JPH08133926A - Composition for cosmetic - Google Patents

Abstract

PURPOSE: To obtain a cosmetic composition having excellent compatibility to skin, slight feeling of physical disorder, excellent water repellency, water resistance and durability by combining a cosmetic base component with a polysiloxane group-containing block copolymer. CONSTITUTION: This cosmetic composition is obtained by using both a base component for cosmetic such as vaseline, lanolin, sericin, squalane or liquid paraffin and a polysiloxane group-containing block copolymer. The block copolymer comprises a polysiloxane group-containing polymer part and a polymer part not containing the polysiloxane group. A polymer part is made from a monomer of formula I or formula II [R1 is H or methyl; R2 is methyl, ethyl, phenyl or a group of formula III (R5 is H, phenyl, etc.; R6 is ethyl or phenyl; (m) is >=1); R3 is H or phenyl; R4 is methyl or phenyl; (n) is >=1] and a vinyl type monomer. The cosmetic composition is applicable as a make-up cosmetic, a foundation cosmetic, a face washing cosmetic or a pack.

Description

Detailed Description of the Invention

[0001]

This invention relates to a foundation,
The present invention relates to a cosmetic composition used as an eye shadow, a milky lotion or the like. Specifically, it has a high affinity for skin,
In addition, the present invention relates to a cosmetic composition having less discomfort and exhibiting high water repellency, and maintaining this property for a long time.

[0002]

2. Description of the Related Art Conventionally, many powders have been used as cosmetic materials. Examples of inorganic powders include natural minerals such as talc, sericite, muscovite, and fine particle powders of metal oxides such as titanium oxide, lead oxide, and zinc oxide.

On the other hand, examples of organic powders include fine powders of natural organic substances such as cellulose and silk. However, in recent years, a large number of various synthetic resins finely divided and finely divided by a special method have been synthesized, and they are actively used for cosmetics.

For example, various (meth) acrylic acid ester polymers obtained by polymerizing monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate, styrene-divinylbenzene copolymers, Examples of the fine particle powder include ethylene-vinyl acetate copolymers, vinyl chloride-vinyl acetate copolymers, various nylon-based polymers, and polymers such as polytetrafluoroethylene and polyethylene (JP-A-57- 98205).

Powders synthesized from these organic polymer compounds are relatively easy to make the particle size and shape uniform in the synthesis stage as compared with the inorganic powders, and their specific gravity is low, so that they can be applied to the skin. The oppressive feeling of is reduced. These powders have been used in large amounts in recent years because they have such many preferable points.

[0006]

However, in the case of the above-mentioned inorganic fine particle powder, regarding the shape and size of the particles,
It has various shapes such as spherical shape, scale shape, needle shape, and amorphous shape, and has a high specific gravity. For this reason, there is a problem in that the skin does not fit well and the user feels rough during use.

Also, in the case of organic fine particle powder, since the surface of the powder does not have a strongly lipophilic group, it has a low affinity with various lipids contained in the skin and is compatible with the skin. It is bad, and improvement is desired.

Furthermore, when these inorganic and organic fine particle powders are applied to cosmetics, they do not have properties such as water resistance retention. The present invention has been made by paying attention to the problems of the conventional techniques as described above. It is an object of the invention to provide a cosmetic composition which has good compatibility with the skin, little discomfort, and excellent water repellency and water resistance.

[0009]

In order to achieve the above object, in the invention of a cosmetic composition according to claim 1, a block comprising a base component and an additive component, the additive component having a polysiloxane group. It contains a copolymer.

Further, in the invention described in claim 2, in the invention described in claim 1, the block copolymer is composed of a polymer portion containing a polysiloxane group and a polymer portion not containing a polysiloxane group. The polymer portion containing a polysiloxane group is one or more kinds of monomers represented by the following general formula (I) or (II), and one or more kinds of vinyl type monomers. The polymer portion containing no polysiloxane group is formed of one or more vinyl type monomers.

The present invention will be described in detail below. The cosmetic composition of the present invention comprises a base component for cosmetics and an additive component. As the base component, petrolatum, lanolin, ceresin, microcrystal wax, carnauba wax, candelilla wax, higher fatty acids, higher alcohols, solids, semisolid oils; squalane, liquid paraffin, ester oil, diglyceride, triglyceride,
A fluid oil such as silicone oil is used.

In the present invention, a block copolymer is used as one of the additional components. The block copolymer is composed of a polymer portion containing a polysiloxane group and a polymer portion formed of a vinyl-type monomer and not containing the polysiloxane group. The polymer part containing a polysiloxane group has properties such as lipophilicity and low friction property, and when the cosmetic composition is used, this polymer part is oriented on the surface, and is well-fitted to the skin. And, it exerts the function of eliminating discomfort. In addition, the polymer portion containing the polysiloxane group enhances the water repellency and water resistance of the cosmetic composition. On the other hand, the polymer portion containing no polysiloxane group, which is formed of a vinyl-type monomer, has an affinity with the cosmetic base material and improves the retention of performance such as water repellency and water resistance.

