JP2002234811A - Cosmetic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic composition for the hair having an excellent set retention power while providing a soft and smooth feeling and a skin/make- up cosmetic composition having improved water resistance, oil resistance and perspiration resistance and excellent makeup lasting properties. SOLUTION: This cosmetic composition is characterized by comprising a colloidal silica core-silicone shell body as a film-forming component composed of (A) 80-5 wt.% of a core of colloidal silica and (B) 20-95 wt.% of a shell of a polyorganosiloxane having an average composition formula represented by R1aSiO(4-a)/2 (R1 is a hydrogen atom or a substituted or nonsubstituted monofunctional hydrocarbon group; a is a number of 1.80-2.20).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic composition containing a colloidal silica core-silicone shell as a film-forming component, and more particularly to a supple, smooth feel and good set holding power. The present invention relates to a cosmetic composition for hair and a cosmetic composition for skin and make-up that has good water resistance, oil resistance and sweat resistance and has excellent makeup.

[0002]

2. Description of the Related Art Generally, hair cosmetic compositions are in a form containing a polymer compound for fixing hair and an oil agent for imparting gloss and smoothness to hair. That is, a high molecular compound such as a polyvinylpyrrolidone-based polymer compound, a polyvinyl ether-based polymer compound, a polyvinyl acetate-based polymer compound, or an acrylic polymer compound is compounded as a hair fixing agent, while the gloss and smoothness of the hair are increased. An oil agent is blended in order to impart such properties.

[0003] Cosmetic compositions for skin and make-up are generally composed of a polymer compound for the purpose of protecting the skin from irritants, imparting moisturizing properties and improving the durability of makeup, It adopts a configuration containing an oil agent for the purpose of improving the feel of use. That is, while a polymer compound such as an acrylic polymer compound or a cellulose polymer compound is blended as a film-forming component, an oil agent such as silicone oil is blended to improve usability and feel during use.

[0004]

However, a hair cosmetic composition comprising a high molecular compound as the hair fixative and an oil agent for imparting gloss and smoothness to the hair is provided in a high set retention. While having power, it is still not satisfactory enough in terms of flexibility and smooth feel. On the other hand, in the case of a conventional cosmetic composition for skin or make-up, there is a tendency for makeup to be easily collapsed due to moisture such as sweat, tears, rain, snow, or other cosmetic oils, skin or sweat. Improvements in water resistance, oil resistance, and sweat resistance have been desired.

The present inventors have conducted intensive studies in response to the above circumstances. As a result, when colloidal silica contained a silica core-silicone shell obtained by bonding a polyorganosiloxane to a siloxane as a film-forming component,
Not only has good set holding power, but also becomes a hair cosmetic composition that is given a supple and smooth feel, or has good water, oil, and sweat resistance, and excellent makeup skin -It has been found that it can be a makeup cosmetic composition.

[0006] The present invention has been made based on this finding, and provides a hair cosmetic composition having a supple and smooth feel while having good set holding power, water resistance, oil resistance and sweat resistance. The purpose of the present invention is to provide a skin / make-up cosmetic composition having a good skin feel and excellent makeup.

[0007]

Means for Solving the Problems The invention of claim 1 is:
(A) a core of colloidal silica of 80 to 5% by weight;
Of the polyorganosiloxane represented by the average composition formula R ¹ _a SiO (4-a) / 2 (wherein R ¹ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and a is a number of 1.80 to 2.20) A cosmetic composition comprising a colloidal silica core-silicone shell composed of 20 to 95% by weight of a shell as a film-forming component.

Here, the colloidal silica core-silicone shell body is mainly composed of colloidal silica as a core and at least a part of its surface covered with silicone, that is, polyorganosiloxane as a shell. It may take a form containing some silicone particles. In the above average composition formula, R ¹ is in the range of 0.01 to 25 mol%, preferably 0.05 to 5 mol% of the total amount, and when substituted with an organic functional group or an ethylenically unsaturated group, it is supple and smooth. Without sacrificing good feel
Improves adhesion to hair and skin.

[0009] The colloidal silica core-silicone shell used in the present invention, after the water is removed,
It is a component that forms an elastomer cured product, and is obtained by covering the colloidal silica of the component (a) with the polyorganosiloxane of the component (b). More specifically, basically, (1) one end of a polyorganosiloxane bonded to a silica surface through a siloxane bond, and (2) one end of a polyorganosiloxane is bonded to a silica surface through a siloxane bond. It is composed of three types: those which are bonded and the other end is blocked by a hydroxyl group; and (3) those in which both ends of the polyorganosiloxane are blocked by a hydroxyl group and have no siloxane bond with the silica surface. Then, the combined use of the 3,4-functional alkoxysilane and the chain stopper increases the types of the above-mentioned forms and makes them complex.

The component (a) of the colloidal silica core-silicone shell according to the present invention, ie, colloidal silica, refers to an aqueous dispersion containing SiO ₂ as a basic unit and has an average particle diameter of 4 to 300 nm. , More preferably
30 to 150 nm. Colloidal silica is classified into acidic and alkaline according to the characteristic classification, and can be appropriately selected and used depending on the conditions at the time of emulsion polymerization when producing a core-shell body. For example, when emulsion polymerization is performed under acidic conditions using an anionic surfactant, use of acidic colloidal silica is preferred.

The component (b) of the colloidal silica core-silicon shell according to the present invention, that is, the shell of the polyorganosiloxane is selected in the range of 20 to 95% by weight. The reason is that if it is less than 20% by weight, the elasticity and the like will be greatly reduced, and a cured product lacking in elastomeric properties will be generated
On the other hand, when the content exceeds 95% by weight, the colloidal silica has insufficient reinforcing properties and becomes an elastomer cured product lacking in mechanical properties. That is, in any case outside of the above range, as a result, a hair cosmetic composition having a desired suppleness and a good set holding power while giving a smooth feel, and water resistance, oil resistance and sweat resistance Does not function as a good cosmetic composition for skin and makeup.

