JP2001278982A - New polymer and cosmetic prepared by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new copolymer excellent in the improving effect on the pigment dispersibility and a cosmetic prepared by blending the same. SOLUTION: The block copolymer has a polysiloxane part and a hydrophilic part containing at least a sulfonic acid group as constituent units and the cosmetic is prepared by blending the above block copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel block copolymer containing a polysiloxane part and a specific hydrophilic part as constituents, and a cosmetic containing the same.
More specifically, the present invention relates to a novel copolymer excellent in the effect of improving pigment dispersibility and a cosmetic containing the same.

[0002]

2. Description of the Related Art Conventionally, methods for improving the dispersion stability of pigments in cosmetics containing pigments include mixing with a mechanical force such as a homomixer, mill, kneader, roller, or the like, a dispersant, and a thickener. And the like.

[0003] However, there is a limit to dispersion by mechanical force alone. In many cases, once dispersed uniformly, aggregation occurs over time. Further, at present, the development of a dispersant having sufficiently high affinity for both the pigment and the dispersion medium is insufficient, and in particular, an effective dispersant for hydrophilic pigments in oil or an effective dispersant for lipophilic pigments in water. Therefore, development of a high-performance base has been eagerly desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer capable of dispersing a hydrophilic pigment stably in oil, and a cosmetic composition containing the polymer.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on the dispersion of a hydrophilic pigment in oil and the dispersion stability thereof. As a result, the polysiloxane moiety and a specific hydrophilic group were used as functional groups. It has been found that a block copolymer containing a hydrophilic portion having as a constituent component can solve the above problems,
The present invention has been completed.

That is, the present invention provides the following general formulas (I) and (I)
A polysiloxane moiety containing any one or more of the repeating units represented by I) and at least a sulfonic acid group (—SO ₃
The present invention provides a block copolymer containing, as a structural unit, a hydrophilic portion containing H).

[0007]

Embedded image

[0008]

Embedded image

In the general formulas (I) and (II), each symbol has the following meaning.

R ¹ : independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group; R ² : a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ³ : 1 carbon atom CO-Y-CO: dibasic acid residue; A: -NH- or -O-: B: alkylene having 1 to 6 carbon atoms which may be connected to an oxygen atom Groups; m: a number of 10,000; p: a number of 0-6.

In the above, an amide group (—CONH ₂ ) and a quaternary ammonium group [—N (R) ₃
⁺ (R: each independently a hydrogen atom or a carbon atom having 1 to 1
6), carboxybetaine [R ′
(R ″) ₂ N ⁺ CH ₂ COO ⁻ (R ′, R ″: each independently an alkyl group having 1 to 6 carbon atoms)], a carboxyl group (—COOH), a phosphate group [—O—PO (O
H) ₂ ], one or more hydrophilic groups selected from a hydroxyl group (—OH) and a nitrogen-containing heterocyclic group having a vinyl group.

The above block copolymer is suitably used as a pigment dispersant.

The present invention also provides a cosmetic containing the above block copolymer.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The polysiloxane part which constitutes one component of the copolymer of the present invention contains at least one of the repeating units represented by the following general formulas (I) and (II).

[0016]

Embedded image

[0017]

Embedded image

In the above formula, R ¹ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R ¹ is preferably a methyl group or a phenyl group.

R ² is a hydrogen atom or a group having 1 to 6 carbon atoms.
Represents an alkyl group. R ² is preferably a methyl group.

R ³ represents an alkyl group having 1 to 6 carbon atoms or a cyano group. R ³ is preferably a cyano group.

CO-Y-CO represents a dibasic acid residue. Specific examples thereof include, but are not limited to, acid residues such as malonic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, and itaconic acid. .

A represents -NH- or -O-, and B represents an alkylene group having 1 to 6 carbon atoms which may be linked through an oxygen atom.

M is a number from 1 to 10,000, and p is 0
Shows the number of ~ 6.

As a preferred embodiment of the polysiloxane part,
A case including the repeating unit represented by the general formula (I),
The repeating unit represented by the general formula (I) and the general formula (II)
And a combination of repeating units represented by

The polysiloxane portion spreads in the dispersion medium (various silicone oils and mineral oils) and has an effect of increasing the affinity of the hydrophilic pigment for the dispersion medium.

The hydrophilic part, which is another component of the copolymer of the present invention, contains at least a sulfonic acid group (-S
O ₃ H).

