JP2799219B2 - Cosmetic composition - Google Patents

Description

The present invention relates to a novel cosmetic composition based on a graft copolymer comprising an organopolysiloxane and an acrylic and / or methacrylic monomer, in particular, The present invention relates to a cosmetic composition for hair, skin and makeup.

This copolymer can impart various properties particularly required for cosmetics due to its skin-forming properties and film properties.

The hair composition has a supple, smooth feel and good set holding power.

In addition, the composition for skin and make-up has good water resistance, sweat resistance and oil resistance, and is excellent in makeup.

[Related Art] A hair cosmetic contains a polymer compound for fixing hair. For example, a polyvinylpyrrolidone-based polymer compound, a polyvinyl ether-based polymer compound, a polyvinyl acetate-based polymer compound, an acrylic polymer compound, and the like.

On the other hand, oil agents and the like are blended for the purpose of giving gloss and smoothness to hair, but hair cosmetics that can give a supple and smooth feel while having high set holding power have not been obtained so far. .

In addition, sweat in skin and makeup cosmetics,
Moisturization of tears, rain, snow, and the like, and sebum, sweat, and other cosmetic oils cause makeup loss. In particular, makeup loss under hot and humid conditions in summer has been desired to be improved as a common problem for women.

[Problems to be Solved by the Invention] In view of such circumstances, the present inventors have proposed hair cosmetics, water resistance, and hair satisfactorily having excellent set holding power and satisfying supple and smooth feel. As a result of intensive research to obtain good oil resistance and good cosmetic skin and makeup cosmetics, radical polymerization of a mixture of a specific organopolysiloxane emulsion and an acrylic and / or methacrylic-based mixed monomer was carried out. The inventors have found that the above object can be achieved by using a graft copolymer obtained by polymerization in the presence of an initiator, and have completed the present invention based on this finding.

[Means for Solving the Problems] That is, the present invention provides (A) a compound represented by the general formula (I): [Wherein, R ¹ , R ² , and R ³ are each one or more groups selected from a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent halogenated hydrocarbon group, Y is one or two or more groups selected from a radical reactive group and an organic group including an SH group, and X is a hydrogen atom, a monovalent lower alkyl group and represented by the formula R ¹ R ² R ⁴ Si Groups (R ¹ and R ² are the same as described above;
⁴ is the same or different group selected from R ^{1 and} Y), m is a positive integer of 10,000 or less, and n is 1
5 to 95 parts by weight of an oil-in-water emulsion represented by the following general formula (II): (Wherein, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a C 1-18
One or more monomers selected from acrylic and methacrylic monomers represented by the following formulas: 70 to 100% by weight b) ethylenically unsaturated amide, ethylenic Alkylol or alkoxyalkyl-substituted compounds of unsaturated amides, ethylenically unsaturated monomers containing oxirane groups, ethylenically unsaturated monomers containing hydroxyl groups, ethylenically unsaturated monomers containing carboxyl groups, polyhydric alcohols and acrylics One or more polyfunctional monomers selected from the group consisting of a perfect ester with an acid or methacrylic acid, diallyl ester of a dibasic acid, allyl acrylate, allyl methacrylate and divinylbenzene 0 to 10% by weight c) A mixed monomer comprising 0 to 20% by weight of one or more ethylenically unsaturated monomers other than the above a) and b) A total of 100 parts by weight of the components [a] to c)] 95 to 5 parts by weight in the presence of a radical polymerization initiator, as a film-forming component. It is a cosmetic composition.

The organopolysiloxane used in the cosmetic composition of the present invention imparts a pleasant feeling to sticky, supple and smooth skin, and improves coating film properties such as water resistance. This is represented by the general formula (I) R ¹ , R ² , R ³ is a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a phenyl group, a tolyl group,
Selected from monovalent hydrocarbon groups having 1 to 20 carbon atoms, exemplified by aryl groups such as xylyl and naphthyl, and groups in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups have been substituted with halogen atoms. X is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a lower alkyl group having 1 to 5 carbon atoms such as a pentyl group, and a triorganosilyl group represented by R ¹ R ² R ⁴ Si. (R ¹ and R ² are the same as above, R ⁴ is R
¹ or Y), wherein Y is a radical reactive group exemplified by a vinyl group, an allyl group, a γ-acryloxypropyl group, a γ-methacryloxypropyl group, a γ-mercaptopropyl group, and SH It is selected from group-containing organic groups.