The above average composition formula, R ¹ _a SiO (4-), which represents the shell of the polyorganosiloxane of the core-shell body.
In a) / 2, R ¹ bonded to a silicon atom is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group.

The unsubstituted monovalent hydrocarbon group includes, for example, a linear or branched alkyl such as methyl, ethyl, propyl, hexyl, octyl, decyl, hexadecyl, octadecyl and the like. Group, phenyl group, naphthyl group, aryl group such as xenyl group, benzyl group, β-phenylethyl group, methylbenzyl group, aralkyl group such as naphthylmethyl group, cyclohexyl group,
And a cycloalkyl group such as a cyclopentyl group.

On the other hand, the substituted monovalent hydrocarbon group includes
In general, a group in which a hydrogen atom of the unsubstituted monovalent hydrocarbon group is substituted with a halogen atom such as fluorine or chlorine, for example, a 3,3,3-trifluoropropyl group, a 3-fluoropropyl group, etc. No. Further, as a modification of the substituted monovalent hydrocarbon group, an organic functional group containing at least one of an oxygen atom and a nitrogen atom or a group containing an ethylenically unsaturated group may be mentioned. In particular, a cosmetic composition using a colloidal silica core-silicone shell containing an organic functional group or an ethylenically unsaturated group has excellent adhesion to hair and skin. The following organic groups are exemplified as the organic functional groups.

--CH ₂ CH ₂ CH ₂ NH ₂ --CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ --CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH
₂ NH ₂

Embedded image

Embedded image

Embedded image

Embedded image —CH ₂ CH ₂ CH ₂ SH Examples of the group containing an ethylenically unsaturated group include the following organic groups. Here, n is an integer of 0 to 10.

CH ₂ ＣＨCH—O— (CH ₂ ) _n —CH ₂ ＣＨCH— (CH ₂ ) _n —

Embedded image

Embedded image Examples of the group represented by CH ₂ ＣＨCH—O— (CH ₂ ) _n — include a vinyloxyethyl group, a vinyloxyethoxyethyl group, and more preferably a vinyloxypropyl group and a vinyloxyethoxypropyl group. Also, CH
_{2 = CH- (CH 2) n} - Examples of the group represented by, homoallyl, 5-hexenyl, 7-octenyl group, more preferably a vinyl group, allyl group.

Further, in the group represented by the chemical formula 5, R ³
Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group. The groups represented by Chemical Formula 5 include a (vinylphenyl) methyl group, an isopropenylvinylphenyl group, a 2- (vinylphenoxy) ethyl group, a 3- (vinylbenzoyloxy) propyl group, and a 3- (isopropenylbenzoyloxy) group. ) A propyl group, more preferably a vinylphenyl group, a 1- (vinylphenyl) ethyl group, a 2- (vinylphenyl) ethyl group.

In the group represented by Chemical formula 6, R ⁵ is an alkylene group having 1 to 6 carbon atoms, —O—, —S—, —N
(R ⁶ ) a group represented by R ⁷ —, wherein R ⁶ has 1 to 1 carbon atoms.
6, a hydrocarbon group or a (meth) acryloyl group, R ⁷
Is an alkylene group having 1 to 6 carbon atoms. Examples of the group represented by Formula 6 include a γ-acryloxypropyl group, a γ-methacryloxypropyl group, an N, N-bis- (methacryloyl) -γ-aminopropyl group, and more preferably N-methacryloyl-N-methyl. -Γ-aminopropyl group and N-acryloyl-N-methyl-γ-aminopropyl group.

The cosmetic composition of the present invention can be generally manufactured as follows. That is, (a) colloidal silica (core component) and (b) R ² _n SiO (4-n) / 2
(Wherein R ² is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, n is a number of 0 to 3), and has 2 to 10 silicon atoms not containing a hydroxyl group. And the respective organosiloxanes are prepared. Next, by conducting polycondensation of the organosiloxane with the colloidal silica in an aqueous medium in the presence of a surfactant,
An emulsion of a colloidal silica core-silicone shell is prepared.

In preparing the above-mentioned colloidal silica core-silicone shell emulsion, acidic colloidal silica is used to keep the colloidal silica in a stable state.
Anionic surfactant, alkaline colloidal silica
Select a combination of cationic surfactants. Also,
The amount of water used in this emulsification / emulsification is the total amount of the colloidal silica component and the organosiloxane component,
50 to 500 parts by weight, preferably 100 to 30 parts by weight per 100 parts by weight
0 parts by weight, and the solid concentration of the emulsion system is 20-70.
%, Preferably 30 to 60% by weight. Further, the temperature for forming a colloidal silica core-silicone shell (such as a condensation reaction) is about 5 to 100 ° C. The organosiloxane component forming the silicone shell may be added with a crosslinking agent such as a silane having a functional group in order to improve the strength of the shell.

The colloidal silica core / silicone shell emulsion prepared above exhibits an acidic or alkaline property, and is neutralized by adding an alkali or acid to maintain long-term stability. Here, examples of the alkaline neutralizing agent include sodium hydroxide, thorium carbonate, thorium hydrogen carbonate, and triethanolamine, and examples of the acidic neutralizing agent include hydrochloric acid, sulfuric acid, nitric acid,
Acetic acid, oxalic acid and the like can be mentioned.

After that, various volatile or non-volatile oils, surfactants, lubricants, preservatives, antioxidants, fragrances, powders and the like used in cosmetics are added according to the intended use. It is optionally blended to produce the required cosmetic composition.
That is, the colloidal silica core-silicone shell is selected in a weight ratio of about 0.5 to 50%, and depending on the application, an oil agent, a surfactant, a lubricant, a preservative, an antioxidant, a fragrance, a powder, etc. And the like are appropriately selected to prepare a desired cosmetic composition.

Specific examples of the polyorganosiloxane as a raw material component of the polyorganosiloxane forming the shell of the core-shell body used in the present invention include the following.

Hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclletetrasiloxane, 1,3, 5,7-tetrabenzyltetramethylcyclotetrasiloxane, 1,3,5,7-
Cyclic compounds such as tris- (3,3,3-trifluoropropyl) trimethylcyclotetrasiloxane may be mentioned, and these may be used alone or as a mixture of two or more.

The following silanes are used as the silane compound used for introducing an organic functional group or a group containing an ethylenically unsaturated group.

As the silane compound containing an organic functional group,
3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-
Aminopropyltrimethoxysilane, N-triethylenediaminepropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trifluoropropyltrimethoxysilane And 3-carboxypropylmethyldimethoxysilane. These may be used alone or in a mixture of two or more.

Examples of the silane compound containing an ethylenically unsaturated group include 3-acryloxypropyltriethoxysilane,
3-methacryloxypropyltrimethoxysilane, (vinyloxypropyl) methyldimethoxysilane, (vinyloxyethoxypropyl) methyldimethoxysilane, P-vinylphenylmethyldimethoxysilane, 1- (m-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethyldimethoxysilane, 3- (p-vinylphenoxy) propylmethyldimethoxysilane, 1- (p-
Vinylphenyl) ethylmethylmethoxysilane, 1- (o-
Vinylphenyl) -1,1,2-trimethyl-2,2-dimethoxydisilane, m-vinylphenyl [(3-triethoxysilyl) propyl] diphenylsilane, [3- (P-isopropenylbenzoylamino) propyl] diphenyl Dipropoxysilane, N-methacryloyl-N-methyl-3-aminopropylmethyldimethoxysilane, N-acryloyl-N-methyl-3-aminopropylmethyldimethoxysilane, N, N-
Bis (methacryloyl) -3-aminopropyltrimethoxysilane, N, N-bis (acryloyl) -3-aminopropylmethyldimethoxysilane, N-methacryloyl-N-methyl-3-aminopropylphenyldiethoxysilane, 1-methacryl Roxypropyl-1,1, -3-trimethyl-3,3-dimethoxydisiloxane, vinylmethyldimethoxysilane, vinylethyldiisopropoxysilane, allylmethyldimethoxysilane, 5-hexenylmethyldiethoxysilane,
3-octenylethyldiethoxysilane and the like,
These may be used alone or in a mixture of two or more.

On the other hand, organosiloxanes containing organic functional groups include trimethyltriphenylcyclotrisiloxane, tris (3,3,3-trifluoropropyl) trimethyltriphenylcyclotrisiloxane, 1,3,5,7- Tetra (3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [N- (2-aminoethyl) -3-
Aminopropyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-mercaptopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-glycidoxypropyl) tetramethylcyclo Examples thereof include cyclic siloxanes such as tetrasiloxane, which may be used alone or in a mixture of two or more. Further, organosiloxanes containing an ethylenically unsaturated group include 1,3,5,7-tetra (3-methacryloxypropyl) tetramethylcyclotetrasiloxane and 1,3,5,7-tetra (3-
Acryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-carboxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (vinyloxypropyl) tetramethylcyclotetrasiloxane 1,3,5,7-tetra (vinyloxyethoxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (P-vinylphenyl) tetramethylcyclotetrasiloxane, 1,3,5,7 -Tetra [1- (m-vinylphenyl) methyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [2- (p-vinylphenyl) ethyl] tetramethylcyclotetrasiloxane, 1,3,5 , 7-tetra [3- (p-vinylphenoxy) propyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [3- (p-vinylbenzoyloxy) propyl] tetramethylcyclotetrasiloxane,
1,3,5,7-tetra [3- (p-isopropenylbenzoylamino) propyl] tetramethylcyclotetrasiloxane,
1,3,5,7-tetra (N-methacryloyl-N-methyl-3-aminopropyl) tetramethylcyclotetrasiloxane,
3,5,7-tetra (N-acryloyl-N-methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,
7-tetra [N, N-bis (methacryloyl) -3-aminopropyl] tetramethylcyclotetrasiloxane, 1,3,5,7-
Tetra [N, N-bis (acryloyl) -3-aminopropyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, octavinylcyclotetrasiloxane, 1,3,5- Trivinyltrimethylcyclotrisiloxane, 1,3,5,7-tetraallyltetramethylcyclotetrasiloxane, 1,3,5,7-tetra (5-hexenyl) tetramethylcyclotetrasiloxane, 1,3,5,7 Cyclic and straight-chain siloxanes such as -tetra (7-oxenyl) tetramethylcyclotetrasiloxane and 1- (p-vinylphenyl) -1,1-diphenyl-3-diethoxydisiloxane; Or 2
It may be used in a mixed system of more than one species.

The above-mentioned organosiloxane containing an organic functional group or an ethylenically unsaturated group includes, among others,
Linear or branched organosiloxane oligomers can also be used. In the case of this organosiloxane oligomer, the molecular chain terminal group is not particularly limited, but from the viewpoint of easy handling and introduction of an organic functional group into the resulting organosiloxane, the molecular chain terminal is an organic group other than a hydroxyl group, for example, an alkoxy group. Those blocked with a group, trimethylsilyl group, dimethylvinylsilyl group, methylphenylvinylsilyl group, methyldiphenylsilyl group, 3,3,3-trifluoropropyldimethylsilyl group are preferred.

In the preparation of the emulsion of the colloidal silica core-silicone shell according to the present invention, an anionic surfactant or a cationic surfactant is appropriately used as a surfactant that mainly plays a role of emulsifying. As described above, when acidic colloidal silica is used as a raw material, use of an anionic surfactant is preferable, and when alkaline colloidal silica is used as a raw material, use of a cationic surfactant is preferable.

Here, as the anionic surfactant,
Preferred are aliphatic substituted benzenesulfonic acids, aliphatic hydrogen sulfates, and mixtures of unsaturated aliphatic sulfonic acids and hydroxylated aliphatic sulfonic acids represented by the following general formulas.