R ₂ , R ₃ and R ₄ in the general formulas (I) and (II) of the monomer forming this block copolymer may be the same among the substituents defined above, It can be different. Moreover, in order to effectively exhibit the function of the polysiloxane group, it is preferable that the polysiloxane group is branchedly bonded to the block copolymer portion.

The polysiloxane group introduction method includes an ionic polymerization method and a polymer reaction method. In consideration of the ease of adjusting the polysiloxane group introduction amount and the ease of synthesis, a radical polymerizable functional group is selected. It is preferable to use the polysiloxane having. As the polysiloxane having a radically polymerizable functional group, the polysiloxane represented by the general formula (I) or (II) is suitable.

The polysiloxane represented by the general formula (I) can be obtained as a commercial product. For example, product names FM0711, FM0 715, FM0721, FM
0725 (manufactured by Chisso Corporation) and the like correspond to this compound.

The polysiloxane of the general formula (I) can be obtained by a generally known reaction. That is, 2 moles of the monomer represented by the following chemical formula 5 is reacted in the temperature range of room temperature to about 60 ° C. in the presence of a basic catalyst such as triethylamine and pyridine with respect to 1 mole of silanol polysiloxane at both ends. Is obtained by Both-end silanol polysiloxane can be obtained as a commercial item (for example, PS series manufactured by Chisso Corporation).

[0017]

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(In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents a methyl group, an ethyl group, or a phenyl group.) The monomer represented by the chemical formula 5 is (meth). It can be obtained by reacting an acrylate ester with a silicon compound. The content of the polysiloxane formed from the monomers represented by the general formulas (I) and (II) in the polysiloxane group-containing polymer portion is not particularly limited, but the performance such as water repellency and water resistance is exhibited. Therefore, it is desirable that the content be 10% by weight or more. Further, when the polysiloxane group exceeds 85% by weight in the polysiloxane group-containing polymer portion,
The tackiness of the polymer makes powdering difficult. Therefore, the preferable range of the polysiloxane group content in the polysiloxane group-containing polymer portion is 10 to 85% by weight. A more preferred range is 20 to 70% by weight.

When the number average molecular weight of the polysiloxane group in the polysiloxane group-containing polymer portion is 300 or less,
Performances such as lipophilicity, low friction, high oxygen and carbon dioxide permeability, and water repellency derived from polysiloxane groups cannot be obtained. On the other hand, when the number average molecular weight exceeds 50,000, it becomes difficult to introduce the polysiloxane group. Therefore, the number average molecular weight is preferably 500 or more and 40,000 or less,
As described above, 30,000 or less is more preferable.

Next, one of the components of the block copolymer, a vinyl-type monomer forming the polysiloxane group-containing polymer portion (hereinafter, this polymer is referred to as an affinity imparting component-1) and a block. The vinyl-type monomer (hereinafter, this polymer is referred to as the affinity-imparting component-2) that forms the polymer portion containing no polysiloxane group, which is the other component of the copolymer, is Is appropriately selected. These monomers have an affinity with the cosmetic base material, and retain the properties such as water repellency and water resistance due to the polysiloxane group for a long time. Affinity imparting component-1 and affinity imparting component-
As 2, a vinyl-type monomer is used in consideration of ease of production and introduction of polysiloxane groups.

As these monomers, for example, methyl (meth) acrylate [hereinafter, methyl methacrylate or methyl acrylate is generically referred to as methyl (meth) acrylate]. ), Lower alkyl (meth) acrylates such as ethyl (meth) acrylate, n-propyl (meth) acrylate and isopropyl (meth) acrylate; (meth) acrylic acid glycidyl ester; (meth) acrylic acid n-butyl, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth ) Higher (meth) acrylates such as lauryl acrylate and stearyl (meth) acrylate; lower fatty acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl butyrate, vinyl caproate 2-ethylhexanoate vinyl, vinyl laurate, stearin Higher fatty acid vinyl ester such as vinyl acrylate; Aromatic vinyl type monomers such as ethylene, vinyltoluene and vinylpyrrolidone; vinyl type monomers containing amide groups such as (meth) acrylamide, N-methylol (meth) acrylamide and N-methoxymethyl (meth) acrylamide; Hydroxyl group-containing vinyl type monomers such as hydroxyethyl (meth) acrylate and hydroxypropylallyl alcohol (meth) acrylate;
(Meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and other carboxylic acid group-containing vinyl type monomers;
Butadiene; Vinyl chloride; Vinylidene chloride; (Meth) acrylonitrile; Dibutyl fumarate; Maleic anhydride;
Dodecyl succinic anhydride; (meth) allyl glycidyl ether; alkali metal salt of radically polymerizable unsaturated carboxylic acid such as (meth) acrylic acid, itaconic acid, crotonic acid,
Ammonium salts, organic amine salts; radically polymerizable unsaturated monomers having a sulfonic acid group such as styrene sulfonic acid, and their alkali metal salts, ammonium salts,
Organic amine salt; quaternary ammonium salt derived from (meth) acrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, meta of alcohol having a tertiary amine group such as methacrylic acid diethylamine ester It is suitable to use acrylic esters, and their quaternary ammonium salts.