Further, m is a positive integer of 10,000 or less, and n is an integer of 1 or more, more preferably 200 <m <8,000, 1
<N <500 is preferable.

The production of the emulsion of the organopolysiloxane represented by the general formula (I) may be performed according to a known method.
One method is to use a low-molecular cyclic siloxane such as octamethylcyclotetrasiloxane and a dialkoxysilane containing a radical reactive group or SH group and / or a hydrolyzate thereof as raw materials, and use a strong alkaline catalyst or a strongly acidic catalyst. The polymerization is carried out in the presence of a catalyst to obtain a high molecular weight organopolysiloxane, which is then emulsified and dispersed in water in the presence of a suitable emulsifier.

Another method uses, for example, the above-mentioned low molecular weight organosiloxane and a dialkoxysilane containing a radical reactive group or an SH group and / or a hydrolyzate thereof as raw materials, and uses a sulfonic acid surfactant and / or Alternatively, it is based on emulsion polymerization in water in the presence of a sulfate ester surfactant.

In addition, in the case of this emulsion polymerization, after using the same raw materials and emulsifying and dispersing in water with a cationic surfactant such as alkyltrimethylammonium chloride or alkylbenzylammonium chloride, an appropriate amount of potassium hydroxide, sodium hydroxide or the like is used. Polymerization can also be carried out by adding a strongly alkaline substance.

The above-mentioned sulfonic acid-based surfactant and sulfate ester-based surfactant serve as an emulsifier and a polymerization catalyst. _{C 10 H 21 (OC 2 H} 4) OSO 3 H, sodium lauryl sulfate, polyoxyethylene dodecyl phenyl sodium sulfate, and the like.

Of these, the sulfates are converted into the corresponding acids by contacting with a cation exchange resin after the emulsification, and function as a polymerization catalyst. After the completion of the emulsion polymerization, the surfactant in the acid form may be neutralized to eliminate the catalytic activity.

Further, as the cationic emulsifier, a quaternary ammonium salt as described above is mainly used, and after the emulsion polymerization, a basic surfactant may be neutralized to eliminate the catalytic activity.

Furthermore, the size of the molecular weight of the organopolysiloxane can be adjusted by the temperature at the time of aging performed after the emulsion polymerization. Therefore, the aging temperature may be set according to the desired physical properties.

Next, the component (B) will be described. This is a mixture of a polymerizable monomer for graft copolymerization with the organopolysiloxane of the component (A).
To (c).

A) The component is represented by the general formula (II) (Wherein, R ⁵ is hydrogen or a methyl group, and R ⁶ is an alkyl group or an alkoxy-substituted alkyl group having 1 to 18 carbon atoms) (meth) acrylic monomer (herein, the expression (meth) acryl is acrylic) And methacryl are collectively represented in the following.) And methyl (meth)
Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
Alkyl (meth) acrylates such as isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate And alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate.
Used in combination of more than one species.

If the compounding amount of component (a) is less than 70% by weight of component (B), acrylic properties, particularly properties such as film forming properties, film strength, sweat resistance, oil resistance, and adhesion to skin are insufficiently imparted. It is.

B) The component is a polyfunctional monomer, and is (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) as an ethylenically unsaturated amide, an alkylol of an ethylenically unsaturated amide or an alkoxyalkyl compound. Acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, etc. As oxirane group-containing unsaturated monomers, glycidyl (meth) acrylate, glycidyl allyl ether, etc. As hydroxyl group-containing unsaturated monomers Polyhydric alcohols such as (meth) acrylic acid, maleic anhydride, crotonic acid, and itaconic acid as carboxyl group-containing ethylenically unsaturated monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; And (meta) acri Ethylene glycol di (meth) acrylate as a full ester of an acid, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and allyl (meth)
Acrylate and divinylbenzene are exemplified.