R ⁸ C ₆ H ₄ SO ₃ H R ⁸ OSO ₃ H R ⁹ CH ＝ CH (CH ₂ ) _n SO ₃ H R ⁹ CH ₂ CH (OH) (CH ₂ ) _n SO ₃ H , R ⁸ has 6 to 30 carbon atoms (preferably 6 to 30 carbon atoms).
~ 18) monovalent aliphatic hydrocarbon group, R ⁹ carbon atom 1 ~
30 (preferably 6 to 18) monovalent aliphatic hydrocarbon groups, n
Is an integer having 6 to 30 carbon atoms.

R ⁸ and R ⁹ are, for example, hexyl, octyl, decyl, dodecyl, cetyl, stearyl, myryl, oleyl, nonenyl, octynyl, phytyl, pentadecadiyl Enyl group and the like. Examples of the anionic surfactant having an R ⁸ group include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, octyl sulfate, lauryl sulfate, oleyl sulfate, and cetyl sulfate. . Examples of the anionic surfactant having an R ⁹ group include tetradecenesulfonic acid and hydroxytetradecanesulfonic acid.

In addition, among the anionic surfactants represented by the above general formula, anionic surfactants having weak catalytic action, for example, sodium dodecylbenzenesulfonate,
Sodium octylbenzenesulfonate, ammonium dodecylbenzenesulfonate, sodium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium tetradecenesulfonate, sodium hydroxytetradecenesulfonate, etc. can be used in combination with a polymerization catalyst. .

Here, the polymerization catalyst used in combination is usually a catalyst used for the polymerization of low molecular weight organosiloxanes, for example, aliphatic substituted benzenesulfonic acid, aliphatic hydrogen sulfates, unsaturated aliphatic sulfonic acid and water. Examples thereof include a mixture with an oxidized aliphatic sulfonic acid, hydrochloric acid, sulfuric acid, and phosphoric acid. These acidic catalysts are preferred, but not limited thereto. That is, any catalyst that can polymerize a low molecular weight organosiloxane in the presence of water can be used in combination.

The anionic surfactant is not limited to those represented by the above general formula. For example, polyoxyethylene (4) lauryl ether sulfate, polyoxyethylene (13) cetyl ether sulfate, polyoxyethylene (6) stearyl ether sulfate, polyoxyethylene (4) sodium lauryl ether sulfate, polyoxyethylene (4) octyl phenyl Polyoxyethylene alkyl ether sulfates such as ammonium ether sulfate or salts thereof, polyoxyethylene (3) lauryl ether carboxylic acid, polyoxyethylene (3) stearyl ether carboxylic acid, polyoxyethylene (6) sodium lauryl ether carboxylate, poly One or a mixture of two or more of polyoxyethylene alkyl ether carboxylate such as sodium oxyethylene (6) octyl ether carboxylate or a salt thereof can also be used.

The amount of the anionic surfactant used depends on the amount of the emulsified
The total amount of colloidal silica forming the core to be emulsified and organosiloxane forming the shell, for example, 1
0.5 to 20 parts by weight (preferably 0.5 to 10 parts by weight)
Parts by weight). Here, when the amount is less than 0.5 part by weight, the stability of the resulting emulsion is inferior and the possibility of separation is recognized.
On the other hand, if it exceeds 20 parts by weight, the resulting emulsion thickens, and the fluidity may decrease. When a polymerization catalyst is used in combination, the amount of the polymerization catalyst used is preferably about 0.05 to 10 parts by weight based on the total amount of colloidal silica forming the core and organosiloxane forming the shell, for example, 100 parts by weight.

On the other hand, as the cationic surfactant, a general formula

Embedded image (Wherein R ¹⁰ is an aliphatic monovalent hydrocarbon group having 6 or more carbon atoms, preferably 8 to 18 carbon atoms, R ¹¹ , R ¹² ,
R ¹³ is a monovalent organic group, and X is a hydroxyl group, a chlorine atom or a bromine atom).

Where R^TenFor example, hexyl
Group, octyl group, decyl group, dodecyl group, cetyl group,
Tearyl, myrisyl, oleyl, nonenyl,
Butynyl, phytyl, pentadecadienyl, etc.
No. Also, R¹¹, R ¹², R¹³Is the same or different
Species of monovalent organic groups such as methyl, ethyl,
Alkyl groups such as propyl group, vinyl group, allyl group, etc.
Alkenyl, phenyl, xenyl, naphthyl
Aryl groups such as cyclohexyl groups
And a kill group.

Examples of the quaternary ammonium surfactant include lauryltrimethylammonium hydroxide, stearyltrimethylammonium hydroxide, dioctyldimethylammonium hydroxide, distearyldimethylammonium hydroxide, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and the like. Cetyltrimethylammonium chloride, dicocoyldimethylammonium chloride, distearyldimethylammonium chloride, benzalkonium chloride,
Stearyl dimethyl benzyl ammonium chloride and the like can be mentioned, and these can be used alone or in a mixture of two or more.

Since the cationic surfactant has a weak catalytic action, a polymerization catalyst such as an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide may be used in combination. Is preferred.

The amount of the cationic surfactant used is as follows:
The total amount of colloidal silica constituting the core to be emulsified and emulsified and organosiloxane constituting the shell, for example, 0.5 to 50 parts by weight (preferably 0.1 to 50 parts by weight) per 100 parts by weight.
5 to 20 parts by weight). Here, when the amount is less than 0.5 part by weight, the cationicity is insufficient, and the resulting emulsion has poor stability and may be separated. On the other hand, if it exceeds 50 parts by weight, the resulting emulsion thickens, and the fluidity may decrease. When a polymerization catalyst is used in combination, the amount of the polymerization catalyst used in combination is the total amount of colloidal silica forming the core and organosiloxane forming the shell, for example,
It is preferably about 0.05 to 10 parts by weight based on 100 parts by weight.