The sulfonic acid group (—SO ₃ H) is particularly excellent in adsorptivity to a hydrophilic pigment. Therefore, in the block copolymer of the present invention, by including a hydrophilic portion containing at least a sulfonic acid group as a functional group, the hydrophilic group portion is adsorbed on the hydrophilic pigment, and especially the dispersibility of the pigment in oil. Can be improved. Therefore, even if the hydrophilic pigment is not subjected to a surface treatment or the like for improving dispersibility,
The dispersibility of these pigments can be improved.

Examples of the compound having a sulfonic acid group include 2- (meth) acrylamide 2-methylpropanesulfonic acid and P-styrenesulfonic acid.
It is needless to say that the present invention is not limited to these examples.

In the present invention, the hydrophilic portion may further contain another hydrophilic group in addition to the sulfonic acid group. Examples of such a hydrophilic group include an amide group (—CONH ₂ ), a quaternary ammonium group [—N (R) ₃ ⁺ (R: each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)], carboxybetaine. _{[R '(R'') 2} N + CH 2 COO
^- (R ', R'': each independently an alkyl group having 1 to 6 carbon atoms)], a carboxyl group (-COOH), a phosphate group [-O-PO (OH) ₂ ], a hydroxyl group (-OH) And one or more selected from nitrogen-containing heterocyclic groups having a vinyl group.

Examples of the compound having an amide group include (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like.

Examples of the compound having a quaternary ammonium group include aminoethyl (meth) acrylate and (meth) acrylate.
N, N-dimethylaminoethyl acrylate, trimethylammonium ethyl chloride (meth) acrylate and the like can be mentioned.

As the compound having aminobetaine,
For example, 2- (meth) acryloxyethyldimethylammonium α-methylcarboxybetaine and the like can be mentioned.

As the compound having a carboxyl group,
For example, (meth) acrylic acid, maleic anhydride and the like can be mentioned.

Examples of the compound having a phosphate group include ethyl (meth) acrylate phosphate.

Examples of the compound having a hydroxyl group include hydroxyethyl (meth) acrylate, vinyl alcohol, and glycerol mono (meth) acrylate.

Examples of the nitrogen-containing heterocyclic group having a vinyl group include vinylpyridine, 2-vinylpyrrolidone, vinylmorpholine and the like.

In addition to the above, polyethylene glycol mono (meth) acrylate is also preferably used as a hydrophilic part monomer.

Among the above hydrophilic groups, an amide group, a quaternary ammonium group, a carboxyl group, a phosphate group and the like are preferably used from the viewpoint of improving pigment dispersibility.

In order to obtain the desired effect of the present invention of pigment dispersibility, the copolymer of the present invention preferably contains about 0.1 to 100 mol% of a sulfonic acid group in the hydrophilic part. Is about 10 to 100 mol%.

The copolymer of the present invention may further contain a hydrophobic part. As the hydrophobic portion, a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 22 carbon atoms, which may contain fluorine, a linear or 1 to 22 carbon atom, Among mono- or di-substituted alkyl (meth) acrylamides having a branched alkyl group, substituted or unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms, and polysiloxane-containing monomers which may contain fluorine. One or more selected ones are mentioned.

1 carbon atom which may contain fluorine
Specific examples of the alkyl (meth) acrylate having a linear or branched alkyl group of from 22 to 22 include methyl (meth) acrylate, stearyl (meth) acrylate, 1H, 1H, 2H, 2H-heptadeca. Examples thereof include fluorodecyl (meth) acrylate, hexyl (meth) acrylate, and dodecyl (meth) acrylate.

Examples of the mono- or di-substituted alkyl (meth) acrylamide having a linear or branched alkyl group having 1 to 22 carbon atoms include N-hexyl (meth) acrylamide, N-stearyl (meth) acrylate,
N, N-dihexyl (meth) acrylate and the like can be mentioned.

Specific examples of the substituted or unsubstituted aromatic hydrocarbon having 6 to 12 carbon atoms include styrene and the like.

In the polysiloxane-containing monomer which may contain fluorine, the polysiloxane is preferably a group represented by the following formulas (7) and (8).

[0045]

Embedded image

In the formula, R ¹⁰ is each independently an alkyl group having 1 to 6 carbon atoms which may contain fluorine, a phenyl group, or —O—Si (R ¹¹ ) ₃ (where R ¹¹ is An alkyl group having 1 to 6 atoms or a phenyl group), and s is a number of 1 to 6. Provided that at least one R ¹⁰ is -OS
i (R ¹¹ ) ₃ .