These polyfunctional monomers are used for the purpose of imparting adhesion to the skin, good holding power of the set, and make-up stickiness. Etc. are improved, but the texture of the decorative coating film is impaired. Therefore, the amount of the polyfunctional monomer used is 0 to 0 in the component (B).
The content is 10% by weight, and when it exceeds 10% by weight, the texture becomes noticeably impaired.

C) the component is another ethylenically unsaturated monomer,
The component (B) is used in the range of 0 to 20% by weight in order to impart a feeling, durability and the like which cannot be exhibited only by the components (a) and (b). Will be impaired.

Examples of such a monomer include styrene, α-methylstyrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, and vinyl persate.

In order to impart flexibility to the film formed by the cosmetic composition, the polymerized product of the component (B) may be softened, and it is desirable to consider the glass transition point of the polymerized product.

Regarding the ratio of the component (A) to the component (B), if the component (A) is less than 5 parts by weight, a sticky feeling, which is a drawback of the acrylic polymer, occurs, and the flexibility becomes poor. It is not practical because the toughness of the film and the stickiness are lost.

Emulsion copolymerization of the components (A) and (B) may be performed by a known emulsion polymerization method using a usual radical initiator.

Examples of the radical polymerization initiator used herein include potassium persulfate, persulfates such as ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, and water-soluble types such as the HCl salt of azobisamidinopropane; Oil-soluble types such as benzoyl peroxide, cumene hydroperoxide, dibutyl peroxide, diisopropyl peroxy dicarbonate, cumyl peroxy neodecanoate, azobisisobutyronitrile and the like can be mentioned. If necessary, sodium acid sulfite, Rongalit, L-
A redox system using a reducing agent such as ascorbic acid, a saccharide, or an amine in combination can also be used.

As the emulsifier, since the emulsifier is contained in the emulsion of the component (A), it is not always necessary to newly use the emulsifier,
A necessary amount of an emulsifier may be added in order to prevent agglomeration during polymerization and to improve emulsion stability. Examples of the emulsifier used herein include, for example, an alkyl or alkyl allyl sulfate or a sulfonate, an anionic emulsifier such as an alkyl allyl succinate, a cationic emulsifier such as an alkyl trimethyl ammonium chloride and an alkyl benzyl ammonium chloride, and polyoxyethylene. Nonionic emulsifiers such as alkyl phenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene carboxylic acid ester are preferred.

If necessary, an aqueous solution of an inorganic salt, a water-soluble organic solvent or the like is added to these emulsion copolymers to aggregate the particles, followed by filtration, washing and drying to obtain a copolymer resin.

Examples of the cosmetic composition according to the present invention include liquid cosmetics such as lotions, essences, and hair stylings; emulsified cosmetics such as emulsions, creams, hair creams, and liquid foundations;
Washing agents such as foundations, eyeliners, mascaras, solid pastes, blushes, etc., and washing agents such as rinses, and the above-defined copolymers are used as main active ingredients or as additives.

The concentration of the copolymer in the cosmetic composition according to the present invention is 0.5
A range of .about.30% by weight is suitable. That is, if the content is 0.5% or less, the effect of the present invention cannot be obtained, and if it is 30% or more, it becomes impossible to constitute a cosmetic composition.

In the hair cosmetic composition, the copolymer facilitates obtaining a good haircut and gives dry hair a supple and smooth feel.

Furthermore, these compositions in the skin and make-up cosmetics impart a pleasant texture to the skin, exhibit excellent water resistance and oil resistance, and exhibit an excellent effect on makeup.

The cosmetic composition of the present invention includes, in addition to a copolymer composed of an organopolysiloxane and an acrylic and / or methacrylic monomer, various volatile or nonvolatile oil agents conventionally used, and a surfactant. Optional components such as an agent, a wetting agent, a preservative, an antioxidant, a fragrance, and a powder can be appropriately blended.

Volatile or non-volatile oils include linear or branched hydrocarbons, linear or cyclic dimethylpolysiloxanes, higher alcohols, higher fatty acids, synthetic ester oils of alcohols and fatty acids, sucrose esters, waxes, waxes And the like. Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, glycerin, fatty acid ester, polyoxyethylene hardened castor oil, and polyoxyethylene sorbitol fatty acid ester. .
Examples of the lubricant include sorbitol, glycerin, propylene glycol, 1,3-butylene glycol, maltitol, lactic acid, sodium lactate, polyethylene glycol and the like. Examples of the preservative include alkyl paraoxybenzoate, sodium benzoate, potassium sorbate, phenoxyethanol and the like. Examples of the antioxidant include tocopherol, lecithin and the like. Examples of the powder include titanium oxide, zinc oxide, ultramarine, chromium oxide, iron oxide, talc, sericite, mica, kaolin, mica, and organic pigments.