The cosmetic composition according to the present invention comprises the above colloidal silica core-silicone shell emulsion, various volatile or non-volatile oils, surfactants, lubricants, preservatives, antioxidants, fragrances, powders It is prepared by blending components such as

The volatile or non-volatile oil agent includes linear or branched hydrocarbons, linear, branched or cyclic polydimethylsiloxane, higher alcohols,
Higher fatty acids, synthetic ester oils of alcohols and fatty acids,
Examples include 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 hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester and the like can be mentioned.

As the lubricant, sorbitol, glycerin, propylene glycol, 1,3-butylene glycol,
Maltitol, lactic acid, sodium lactate, polyethylene glycol and the like can be mentioned. Examples of the preservative include alkyl paraoxybenzoate, sodium benzoate, potassium sorbate, and phenoxyethanol. Furthermore, as antioxidants, tocopherol, lecithin, etc., and as powders, titanium oxide, zinc oxide, ultramarine, chromium oxide, iron oxide, talc, sericite, mica, kaolin, organic pigments, polymethylsilsesquioki Sun and the like.

In the preparation of the cosmetic composition, in order to improve the stability of the cosmetic composition, before emulsification / emulsification or after emulsification / emulsification of the core colloidal silica and the shell organosiloxane. Alternatively, a nonionic surfactant may be added and used in combination. When added before emulsification / emulsification,
Since the catalytic action of the anionic or cationic surfactant may be impaired, it is preferable to use the anionic or cationic surfactant in an amount of 0 to 500 parts by weight per 100 parts by weight of the anionic or cationic surfactant.

Here, nonionic surfactants include:
For example, polyoxyethylene (6) lauryl ether, polyoxyethylene (7) cetyl ether, polyoxyethylene (20) stearyl ether, polyoxyethylene
(3) octyl phenyl ether, polyoxyethylene (1
8) Nonylphenyl ether, polyethylene glycol monostearate (EO14), polyethylene glycol distearate (EO80), polyoxyethylene (20) sorbitan, polyoxyethylene (20) hydrogenated castor oil, polyoxyethylene monolaurate (20) sorbitan , Polyoxyethylene monobalmitate (20) sorbitan, polyoxyethylene monostearate (6) sorbitan, polyoxyethylene trioleate (20) sorbitan, polyoxyethylene tetraoleate (40) sorbit, polyoxyethylene monooleate (15) glyceryl, polyoxyethylene monostearate (15) glyceryl, sorbitan monobalmitate, polyoxyethylene (10) behenyl ether, polyoxyethylene (10) phytosterol, polyoxyethylene (10) polyoxypropylene (4) cetyl ether, polyoxyethylene (5) stearyl amine, polyoxyethylene (8) stearyl propylenediamine,
Polyoxyethylene (5) cetyl ether sodium phosphate and the like. Among these nonionic surfactants, those having an HLB of 6 to 20 are preferably used in combination because the stability of the obtained core-shell emulsion is good.

The cosmetic composition according to the present invention comprises, as an essential component, a colloidal silica as a core, and a shell in which the core is covered with a silicone shell via a siloxane bond. Therefore, with good adhesion to the makeup object, there is no stickiness, a supple and smooth feel is exhibited, and a film excellent in strength, oil resistance, sweat resistance, water resistance, flexibility, etc. is easily formed. . For example, in the case of a hair cosmetic composition, the colloidal silica core-silicone shell facilitates good haircuts and gives dry hair a supple and smooth feel. In the case of the cosmetic composition for skin and make-up, the colloidal silica core-silicone shell not only gives the skin a pleasant touch, but also has excellent oil resistance, sweat resistance, water resistance, etc. Presents long-lasting makeup.

Specific examples of the cosmetic composition according to the present invention include liquid cosmetics such as lotions, essences, and hair styling solutions, emulsified cosmetics such as emulsions, creams, hair creams, and liquid foundations, and lipsticks and foundations. -Eyeliners, mascaras, solid whites, blushes, etc., kneaded or solid cosmetics, shampoos, rinses, conditioners, etc., detergents.

[0051]

Embodiments of the present invention will be described below.

Parts and% in Examples are parts by weight and% by weight unless otherwise specified.

The average particle size of the colloidal silica and the colloidal silica core / silicone shell used as a raw material is determined by a laser particle size analysis system employing a dynamic light scattering method.
It was measured with LPA-3000S / 3100 (manufactured by Otsuka Electronics Co., Ltd.).

When the colloidal silica core-silicone shell is regarded as a graft polymer, in other words, the graft ratio and the graft efficiency when the colloidal silica core is a trunk polymer and the silicone shell is a branch polymer are as follows. I asked for it. That is, a certain amount (Y) of the colloidal silica core-silicone shell (dry matter) obtained by drying the emulsion containing the colloidal silica core-silicone shell under reduced pressure at 40 ° C./0.5 mmHg for 5 hours is introduced into cyclohexane. Then, set on a shaker and shake for 24 hours. By this shaking, the free polyorganosiloxane is dissolved in cyclohexane,
Using a centrifuge, centrifuge at 23,000 rpm for 30 minutes to collect insolubles. Next, use a vacuum dryer at 120 ℃, 1
The weight (M) of the insoluble content obtained by drying for a time was measured, and the graft ratio and the graft efficiency were calculated by the following formulas.

[0055]

(Equation 1)

(Equation 2) The shell ratio of the colloidal silica core-silicone shell was calculated by the following procedure. The non-volatile content [%] was determined by measuring three samples of 2 g each at 105 ° C.
This is the average of the values obtained when heating is performed for an hour.