[0047]

Embedded image

In the formula, R ¹² is independently an alkyl group having 1 to 6 carbon atoms or a phenyl group which may contain fluorine, and Z is an alkyl group having 1 to 6 carbon atoms or-
(CH _{2) u} -O-, _u is the number of 1 to 6, v is 5～1,00
Indicates the number of 0.

When the above polysiloxane is used as the hydrophobic group, there is an effect that the compatibility between the silicone oil and the wax can be efficiently increased.

Specific examples of the polysiloxane-containing monomer which may contain fluorine include 3-methacryloxypropyl (tristrimethylsiloxy) silane,
Methacryloxypropyl polydimethylsiloxane and the like.

When these hydrophobic parts are contained, it is preferable that they are copolymerized (randomly or blocked) as monomers together with the hydrophilic parts and contained.

The content of the hydrophobic part can be blended within a range that does not impair the desired effect of the copolymer of the present invention, ie, the effect of improving the pigment dispersing effect, and the blending amount also varies depending on the kind of the hydrophobic part. However, the content of the hydrophobic part in the copolymer of the present invention is preferably about 0.1 to 90% by weight, particularly preferably 1 to 1% by weight.
It is about 0% by weight. By incorporating a hydrophobic part in this manner, when an oil component is blended in the formulation, it becomes possible to have an affinity for both water and the oil component.

In the copolymer of the present invention, a polysiloxane part containing at least one of the repeating units represented by the above general formulas (I) and (II) and another copolymer part (hydrophilic part, hydrophobic part) Component part, etc.), depending on the purpose, the polysiloxane part: the other copolymer part = 99.9: 0.1 to
1:99 (weight ratio), preferably 99.9:
It can be changed in the range of 0.1 to 10:90 (weight ratio).

In the copolymer of the present invention, the copolymer portion other than the above-mentioned polysiloxane portion may include only the above-mentioned hydrophilic portion or both the hydrophilic portion and the hydrophobic portion. Sex part: hydrophobic part: 0: 100 to 99.9:
0.1 (molar ratio) is preferred, and especially 50:50 to 9
9: 1 (molar ratio) is preferred.

In the copolymerized portion other than the polydimethylsiloxane portion, the ratio of the hydrophilic portion (monomer) containing at least a sulfonic acid group to the other monomer is such that the ratio of the hydrophilic portion: the other monomer is 100: 0. ~ 0.1: 99.9
(Molar ratio) is preferred, and especially 100: 0 to 10:90.
(Molar ratio) is preferred.

The production of the block copolymer of the present invention is preferably carried out by copolymerizing an azo group-containing polysiloxane compound and a hydrophilic part containing at least a sulfonic acid group.

As the azo group-containing polysiloxane compound, for example, the following general formula (IV)

[0058]

Embedded image

(Wherein R ¹ , R ² , R ³ , A, B, p, m
Are the same as defined in the above general formula (I)), or a compound having a repeating unit represented by the general formula (IV)
And the like are preferred. Compounds comprising a combination of the repeating unit represented by the general formula (II) with the repeating unit represented by the general formula (II) are preferred.

The azo group-containing polysiloxane compound having a repeating unit represented by the general formula (IV) is described in, for example, JP-A-4-372675 and JP-A-6-93100.
It can be easily manufactured by the manufacturing method described in JP-A-6-3220809 and the like.

That is, for example, the following general formula (V)

[0062]

Embedded image

(Wherein D represents an NH ₂ or OH group;
R ¹ , B and m are as defined above) and a diamine or diol compound containing a polysiloxane moiety represented by the following general formula (VI):

[0064]

Embedded image

(Wherein X represents a halogen atom or —OH, and R ² , R ³ and p are as defined above) in a solvent, preferably basic It can be obtained by reacting in the presence of a catalyst. Examples of the solvent include ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and dimethoxyethane; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, ethylene dichloride, and tricrene; benzene, toluene, xylene, and the like. Hydrocarbons; esters such as ethyl acetate, butyl acetate and methyl propionate; acetonitrile, N,
N-dimethylformamide and the like. Examples of the basic catalyst include organic amines such as triethylamine, N, N-dimethylaniline, piperidine and pyridine, and basic alkali metal compounds such as n-butyllithium.