[Examples] Next, reference examples for producing the copolymer used in the present invention and examples of the present invention will be described more specifically.
All parts in the examples are parts by weight, and all parts are percentages by weight.

Reference Example (Preparation of organopolysiloxane emulsion) 1500 parts of octamethylcyclotetrasiloxane, 3.8 parts of cyclic methacryloxypropylmethylpolysiloxane and 1500 parts of pure water were mixed, and sodium lauryl sulfate 15 was added thereto.
After adding 10 parts of dodecylbenzenesulfonic acid, the mixture was emulsified by stirring with a homomixer, and then passed twice through a homogenizer at a pressure of 3,000 psi to form a stable emulsion. After heating at 70 ° C for 12 hours, cooling to 25 ° C and aging for 24 hours, the pH of this emulsion was adjusted to 7 using sodium carbonate, and nitrogen gas was blown for 4 hours, followed by steam distillation. The volatile siloxane was distilled off, and then pure water was added to adjust the nonvolatile content to 45%. As a result, an emulsion of a polysiloxane containing 0.1 mol% of methacryl groups was obtained (hereinafter referred to as E-1). Abbreviated).
Also, as shown in Table 1, polysiloxane emulsions E-2 to E-5 were obtained in the same manner as in E-1, except that the kind, amount and aging conditions of siloxane were changed.

(Production of Copolymer by Emulsion Copolymerization) In a reactor equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet, 333 parts of the emulsion E-1 obtained above (150 parts of siloxane) and 517 parts of pure water After adjusting the inside temperature to 30 ° C. under a nitrogen gas stream, 1.0 part of t-butyl hydroperoxide, 0.5 part of L-ascorbic acid and 0.002 part of ferrous sulfate heptahydrate were added. While keeping the internal temperature at 30 ° C., 129.5 parts of ethyl acrylate, 133.0 parts of butyl acrylate, 77.0 parts of methyl methacrylate and 10.5 parts of methacrylic acid were added dropwise over 3 hours, and after the addition was completed, stirring was continued for another 1 hour to carry out the reaction. Completed.

The obtained graft copolymer emulsion (hereinafter referred to as P
(Abbreviated as -1), the solid content concentration was 39.7%, and the calculated glass transition point of a polymerized product such as an acrylic monomer was -12.7 ° C. In the same manner, copolymerization was carried out with the types and amounts of the polysiloxane emulsion and acrylic monomer shown in Table 2,
Copolymer emulsions P-2 to P- having a solid content of 39 to 40%
6 was obtained.

Example 1 (Hair setting) 1. Copolymer emulsion (P-1) 2.0% 2. Hydroxyethyl cellulose 0.2 3. Ethyl alcohol 10.0 4. Fragrance 0.2 5. Purified water Residue Polypropylene is used in the production of copolymer emulsion (P-1). Except for siloxane emulsion E-1, excluding the conventional hair set using a copolymer polymerized only with acrylic and methacrylic monomers, it has a refreshing feeling and is excellent in smoothness and set holding power. It was a hair set.

Example 2 (Shampoo) 1. Copolymer emulsion (P-2) 2.0% 2. Polyoxyethylene lauryl ether 14.0 3. Diethanolamide laurate 5.0 4. Perfume 0.2 5. Purified water Residue Style retention compared to conventional shampoo It was a stable shampoo that could give formability and a smooth feel.

Example 3 (Foundation) 1. Copolymer emulsion (P-3) 30.0% 2. Liquid paraffin 12.0 3. Paraffin wax 2.0 4. Palmitic acid 3.0 5. Propylene glycol 8.0 6. Polyoxyethylene sorbitan monostearate 2.0 7. Diethanolamine 1.0 8.Talc 15.0 9.Iron oxide 3.0 10.Fragrance 0.5 11.Purified water Residue The obtained foundation grows very evenly,
The adhesiveness to skin, water resistance and oil resistance were high, and there was no stickiness.