Calculation of Effective Colloidal Silica [Parts] The effective amount of colloidal silica dispersion [parts] × the effective amount of colloidal silica [%] is determined. Calculation of theoretical nonvolatile content [%] {(effective amount of colloidal silica [parts] + amount of organosiloxane [parts] + amount of emulsifier [parts]) / total raw material parts [parts]} × 100 amount of unpolymerized organosiloxane [ Parts) (total raw material parts [parts] × theoretical nonvolatile content [%] − nonvolatile content [%]) / 100 Calculation of the amount of polymerized organosiloxane [parts] The amount of organosiloxane used [parts] −unpolymerized organosiloxane Amount [parts] Calculation of polymerization rate Amount of polymerized organosiloxane [parts] / Amount of organosiloxane used [parts] Calculation of shell part ratio Amount of polymerized organosiloxane [parts] / (amount of polymerized organosiloxane [parts] + effective amount of colloidal silica] [Part]) × 1
00

Reference Example 1 (Preparation of polyorganosiloxane emulsion (E-1)) Acid colloidal silica, Snowtex OL-40 (manufactured by Nissan Chemical Industries, Ltd., average particle diameter 84 nm, SiO ₂ 40.8%,
_{Na 2 O 0.0049%, pH 2.3} ; silica -1 for short) 500 parts,
500 parts of ion-exchanged water, n-dodecylbenzenesulfonic acid (manufactured by Nissan Chemical Industries, Ltd., Soft Oarai 5S; abbreviated as emulsifier 1) was mixed with 8.2 parts of octamethylcyclotetrasiloxane (abbreviated as b-1). ) 204 parts were added, and the mixture was preliminarily stirred by a homomixer. And then to the homogenizer
The emulsion was emulsified and dispersed by passing twice at a pressure of 300 kgf / cm ² .

Next, the emulsified / dispersed liquid was transferred into a separable flask equipped with a condenser, a nitrogen gas inlet and a stirrer, heated at 85 ° C. for 5 hours while stirring and mixing, and then cooled at 5 ° C. for 48 hours. To carry out polymerization. Next, an aqueous solution of sodium carbonate was added to the separable flask to neutralize the polyorganosiloxane-based emulsion to pH 7.
The obtained polyorganosiloxane emulsion
The nonvolatile content of (E-1) at 105 ° C for 3 hours is 34.2%,
The conversion of octamethylcyclotetrasiloxane is
99.4%.

Further, when the particle size was analyzed by a laser particle size analysis system, the monodisperse particle size distribution having a peak at around 84 nm of the average particle size of the colloidal silica of the material completely disappeared, and the particle size distribution reached around 153 nm. A monodisperse particle size distribution with a peak appeared newly. When observed with an electron microscope, only the silicone particle image was confirmed, and no colloidal silica particle image of the material was observed.
From these facts, the non-volatile content of the polyorganosiloxane emulsion (E-1) was changed to the colloidal silica core-
It was found to be a silicone shell.

On the other hand, a part of the polyorganosiloxane-based emulsion (E-1) was poured into a large amount of acetone to precipitate a colloidal silica core-silicone shell body, which was collected by filtration. After drying for an hour, a colloidal silica core-silicone shell aggregate was obtained. Then, when this aggregate was regarded as a graft polymer, the graft ratio and the graft efficiency were 41.7%, respectively.

Reference Examples 2 to 5 (Preparation of Polyorganosiloxane Emulsions (E-2 to E-5)) In the same manner as in Reference Example 1, except that the composition ratio of each material was changed. Under the conditions, four types of polyorganosiloxane emulsions (E-2, E-3, E-4, E-5) were prepared.

Each polyorganosiloxane emulsion
When (E-2, E-3, E-4, E-5) were examined for their properties by particle size analysis based on dynamic scattering and electron microscopy, they had a monodisperse particle size distribution. The colloidal silica core-silicone shell was confirmed.

Further, with respect to each of these colloidal silica core-silicone shell bodies, as in Reference Example 1,
The measurement results of the nonvolatile content, the polymerization rate of the siloxane as the material, and the average particle size are shown in Table 1 together with the case of Reference Example 1.

Reference Examples 6, 7 (Polyorganosiloxane emulsions (E-6, E-7))
In Reference Example 1, 3-aminopropylmethyldimethoxysilane (abbreviated as b-2) or 4-ethenylphenylmethyldimethoxysilane (abbreviated as b-3) was added to octamethylcyclotetrasiloxane (abbreviated as b-1). Except that 2.1 parts were previously added and blended, two kinds of polyorganosiloxane emulsions were prepared under the same conditions as in Reference Example 1.
(E-6, E-7) were prepared.

Each polyorganosiloxane emulsion
The properties of (E-6, E-7) were examined by particle size analysis based on dynamic scattering and electron microscopic observation. As a result, a colloidal silica core-silicone shell having a monodisperse particle size distribution was obtained. It was confirmed that there was.

Further, with respect to each of these colloidal silica core-silicone shell bodies, as in Reference Example 1,
Table 1 also shows the results of measuring the nonvolatile content, the polymerization rate of the siloxane as the material, the average particle size, and the like.

Reference Example 8 (Preparation of polyorganosiloxane emulsion (E-8)) Alkaline colloidal silica, Snowtex 2OL
(Nissan Chemical Industries, Ltd., average particle size 72nm, SiO ₂ 20.4
_{%, Na 2 O 0.0022%,} pH 9.9; abbreviated as silica -2) 1000
Part, 30% cetyltrimethylammonium chloride aqueous solution (manufactured by Kao Corporation, Coatamine 60W, active ingredient 30%; abbreviated as emulsifier 2) 54.7 parts, polyoxyethylene (18) nonylphenyl ether (manufactured by Nikko Chemicals Co., Ltd., NIKKOL) NP-
18TX, HLB19; abbreviated as emulsifier 3) To a mixed system of 32.8 parts and potassium hydroxide 6.0 parts, 204 parts of octamethylcyclotetrasiloxane (abbreviated as b-1) was added and premixed with a homomixer. . Thereafter, the mixture was passed twice through a homogenizer at a pressure of 300 kgf / cm ² to be emulsified and dispersed.

Next, the emulsified / dispersed liquid was transferred into a separable flask equipped with a condenser, a nitrogen gas inlet and a stirrer, heated at 85 ° C. for 5 hours while stirring and mixing, and then cooled at 5 ° C. for 48 hours. To carry out polymerization. Next, an aqueous solution of acetic acid was added to the separable flask to neutralize the polyorganosiloxane emulsion to pH 7. 105 of the polyorganosiloxane emulsion (E-8) thus obtained.
The nonvolatile content at 3 ° C. × 3 hours was 35.5%, and the conversion of octamethylcyclotetrasiloxane was 98.5%.