Then, the above-mentioned azo machine-containing polysiloxane compound and the above-mentioned hydrophilic part having at least a sulfonic acid group may be subjected to a polymerization reaction in a solvent, preferably under an inert gas atmosphere, according to a conventional method.

As the solvent, the same solvents as those used in the production of the azo group-containing polysiloxane compound can be used. Examples of the inert gas include a nitrogen gas and an argon gas.

The azo group-containing polysiloxane compound having a repeating unit represented by the above general formula (IV) (macroazo polymerization initiator) easily generates N ₂ by heating or irradiation with light and is decomposed to give a radical species (the above general formula). (Polysiloxane portion having a repeating unit represented by the formula (I)), and at that time, the polymer is promptly polymerized with the above-mentioned hydrophilic portion having at least a sulfonic acid group to form the block copolymer of the present invention. .

When the above production is carried out by heating, the reaction temperature is usually about 30 to 130 ° C., preferably 50 to 130 ° C.
The temperature is about 100 ° C., and may be changed as the polymerization proceeds. The reaction time is generally about 1 to 48 hours, preferably about 1 to 24 hours. When the above-mentioned production is carried out by light irradiation, the reaction temperature is usually about 0 to 60 ° C, preferably about 20 to 50 ° C. As a light source used for light irradiation, for example, a high-pressure mercury lamp can be used. The irradiation light is preferably UV light in order to promptly decompose the azo group-containing polysiloxane compound and copolymerize the hydrophilic part.

The average molecular weight of the azo group-containing polysiloxane compound at the time of the polymerization reaction is not particularly limited.
About 200,000, preferably 3,000 to 150,
About 000 are suitably used. If the molecular weight is too small, the production efficiency of the block copolymer decreases, while if the molecular weight is too large, the solubility in the solvent decreases, and the viscosity of the solution also increases, so it is necessary to perform the block copolymerization at a low concentration, It is not preferable because the polymerization rate with the hydrophilic portion is reduced.

Preferred specific examples of the copolymer of the present invention thus obtained include a block copolymer having a structural unit represented by the following general formula (VII).

[0072]

Embedded image

(Wherein R ¹ , R ² , R ³ , m and p are as defined above. R ⁴ represents a hydrogen atom or a carbon atom, and R ⁵ represents a hydrophilic group containing at least a sulfonic acid group. And q represents a number of 1 to 200.) The copolymer of the present invention has a hydrophilic part-polysiloxane part-hydrophilic part type (ABA) as shown in the general formula (VII).
Block copolymer of type (A), but a copolymer of the type of hydrophilic part-polysiloxane part-hydrophilic part-polysiloxane part-hydrophilic part (ABABA type) is also preferable. .

The copolymer of the present invention has a molecular weight of 1,000 to 1,
It is preferably about 1,000,000, and especially 2,000 to 1
It is about 00,000. The molecular weight is appropriately determined according to the purpose.
The molecular weight of the produced copolymer increases as the amount of monomer added during polymerization increases.

In the block copolymer of the present invention, the polysiloxane moiety has the effect of increasing the affinity of the block copolymer for the dispersion medium. In addition, since the sulfonic acid group as an essential component has a high adsorptivity to a pigment, particularly a hydrophilic pigment, the hydrophilic pigment can be uniformly dispersed.

Other parts other than the above are the properties of the base, the dosage form (O / W, W / O, water-based, oil-based, alcohol-based),
The composition of the drug can be changed according to the polarity and purpose of the drug.

[0077] The block copolymer of the present invention is suitably blended in cosmetics. The copolymer used in the present invention is particularly W /
When a hydrophilic pigment is blended in the aqueous phase (inner phase) in the O-type, the hydrophilic pigment can be effectively and uniformly dispersed.