Further, in consideration of skin irritation, preferred monomers are methyl (meth) acrylate,
Lower alkyl (meth) acrylates such as ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate; (meth) acrylic acid glycidyl ester; (meth) acrylic acid n-butyl, (meth ) Isobutyl acrylate, ter (meth) acrylate
t-butyl, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid 2
-Higher (meth) acrylates such as ethylhexyl, octyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; lower fatty acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl butyrate, vinyl caproate. Higher fatty acid vinyl esters such as vinyl 2-ethylhexanoate, vinyl laurate and vinyl stearate; hydroxyethyl (meth) acrylate,
It is suitable to use a hydroxyl group-containing vinyl type monomer such as hydroxypropylallyl alcohol (meth) acrylate.

The proportion of the affinity-imparting component-1 in the polysiloxane group-containing polymer portion is preferably 90 to 15% by weight, more preferably 80 to 30% by weight. If the proportion of the affinity imparting component-1 exceeds 90% by weight, the performance such as water repellency and low friction property based on the polysiloxane group deteriorates, and if it is less than 15% by weight, conversion of the polysiloxane to the polymer portion is caused. The rate drops. Further, other vinyl type monomers can be copolymerized to the extent that the affinity with the cosmetic base material is not impaired.

The ratio of the polysiloxane group-containing polymer portion to the polymer portion not containing the polysiloxane group, which is the other component forming the block copolymer, is 2 by weight.
It is preferably 5/75 to 90/10. When the content of the polysiloxane group-containing polymer portion is less than 25% by weight, when it is used as a fine particle powder for cosmetics, the lipophilicity, low friction property, water repellency, etc., which are the properties of polysiloxane, are not exhibited, and it exceeds 90% by weight. Then, it becomes difficult to manufacture the fine particles. This polymer part has a good affinity for cosmetic substrates.

The ratio of the affinity imparting component-1 in the polysiloxane group-containing polymer portion to the affinity imparting component-2 in the polymer portion not containing the polysiloxane group is 3.75 / weight ratio. 96.25 to 81/19 are preferable, and 7.
5 / 92.5 to 72/28 are more preferable. If this weight ratio exceeds 81/19, the performance such as water repellency and low friction property based on the polysiloxane group deteriorates, and the weight ratio is 3.7.
If it is less than 5 / 96.25, the conversion rate of the polysiloxane to the polymer portion is lowered.

The block copolymer in the present invention is synthesized by a conventional method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method. For example, in the case of the solution polymerization method, a desired block copolymer can be obtained by carrying out two-step polymerization using a polymer peroxide as an initiator.

The polymer peroxide used in the production of the block copolymer in the present invention is a compound having two or more peroxide bonds in one molecule.
Examples of the polymer peroxide include those having a structure represented by the following general formulas (1) to (7).

— (COR ₁ CO ₂ R ₂ OCOR ₁ COOO) _n − (1) [wherein, R ₁ is an alkyl group having 1 to 18 carbon atoms, or a substituted alkylene group, 3 to 15 carbon atoms] Represents a cycloalkylene group, a substituted cycloalkylene group, a phenylene group, or a substituted phenylene group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, or a substituted alkylene group, — (CR ₃ HCH ₂ O) _m R ₄ — (In the formula, R ₃ is a hydrogen atom or a methyl group, and R ₄
Is an alkyl group having 2 to 10 carbon atoms or a substituted alkyl group. Also, m = 1 to 13. ),

[0029]

[Chemical 6]

Or

[0031]

[Chemical 7]