The properties of the polyorganosiloxane emulsion (E-8) were examined by particle size analysis based on dynamic scattering and observation with an electron microscope. As a result, a colloidal silica core having a monodispersed particle size distribution was obtained. -It was confirmed that it was a silicone shell.

Further, with respect to each of these colloidal silica core-silicone shell bodies, as in Reference Example 1,
Table 1 also shows the measurement results of the nonvolatile content, the polymerization rate of the siloxane as the material, the average particle diameter, and the like.

Reference Example 9 (Preparation of polyorganosiloxane emulsion (E-9)) n-dodecylbenzenesulfonic acid (abbreviated as emulsifier 1)
204 parts of octamethylcyclotetrasiloxane (abbreviated as b-1) was added to a mixture of 4.1 parts and 337 parts of ion-exchanged water, and the mixture was preliminarily stirred by a homomixer. afterwards,
Pass twice through the homogenizer at a pressure of 300 kgf / cm ² ,
Emulsified and dispersed.

Next, the emulsified / dispersed liquid was transferred into a separable flask equipped with a condenser, a nitrogen gas inlet and a stirrer, heated at 85 ° C. for 5 hours while stirring and mixing, and then cooled at 5 ° C. for 48 hours. To carry out polymerization. Thereafter, a 10% aqueous solution of sodium carbonate was added to the separable flask to neutralize the polyorganosiloxane emulsion to pH 7.

The thus obtained polyorganosiloxane-based emulsion (E-9) had a nonvolatile content of 34.4 at 105 ° C. × 3 hours.
%, Average particle diameter was 260 nm. Further, the polyorganosiloxane emulsion (E-9) was broken with isopropyl alcohol, and the polyorganosiloxane polymer was taken out and subjected to GPC (molecular weight) measurement. As a result, the weight average molecular weight was 520,000.

Table 1 shows the results of measurement and evaluation of the polyorganosiloxane-based emulsion (E-9), in the same manner as in Reference Example 1, such as the degree of polymerization of siloxane and the particle size distribution of the material. Shown.

Reference Example 10 (Preparation of Polyorganosiloxane Emulsion (E-10) by Mixing Polyorganosiloxane Emulsion and Colloidal Silica) Polyorganosiloxane emulsion (E-10) produced under the same conditions as in Reference Example 9 -9) to 5
45 parts were prepared and added to Snowtex OL-40 (manufactured by Nissan Chemical Industries, Ltd., average particle diameter 84 nm, SiO ₂ 40.8%, Na ₂ O
0.0049%, pH 2.3; abbreviated as silica-1) 500 parts, ion-exchanged water 500 parts, sodium n-dodecylbenzenesulfonate (manufactured by Lion Corporation, Lipon LS-250; abbreviated as emulsifier 4) 4.1 parts and ion exchange The mixed system to which 163 parts of water was added was placed in a separable flask equipped with a stirrer, and stirred at room temperature for 15 minutes to prepare a polyorganosiloxane-based emulsion (E-10).

The nonvolatile content of this polyorganosiloxane emulsion (E-10) at 105 ° C. for 3 hours was 32.6%. As a result of the particle size analysis, the peak having a particle size of 84 nm due to colloidal silica and A peak with a particle diameter of 260 nm due to the organosiloxane emulsion was confirmed (non-monodispersion).

Further, with respect to this polyorganosiloxane emulsion (E-10), the results of measurement and evaluation of the polymerization rate and average particle diameter of the siloxane as the raw material are shown in Table 1 in the same manner as in Reference Example 1. Show.

[Table 1]

Examples 1 to 6 and Comparative Examples 1 to 4 (Hair setting composition) The polyorganosiloxane emulsion (E
-1 to E-10), hydroxyethylcellulose, ethyl alcohol, fragrance and ion-exchanged water were selected in the composition ratio (%) shown in Table 2, and these were stirred and mixed to prepare 10 types of hair set compositions.

[Table 2]

The results of test evaluation of these ten hair set compositions according to the following evaluation methods and evaluation criteria are shown in Table 2. "Suppleness" Spray 4g of hair set composition evenly from a distance of 20cm to 2g of hair 25cm in length and then coat the hair with a commercially available comb before drying. It was dried for 60 minutes and evaluated according to the following evaluation criteria. …: There is no stiffness when touched by hand, and the feel is natural. Δ: There is slight stiffness when touched by hand. ×: Roughness is severe when touched by hand, giving a hard feel. "Smoothness (combability)" After uniformly spraying and applying 4 g of the hair setting composition from a distance of 20 cm to 2 g of hair having a length of 25 cm, the hair is dried with warm air at 40 ° C for 60 minutes, Using a commercially available comb, the condition of the comb was evaluated according to the following evaluation criteria. …: There is no snag, and the comb passes smoothly. △: Comb can be passed though there is a catch. ×: Comb does not pass. “Set holding power” After uniformly spraying and applying 4 g of the hair setting composition from a distance of 20 cm to 2 g of hair having a length of 25 cm, the hair was turned to an outer diameter of 1.2 g.
It was wound on a curler of cm and dried with warm air at 40 ° C. for 60 minutes. Then, remove the hair from the curlers, the temperature 30 ° C., and the length L ₁ immediately suspended vertically in 80% relative humidity atmosphere, 1
The time allowed length after L ₂ was calculated measured curl retention from the following equation. Curl retention of 60% or more was evaluated as acceptable (合格), and less than 60% was evaluated as unacceptable (x). Curl Retention (%) = (25-L 2) / (25-L 1) × 1
00

Examples 7 to 12 and Comparative Examples 5 to 8 (Foundation compositions) The above-prepared polyorganosiloxane-based emulsions (E
-1 to E-10), liquid paraffin, paraffin wax, palmitic acid, propylene glycol, polyoxyethylene sorbitan monostearate, diethanolamine,
Talc, iron oxide, fragrance, and ion-exchanged water were selected in the composition ratio (%) shown in Table 3, and these were stirred and mixed to prepare 10 types of foundation compositions.

