block formed from the polymerized by the radical mechanism of monomer, b is a polysiloxane block, L is a divalent connecting group which connects the blocks a and b through links O-Si, N-Si and S-Si unit, and which is selected from R¹⁵-C(O)-O-; -R¹⁵-O-C(O)-O-; -R¹⁵-C(O)-N(R¹⁶)-; -R¹⁵-O-C(O)-N(R¹⁶)or R¹⁵-N(R¹⁶)-C(O)-N(R¹⁷)-, where R¹⁵represents a divalent, possibly substituted, linear or branched hydrocarbon, C_1-18radical, and R¹⁶and R¹⁷independently from each other are selected from monovalent, possibly substituted, linear or branched hydrocarbon, C_1-18-radicals.

5. Cosmetic and intended for personal hygiene composition containing polysiloxane block copolymer according to claim 3 or 4.

6. Cosmetic and intended for personal hygiene composition according to claim 5 in the form of a hairspray in AE is Solineu packaging gel or mousse.