Represents Also, n = 2 to 30. ] - _{[COR 1 COOOC (CH 3) 2} R 5 C (CH 3) 2 OO ] _n - · · · (2) wherein, R ₁ is the same group as R ₁ in the general formula (1) Is. R ₅ represents an ethylene group, a phenyl group, or an acetylene group. Also, n = 2 to 30. ] _{(CH 3) 3 COO (COR} 1 COOO) n C (CH 3) 3 ··· (3) wherein, R ₁ is the same group as R ₁ in the general formula (1). Also, n = 2 to 30. ] - _{[COR 1 COOOC (CH 3) 2} CH 2 CH 2 C (CH 3) 2 OOCOR 1 CO OO ] _n - · · · (4) wherein, R ₁ is in the general formula (1) R _It is the same group as ₁ . Also, n = 2 to 30. ] _{- (COR 1 COOO) n -} ··· (5) wherein, R ₁ is the same group as R ₁ in the general formula (1). Also, n = 2 to 30. ]

[0033]

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[In the formula, X represents a hydrogen atom, a methyl group or a chlorine atom. Also, n = 2 to 30. ] _{[C (R 6) 2 R 5} C (R 6) 2 OOCONHR 1 NHCO (OCH 2 CR 7 H) p OCONHR 1 NHCOOO ] _n - ··· (7) wherein, R ₁ is the formula ( It is the same group as R _{1 in} 1). R ₅ is the same group as R ₅ in the general formula (2).
R ₆ and R ₇ represent a hydrogen atom or a methyl group. Also, n = 2 to 30 and p = 1 to 100. Specific examples of the polymer peroxide represented by the general formula (1) include those shown below. In both formulas, n = 2 to 30.

[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical 12]

[0039]

[Chemical 13]

[0040]

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[0041]

[Chemical 15]

[0042]

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[0043]

[Chemical 17]

[0044]

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[0045]

[Chemical 19]

[0046]

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[0047]

[Chemical 21]

[0048]

[Chemical formula 22]

[0049]

[Chemical formula 23]

[0050]

[Chemical formula 24]

Of these, general formulas 9 to 18 and 2
The compounds represented by Nos. 1 and 24 are preferable because their decomposition temperatures are not too low or too high and there is no difficulty in production.

Specific examples of the polymer peroxide represented by the general formula (2) include those shown in the following Chemical Formulas 25 to 36. In any formula, n =
2 to 30.

[0053]

[Chemical 25]

[0054]

[Chemical formula 26]

[0055]

[Chemical 27]

[0056]

[Chemical 28]

[0057]

[Chemical 29]

[0058]

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[0059]

[Chemical 31]

[0060]

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[0061]

[Chemical 33]

[0062]

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[0063]

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[0064]

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Among these, the polymer peroxides represented by the general formulas 25, 26, 29, 34 and 35 are preferable for the same reason as above. Specific examples of the polymer peroxide represented by the general formula (3) include those represented by Chemical Formulas 29 to 34 below. In both formulas, n = 2 to 30.

[0066]

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[0067]

[Chemical 38]

[0068]

[Chemical Formula 39]

[0069]

[Chemical 40]

[0070]

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[0071]

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Of these, the polymer peroxides represented by the general formulas 37 to 39 are preferable for the same reason as above. Specific examples of the polymer peroxide represented by the general formula (4) include those represented by the following Chemical Formulas 43 to 48. In both formulas, n = 2 to 30.

[0073]

[Chemical 43]

[0074]

[Chemical 44]

[0075]

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[0076]

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[0077]

[Chemical 47]

[0078]

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Of these, the polymer peroxides represented by the general formulas 43 to 45 are preferable for the same reason as above. Specific examples of the polymer peroxide represented by the general formula (5) include those represented by the following Chemical Formulas 49 to 56. In both formulas, n = 2 to 30.

[0080]

[Chemical 49]

[0081]

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[0082]

[Chemical 51]

[0083]

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[0084]

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[0085]

[Chemical 54]

[0086]

[Chemical 55]

[0087]

[Chemical 56]

Of these, the polymer peroxide represented by the general formula 49 is preferable for the same reason as above.
Specific examples of the polymer peroxide represented by the general formula (6) include those represented by the following Chemical Formulas 57 to 59, which are preferably used. In both formulas, n = 2 to 30.

[0089]

[Chemical 57]

[0090]

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[0091]

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Further, specific examples of the polymer peroxide represented by the general formula (7) include those represented by the following chemical formulas 60 to 67. In both formulas, n = 2 to 30.

[0093]

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[0094]

[Chemical formula 61]

[0095]

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[0096]

[Chemical formula 63]

[0097]

[Chemical 64]

[0098]

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[0099]

[Chemical formula 66]

[0100]

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Of these, the general formula 6
Polyperoxides represented by 0, 62, 64 and 66 are preferable. The above polymer peroxides can be used alone or in combination of two or more when used.

The amount of the polymer peroxide used in the block copolymerization is usually 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. The polymerization temperature for forming one polymer portion of the block copolymer is 6
The polymerization time is 0 to 130 ° C. and the time is about 2 to 10 hours.
The polymerization temperature for forming the other polymer portion of the block copolymer is 60 to 140 ° C., and the polymerization time is about 3 to 15 hours.