[Table 3]

The results of test evaluation of these 10 types of foundation compositions according to the following evaluation methods and evaluation criteria are shown in Table 3. "Adhesiveness" After the foundation composition was applied to the wrist and dried, the bending operation was performed 30 times, the state was observed, and the evaluation was made according to the following evaluation criteria. ◎… Very good ○… Good △… Normal ×… Poor “Water resistance” An appropriate amount of the foundation composition was collected on a nylon resin plate surface, thin-filmed with a 6-mil doctor blade, dried, and then ion-exchanged. Immerse in water and shake. From the peeling time of the coating at this time, evaluation was made according to the following evaluation criteria. ◎: Very good ○: Good △: Normal ×: Poor “Oil resistance, sweat resistance” An appropriate amount of the foundation composition was sampled on a nylon resin plate surface, thin-coated with a 6-mil doctor blade, and dried. Thereafter, artificial sebum was further applied with a 6-mil doctor blade, and after a certain period of time, the sample was collected with a finger, and the state was evaluated according to the following evaluation criteria. ◎… Very good ○… Good △… Normal ×… Poor “Sensory evaluation” Actually used by 30 female panelists, “Ease of application”, “Discomfort of makeup film”, “Make up”, “Make up” Sensory evaluation was performed on four items of "naturalness of collapse". In other words, each panelist is very good about each item.
3 points for good, 3 points for good, 2 points for bad, and 1 point for bad, and the following evaluation criteria were evaluated from their average. ◎: 3.5 or more on average ○: 2.5 to less than 3.5 △: 1.5 to less than 2.5 ×: Less than 1.5 on average

Example 13 and Comparative Example 9 (Shampoo composition) The polyorganosiloxane emulsion (E-1) or the polyorganosiloxane emulsion (E-10) was added to 3.0.
%, Polyoxyethylene lauryl ether 15.0%, lauric acid diethanolamide 5.0%, fragrance 0.2%, and ion-exchanged water 76.8% were stirred and mixed to prepare two types of shampoo compositions. Shampoo composition containing polyorganosiloxane emulsion (E-1) as one component (Example 1)
In 3), excellent style holding formability and a smooth feel could be imparted, and the stability was also good. In contrast, polyorganosiloxane emulsions (E
Shampoo composition containing -10) as one component (Comparative Example 9)
Although a slightly good degree of smooth feel could be imparted, the style retention formability and stability were insufficient.

Example 14, Comparative Example 10 (Mascara composition) A polyorganosiloxane emulsion (E-1) or a polyorganosiloxane emulsion (E-10) was added to 50.0%
%, Polyoxyethylene sorbitan monooleate 2.0
%, Polyethylene glycol 5.0%, ethyl alcohol
2.0%, iron oxide 13.0%, fragrance 0.3% and ion exchange water
27.7% was stirred and mixed to prepare two types of shampoo compositions.

Polyorganosiloxane emulsion
Mascara composition containing (E-1) as one component (Example 14)
Showed excellent water resistance and oil resistance as well as good usability and finished state. On the other hand, the mascara composition containing one component of the polyorganosiloxane emulsion (E-10) (Comparative Example 10) was excellent in water resistance and oil resistance, but poor in usability and finished state. there were.

Example 15 and Comparative Example 11 (Eyeliner composition) A polyorganosiloxane-based emulsion (E-1) or a polyorganosiloxane-based emulsion (E-10) was used at 25.0%.
%, Beeswax 8.0%, polyoxyethylene sorbitan monostearate 2.0%, polyoxyethylene oleyl ether 1.0%, 1,3-butylene glycol 5.0%, iron oxide 10.0
%, Perfume 0.2% and ion-exchanged water 48.8% were stirred and mixed to prepare two types of eyeliner compositions.

Polyorganosiloxane emulsion
Eyeliner composition containing (E-1) as one component (Example 1
5) was resistant to friction, water and oil, and had little sticky feeling after application. On the other hand, the eyeliner composition containing a polyorganosiloxane-based emulsion (E-10) as one component (Comparative Example 11) had some resistance to friction, water and oil, but the silicone was not coated after application. It bleed and was very sticky. It should be noted that the present invention is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the invention. For example, a colloidal silica, an organosiloxane, a crosslinkable organosilane, or the like is replaced with another colloidal silica, an organosiloxane, or a crosslinkable organosilane to prepare a similar core-shell body to obtain a cosmetic composition. .

[0087]

As can be seen from the above examples, according to the present invention, a film having high adhesion to hair and skin, having no stickiness, and having a supple and smooth feel can be formed. . In other words, the inclusion of a silica core-silicone shell formed by bonding a polyorganosiloxane with a siloxane bond to colloidal silica as a film-forming component provides excellent film strength, oil resistance, sweat resistance, water resistance, and flexibility. A coated film is easily formed. As a result, a hair cosmetic composition having good set holding power while having a non-sticky, supple and smooth feel, or a skin with good oil resistance, sweat resistance, water resistance, and good make-up And a makeup cosmetic composition.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C083 AB032 AB171 AB172 AB232 AB312 AB432 AC012 AC022 AC102 AC122 AC182 AC242 AC442 AC542 AC642 AC692 AC792 AC912 AD042 AD172 AD282 CC01 CC12 CC14 CC32 CC38 EE06 EE07 EE28

Claims (1)

[Claims] And 1. A (A) Core 80-5 wt% of colloidal silica, (B) the average compositional formula _{^{R 1 a SiO (4-a}} ) / 2 ( wherein R ¹ is a hydrogen atom or a substituted or unsubstituted A monovalent hydrocarbon group, wherein a is a number of 1.80 to 2.20), wherein a colloidal silica core-silicone shell comprising 20 to 95% by weight of a polyorganosiloxane shell is contained as a film-forming component. Cosmetic composition.