Example 4 (Mascara) 1. Copolymer emulsion (P-4) 50.0% 2. Polyoxyethylene sorbitan monooleate 2.0 3. Polyethylene glycol 5.0 4. Ethyl alcohol 2.0 5. Iron oxide 13.0 6. Fragrance 0.3 7. Purification Water Residue The obtained mascara had good usability and finished condition, and was further high in water resistance and oil resistance.

Example 5 (Eyeliner) 1. Copolymer emulsion (P-5) 20.0% 2. Beeswax 7.0 3. Polyoxyethylene sorbitan monostearate 2.0 4. Polyoxyethylene oleyl ether 1.0 5.1,3 Butylene glycol 6.0 6. Oxidation Iron 15.0 7. Fragrance 0.2 8. Purified water Residue The obtained eyeliner coating film was resistant to friction, water and oil, and had little stickiness after application.

Example 6 (Eye shadow) 1. Acrylic grafted organopolysiloxane 10.0% obtained by salting out copolymer emulsion (P-6) 2. Diisopropyl adipate 20.0 3. Cyclic dimethylpolysiloxane 23.0 4. Carnauba wax 8.0 5. Celesin 5.0 6. Iron oxide 20.0 7. Mica 12.0 8. Titanium oxide 1.8 9. Fragrance 0.2 Acrylic grafted organopolysiloxane is placed in a container equipped with a stirrer and heated to 60 ° C with 500 parts of copolymerized emulsion (P-6). Then, a solution prepared by dissolving 62 parts of sodium sulfate in 380 parts of pure water was added thereto to precipitate a graft polymer, which was obtained by repeating filtration and washing, followed by drying at 60 ° C.

This eye shadow had no stickiness with high adhesion to the skin, high water resistance and high oil resistance.

[Effects of the Invention] The cosmetic composition of the present invention is a hair cosmetic which is more excellent than ever and gives the hair suppleness and smoothness and has excellent set holding power to the hair. It is a skin and makeup cosmetic which is excellent in water resistance, sweat resistance and oil resistance, has excellent makeup, has little makeup loss, and is stable and excellent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A61K 7/11 A61K 7/11 (72) Inventor Kiyoji Suemoto 2-17-33 Kitafu, Takefu-shi, Fukui Pref. In-company (56) References JP-A-2-25411 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A61K 7/00-7/50

Claims (2)

(57) [Claims] (A) The general formula (I) [Wherein, R ¹ , R ² , and R ³ are each one or more groups selected from a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent halogenated hydrocarbon group, Y is one or two or more groups selected from a radical reactive group and an organic group including an SH group, and X is a hydrogen atom, a monovalent lower alkyl group and represented by the formula R ¹ R ² R ⁴ Si Groups (R ¹ and R ² are the same as described above;
R ⁴ is the same or different group selected from R ^{1 and} Y), m is a positive integer of 10,000 or less, and n is 1
5 to 95 parts by weight of an oil-in-water emulsion represented by the following general formula (II): (Wherein, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a C 1-18
One or two or more monomers selected from acrylic and methacrylic monomers represented by the following formulas: 70 to 100% by weight b) ethylenically unsaturated amide, ethylene Alkylol or alkoxyalkyl-substituted compounds of unsaturated amides, oxirane group-containing ethylenically unsaturated monomers, hydroxyl group-containing ethylenically unsaturated monomers, carboxyl group-containing ethylenically unsaturated monomers, and polyhydric alcohols. One or more polyfunctional monomers selected from the group consisting of complete esters with acrylic acid or methacrylic acid, diallyl esters of dibasic acids, allyl acrylate, allyl methacrylate and divinylbenzene 0 to 10% by weight c A) a mixed monomer comprising 0 to 20% by weight of one or more ethylenically unsaturated monomers other than the above a) and b) A total of 100 parts by weight of (a) to (c)] 95 to 5 parts by weight in the presence of a radical polymerization initiator. Cosmetic composition. 2. In the general formula (I), m and n each represent 20
2. The cosmetic composition according to claim 1, wherein 0 <m <8,000 and 1 <n <500.