The solvent at the time of polymerization is preferably a solvent having a boiling point of 150 ° C. or lower in order to accelerate the drying time for powdering. Examples of the low boiling point solvent include ethyl alcohol, propyl alcohol, 2-propyl alcohol, 1-butyl alcohol, 2-butyl alcohol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, cyclopentanol, 2-hexanol, 3-hexanol, cyclohexanol, methyl cellosolve, acetone, 2-butanone, 3-methyl-2-butanone, 2-pentanone, 3-pentanone, 2-methyl-3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2,4-dimethyl-3-pentanone, 4,4
-Dimethyl-2-pentanone, 2-hexanone, 3-hexanone, cyclopentanone, cyclohexanone, 2-
Heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-hexanone, 5-methyl-2-hexanone,
5-methyl-3-hexanone, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, trimethyl methyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propion Propyl acid, butyl propionate, isobutyl propionate, tert-butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, methyl isobutyrate, ethyl isobutyrate, 2-methyl-methyl butyrate, methyl caproate, toluene, Examples include ethylbenzene and xylene. These low boiling solvents are used alone or in combination of two or more.

The content of the low boiling point solvent is preferably 30 to 90% by weight, more preferably 50 to 80% by weight.
Here, the case of the solution polymerization method will be described as a specific example. First, using a polymer peroxide as shown in the following chemical formula 68, one or two or more of the affinity imparting component-2 that forms a polymer portion having an affinity with the cosmetic base material is polymerized. At this time, a polymer containing a peroxide bond can be obtained by stopping the polymerization when the active oxygen amount of the polymer peroxide remains at about 50%.

[0105]

[Chemical 68]

Further, using this polymer as a polymerization initiator,
One or more polysiloxanes represented by the above general formulas (I) and (II) for forming a polysiloxane group-containing polymer portion, and further, if necessary, an affinity imparting component-1.
One or more of the monomers shown in 1 above and other monomers are copolymerized. As a result, a block copolymer composed of a polysiloxane group-containing polymer portion and a polymer portion having an affinity for the cosmetic base material can be obtained. The polymer peroxide may be used to obtain a polysiloxane group-containing polymer containing a peroxide bond by the first stage polymerization, and then the polymer portion having an affinity for the cosmetic base material may be blocked.

Next, the block copolymer is pulverized by the following method. That is, the block copolymer solution synthesized as described above is reprecipitated with a solvent insoluble in the block copolymer solution, and then purified and dried. By pulverizing the obtained powder with a ball mill, fine powder is obtained. Further, the block copolymer may be pulverized into fine particles with a spray dryer.

The particle size of the cosmetic composition powder of the present invention is not particularly limited, but is preferably in the range of 0.1 to 100 μm (average particle size). The range of 1 to 50 μm (average particle size) is more preferable. If the average particle size is less than 0.1 μm, the smoothness of the resulting powder may be impaired, and if it exceeds 100 μm, it is not preferable because a rough feel occurs.

Next, the cosmetic composition of the present invention contains the cosmetic composition powder obtained as described above. The content is appropriately determined depending on the kind of the intended cosmetic composition, but it is usually preferably 0.1 to 99% by weight, more preferably 1 to 50% by weight in the cosmetic composition. Is.

Further, as an additive component other than the cosmetic composition powder in the cosmetic composition, a component appropriately selected from the components to be added to a usual cosmetic composition according to the kind of the intended cosmetic composition. Can be blended. Such components include, for example, perfluoropolyether,
Fluorine-based oil agents such as perfluorodecalin and perfluorooctane; water-soluble and oil-soluble polymers, surfactants,
Permanent and organic pigments, permanent and organic pigments treated with silicon or fluorine compounds, colorants such as organic dyes, ethanol, preservatives, antioxidants, pigments, thickeners, pH adjusters, fragrances, UV absorbers, Moisturizers, blood circulation promoters, cooling agents, antiperspirants, bactericides, skin activators and the like can be mentioned. These components are blended within a range that does not impair the objects and effects of the present invention.

The cosmetic composition of the present invention can be produced by a conventional method, and can be used for makeup cosmetics such as foundation, eye shadow, blusher, lipstick, powder, emulsions, creams, lotions, beauty essences and the like. Basic cosmetics, etc.
In addition, it can be applied to face wash, pack material and the like.

[0112]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. All parts and% in the examples and comparative examples are based on weight. Example 1 (A) Synthesis of Peroxide Bond-Containing Polymer A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 57 g of methyl ethyl ketone and heated to 70 ° C. while blowing nitrogen gas. Then, a mixed solution of 57 g of methyl ethyl ketone, 48 g of methyl methacrylate, 32 g of the compound shown in Chemical formula 69 below, and 6 g of the polymer peroxide shown in Chemical formula 70 was charged over 2 hours, and a polymerization reaction was further performed for 4 hours.

[0113]

[Chemical 69]

[0114]

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Next, methyl ethyl ketone was removed from the polymer solution under reduced pressure at room temperature using an evaporator. Then, the solid of the obtained polymer was pulverized. Further, 20 g of the obtained powder was charged in the reactor. Then, 300 g of n-hexane was added, and the mixture was stirred at room temperature for 20 hours to extract unreacted polysiloxane.

After fractionation of the fine powder, n-hexane was distilled off from the recovered n-hexane solution, and 5.3 g of a sticky compound was obtained. As a result of NMR analysis and GPC (gel permeation chromatograph) analysis, it was revealed that this compound contained 15% by weight of low molecular weight polymethylmethacrylate and 85% by weight of unreacted polysiloxane.

As a result of NMR analysis, the fine powder separated and taken out was found to be a polymer in which the weight ratio of polymethyl methacrylate to polysiloxane was about 75/25. Also, this fine powder has an active oxygen content of 0.14%,
It was shown to have a peroxide bond. The polystyrene-equivalent number average molecular weight measured by GPC was 21,000. (B) Synthesis of block copolymer 14 g of fine powder obtained in (A) from which unreacted polysiloxane has been removed, 7 g of methyl methacrylate, 29 g of toluene
After mixing and dissolving, the mixture was charged into an ampoule purged with nitrogen. Then, stirring this at 70 ° C. for 4 hours, and further 80
A block copolymer was synthesized by reacting at 4 ° C for 4 hours.
The obtained polymer solution was colorless and transparent. The measurement of residual methyl methacrylate by GC (gas chromatograph) revealed that the polymerization conversion rate was 98%, and the measurement of GPC revealed that the number average molecular weight was 32000.

The obtained polymer solution was reprecipitated in methanol, sufficiently purified and dried, and then the obtained polymer was pulverized by a ball mill to obtain fine particle powder. About this powder N
As a result of MR analysis, it was shown that the weight ratio of polymethylmethacrylate to polysiloxane was about 82/18. From these results, the obtained polymer is a block copolymer of a polymer portion in which polysiloxane is branchedly grafted to polymethylmethacrylate (weight ratio 70/30) and a polymer portion made of polymethylmethacrylate. It was a polymer, and it was revealed that the weight ratio of both polymer portions was about 70/30. (C) Next, using the fine particle powder synthesized as described above, a cream was prepared according to the following formulation.

Fine powder 12.0%, solid paraffin 5.0%, petrolatum 14.0%, liquid paraffin
40.0%, glycerin monostearate 2.0%,
Polyoxyethylene sorbitan monoole 2.0%,
Purified water 23.7%, soap powder 0.1%, borax
0.2%, fragrance 1.0%, proper amount of antioxidant and preservative.

Powder was prepared according to the following formulation. Fine particle powder 80.0%, zinc white 5.0%, zinc stearate 5.0%, rice starch 10.0%, fragrance and colorant (Example 2) Chemical formula charged in Example 1 (A) Instead of 32 g of the monomer represented by the chemical formula 69, 16 g of the monomer similarly represented by the chemical formula 69 and the following chemical formula 71
A block copolymer powder was synthesized in the same manner as in Example 1, except that 16 g of the monomer (Mn = 5000) represented by

[0121]

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Then, in the same manner as in Example 1, analysis was performed after removing the unreacted polysiloxane. As a result, the weight ratio of polymethylmethacrylate to polysiloxane in the peroxide bond-containing copolymer was about 67/33.

The active oxygen content was 0.14% and the number average molecular weight was 34,000. Furthermore, from the result of analysis after synthesis of the block copolymer, a block copolymer composed of a polymer portion in which polysiloxane is branched-bonded to polymethylmethacrylate, and a polymer portion made of polymethylmethacrylate, It was revealed that the weight ratio of both polymer parts in the block copolymer was about 70/30. The number average molecular weight of the block copolymer was 42000. Further, in the same manner as in Example 1, fine particle powder, cream and powder were prepared. (Example 3) (A) Synthesis of polymer containing peroxide bond: 400 parts of toluene was charged in the same reactor as in Example 1,
It heated at 70 degreeC, blowing in nitrogen gas. in addition,
170 parts of toluene, 160 parts of methyl methacrylate, 180 parts of n-butyl methacrylate, 60 parts of 2-hydroxyethyl methacrylate, and 30 parts of polymer peroxide represented by the following chemical formula 72 were charged over 2 hours and polymerization was continued for 4 hours. The reaction was carried out.

[0124]

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The polymerization conversion ratio was 96%, and the number average molecular weight of the obtained polymer was 14,000. (B) Synthesis of Block Copolymer 50 parts of the polymer solution synthesized above was charged into the same reactor as above. While blowing nitrogen gas into this, 70
18 parts of polysiloxane (number average molecular weight 10,000) at 6 ° C, 6 parts of methyl methacrylate, 6 parts of n-butyl methacrylate,
A mixture having a composition of 45 parts of toluene was charged over 30 minutes,
Further, a polymerization reaction was carried out at 70 ° C. for 3 hours. After the reaction,
The polymer content was 39.2%. Further, in the same manner as in Example 1, fine particle powder, cream and powder were prepared. Example 4 A block copolymer was synthesized under the same conditions as in Example 3 except that the polysiloxane (B) of Example 3 (number average molecular weight 10,000) was changed to a number average molecular weight 500. The content of the polymer was 39.4%. Further, in the same manner as in Example 1, fine particle powder, cream and powder were prepared. (Example 5) A block copolymer was synthesized under the same conditions as in Example 3 except that the polysiloxane (B) of Example 3 (number average molecular weight 10,000) was changed to one having a number average molecular weight of 50,000. The content of the polymer was 39.5%.
Further, in the same manner as in Example 1, fine particle powder, cream and powder were prepared. (Example 6) Example 6 was repeated except that the polysiloxane of (B) in Example 3 was changed to 9 g of the polysiloxane represented by the chemical formula 69 and 9 g of the chemical formula 71 having a number average molecular weight of 10,000. A block copolymer was synthesized under the same conditions as in 3. The solid content concentration after completion of the polymerization was 39.3%. Then, in the same manner as in Example 1, fine particle powder, cream and powder were prepared. (Example 7) (A) Synthesis of polymer containing peroxide bond In the same reactor as in Example 1, methyl ethyl ketone (17) was added.
0 part was charged and heated at 70 ° C. while blowing nitrogen gas. Then, a mixed solution consisting of 185 parts of methyl ethyl ketone, 80 parts of methyl methacrylate, 80 parts of polysiloxane (used in Example 3 (B)), and 15 parts of the polymer peroxide represented by the chemical formula 72 was used for 2 hours. Then, the polymerization reaction was continued for 4 hours. Then, by the same operation as in Example 1, the unreacted polysiloxane was removed to obtain a fine powder. As a result of NMR measurement, this fine powder had a weight ratio of polymethylmethacrylate and polysiloxane of 57.
The polymer was / 43. (B) Synthesis of Block Copolymer The fine powder obtained by removing the unreacted polysiloxane obtained in (A) above was dissolved in toluene to prepare a 40 wt% solution. This polymer solution was charged into the same reactor as the above (A), and while blowing nitrogen gas at 70 ° C., 27 parts of methyl methacrylate, 27 parts of n-butyl methacrylate and 54 parts of toluene.
A portion of the mixture was charged over 30 minutes. 7 more
Polymerization reaction was carried out by heating at 0 ° C. for 5 hours and at 80 ° C. for 3 hours. As a result of measuring the polymerization conversion rate of the obtained polymer, the polymerization conversion rate was 97%, and the content of the polysiloxane group polymer portion in the polymer was 51%. Further, in the same manner as in Example 1, fine particle powder, cream and powder were prepared. (Example 8) The same conditions as in Example 7 except that the polysiloxane of (A) of Example 7 was changed to 40 parts of the polysiloxane represented by the chemical formula 69 and 40 parts of the polysiloxane represented by the chemical formula 71. A block copolymer was synthesized by. The solid content concentration after completion of the polymerization was 39.2.
%Met. Further, in the same manner as in Example 1, fine particle powder, cream and powder were prepared. (Comparative Example 1) A block copolymer was synthesized under the same conditions as in Example 5 except that the polysiloxane of (B) in Example 3 was not added. Further, in the same manner as in Example 1, fine particle powder, cream and powder were prepared.

Next, the above Examples 1 to 8 and Comparative Example 1
A so-called panel test was conducted on the three types of fine particle powder, cream, and powder synthesized in 1. That is, as a test, the powder was applied to the backs of the hands of 10 women, and while being sufficiently rubbed, they were evaluated for the four items of good familiarity to the skin at that time, soft feeling on the skin, water repellency, and water resistance. It was The evaluation standard is good: 5 points, fair: 3 points
Poor / Poor: 1 point, and the average of those points is shown in Table 1 below.

[0127]

[Table 1]

As shown in Table 1, in the case of using only the fine particle powder, all of Examples 1 to 8 are well suited to the skin, give a soft feeling, and have high water repellency and water resistance. An evaluation was obtained. Among them, the one of Example 8 obtained a good evaluation. On the other hand, the fine particle powder of Comparative Example 1 had a low rating such that it was poorly fit to the skin and had no water resistance.

In the case of a cream, the fine particle powders of any of Examples 1 to 8 have a high affinity with the cosmetic base material, and the obtained cream has a high evaluation. On the other hand, the fine particle powder of Comparative Example 1 had a low rating.

In the case of powder, all of the powders of Examples 1 to 8 were well adapted to the skin and were highly evaluated.
On the other hand, the fine particle powder of Comparative Example 1 had a low rating.
From the above, the fine particle powder according to the present invention has good compatibility with the skin, less discomfort, and high water repellency.
Moreover, since the fine particle powder has a high affinity with the base material for cosmetics and the like, it has an excellent feature that this property can be maintained for a long period of time, and that it has the performance required as a powder for cosmetics. I understand.

From these results, it is clear that the fine particle powder of the present invention imparts a longer lasting property of polysiloxane than the block copolymer containing only the graft copolymer of Comparative Example 1. . From the viewpoint of imparting initial physical properties, the higher the molecular weight of polysiloxane, the better, but if it is too high, tackiness tends to occur.
On the other hand, if the molecular weight of the polysiloxane is too low, the initial physical properties tended to deteriorate slightly.

As described above, the fine particle powder of the block copolymer having a polysiloxane group used in the present invention has a high affinity to the skin, has less discomfort, and is hard to drop in water. Furthermore, since the block copolymer has a polymer portion having an affinity for the cosmetic base material, these properties can be maintained for a long time, which is useful as a cosmetic composition.

The technical ideas other than the claims will be described below along with their effects. (1) The block copolymer is obtained by a two-step polymerization using a polymer peroxide.
The cosmetic composition according to. According to this structure, a block copolymer can be efficiently obtained with a high block rate. (2) In the first stage polymerization, about 50% of the polymer peroxide
%, The cosmetic composition according to (1) above, wherein a polymer having a peroxide bond is obtained. According to this structure, the desired block copolymer can be obtained more reliably. (3) The cosmetic composition according to claim 2, wherein the polysiloxane group content in the polysiloxane group-containing polymer portion is 10 to 50% by weight. According to this structure, the properties of the cosmetic composition such as water repellency and water resistance can be effectively exhibited, and those properties can be maintained for a long time. (4) The cosmetic composition according to claim 2, wherein the polysiloxane group in the polysiloxane group-containing polymer portion has a number average molecular weight of 500 to 40,000. With this configuration, properties such as lipophilicity and low friction property derived from the polysiloxane group can be effectively exhibited.

[0134]

As described above in detail, according to the invention of the cosmetic composition according to claim 1, the effect of being well-adapted to the skin, having less discomfort, and having excellent water repellency and water resistance. Play.

According to the second aspect of the invention, there is an excellent effect that characteristics such as water repellency and water resistance are exhibited for a long time.

Claims (2)

[Claims] 1. A cosmetic composition comprising a base material component and an additive component, the additive component containing a block copolymer having a polysiloxane group. 2. The block copolymer is a polysiloxane group.
Containing no polymer part and polysiloxane group
A polysiloxane group consisting of a polymer part and containing a polysiloxane group.
The united portion is represented by the following general formula (I) or (II).
1 type or 2 or more types of monomers and 1 type of vinyl type monomer.
Or two or more, and contains polysiloxane groups
The polymer portion that does not include one or more vinyl type monomers
The cosmetic composition according to claim 1, which is formed from above. [Chemical 1][In the formula, R₁Is a hydrogen atom or a methyl group, R₂Is methyl
Group, ethyl group, phenyl group or(In the formula, R_FiveIs a hydrogen atom, a phenyl group or C
_PH_{2P + 1}, R₆Is methyl, ethyl or phenyl
Group, m is an integer of 1 or more, p is an integer of 1 to 10.
It ), R ₃Is a hydrogen atom, a phenyl group or C
_QH_{2Q + 1}, R_FourIs methyl, ethyl or phenyl
Group, n is an integer of 1 or more, and Q is an integer of 1 to 10. ] [Chemical 3][In the formula, R₁Is a hydrogen atom or a methyl group, R₂Is methyl
Group, ethyl group, phenyl group or(In the formula, R_FiveIs a hydrogen atom, a phenyl group or C
_PH_{2P + 1}, R₆Is methyl, ethyl or phenyl
Group, m is an integer of 1 or more, p is an integer of 1 to 10.
It ), R ₃Is a hydrogen atom, a phenyl group or C
_QH_{2Q + 1}, N is an integer of 1 or more, and Q is an integer of 1 to 10.
It ]