The pigment is not particularly limited as long as it can be generally used for cosmetics. Specific examples include organic powders such as polyamide resin powder (nylon powder), copolymer resin powder of styrene and acrylic acid, and cellulose powder, as well as various inorganic powders and metal powders. These inorganic powders and the like can be used in any of hydrophobic treatments and untreated ones. Examples of the powder components include talc, carion, mica, sericite, and sericite.
Muscovite, Phlogopite, Synthetic mica, Phlogopite, Biotite, Lithium mica, Permiculite, Magnesium carbonate, Calcium carbonate, Aluminum silicate, Barium silicate, Calcium silicate, Magnesium silicate, Strontium silicate, Metal tungstate , Magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluorapatite, hydroxyapatite, ceramic powder, metal soap (zinc myristate, calcium palmitate, aluminum stearate, etc.), boron nitride, etc. Inorganic powders; inorganic white pigments such as titanium dioxide and zinc oxide; inorganic red pigments such as iron oxide (iron oxide) and iron titanate; inorganic brown pigments such as γ-iron oxide; and inorganic yellow pigments such as yellow iron oxide and loess Pigment;
Inorganic black pigments such as black iron oxide, carbon black, and lower titanium oxide; inorganic purple pigments such as mango violet and baltic violet; inorganic green pigments such as chromium oxide, chromium hydroxide, and cobalt titanate; ultramarine, navy blue Inorganic blue pigments such as titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil and other pearl pigments; metal powders such as aluminum powder and copper powder Pigments and the like. One or more pigments can be used.

The block copolymer of the present invention is suitably blended in cosmetics. The copolymer used in the present invention is excellent in pigment dispersibility. In particular, makeup cosmetics such as foundations, lipsticks, blushers, and eye shadows, skin care creams, skin lotions, skin protection cosmetics such as sunscreens, and nail enamels. And the like, and can improve the usability of these cosmetics. One or more of the copolymers of the present invention can be incorporated into cosmetics.

To the cosmetic of the present invention, in addition to the copolymer of the present invention, additional components which are usually used in cosmetics can be arbitrarily added as long as the effects of the present invention are not impaired. Such components include, for example, vitamins, fats and oils,
Waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicones, humectants, anionic surfactants, cationic surfactants, amphoteric surfactants, lipophilic nonionic surfactants, hydrophilic nonionic interfaces Activators, preservatives,
Anti-inflammatory, whitening agent, plant extract, activator, blood circulation promoter, antiseborrheic, natural water-soluble polymer, semi-synthetic water-soluble polymer, synthetic water-soluble polymer, inorganic water-soluble polymer, Examples include a viscosity agent, a powder component, and a sequestering agent. The dosage form is not particularly limited, and examples thereof include oily cosmetics, water-in-oil emulsified cosmetics, oil-in-water emulsified cosmetics, aqueous cosmetics, solid cosmetics, and oily solid cosmetics.

As the block copolymer of the present invention, only one kind may be used as a dispersant, or two or more kinds may be used in combination.

The block copolymer according to the present invention is a compound capable of uniformly dispersing a pigment. According to the present invention, a new formulation which has been limited in the past can be realized.

[0083]

EXAMPLES Hereinafter, the present invention will be further described with reference to specific examples, but the present invention is not limited thereto. In addition, the following compounding amounts are shown by weight% unless otherwise specified.

In this example, as the azo group-containing polysiloxane compound, a polymer azo initiator (“VS
P "series (manufactured by Wako Pure Chemical Industries, Ltd.), prepared by changing the molecular weight of the polydimethylsiloxane moiety.

[Synthesis Example 1] Polydimethylsiloxane
2-acrylamide 2-methylpropanesulfonic acid block copolymer poly [polydimethylsiloxane-4,4'-azobis (4-cyanopentanoamidopropyl)] (polydimethylsiloxane part average molecular weight 10,000) 10 g, 2-
1 g of acrylamide 2-methylpropanesulfonic acid was dissolved in a mixed solution of 200 ml of toluene and 100 ml of dimethylformamide, and the mixture was stirred at room temperature under a nitrogen stream for 1 hour, then gradually heated, and heated and stirred at 90 ° C. for 12 hours. The reaction solution was cooled, concentrated under reduced pressure, and the resulting precipitate was washed with ethanol, collected by filtration, and dried under reduced pressure to obtain the desired product.

[Synthesis Example 2] Polydimethylsiloxane
2-acrylamide 2-methylpropanesulfonic acid-acrylic acid block copolymer 10 g of poly [polydimethylsiloxane-4,4'-azobis (4-cyanopentanoamidopropyl)] (polydimethylsiloxane part average molecular weight 10,000) , 2-
1 g of acrylamide 2-methylpropanesulfonic acid and 4 g of acrylic acid were dissolved in a mixed solution of 200 ml of toluene and 100 ml of dimethylformamide, and the mixture was stirred at room temperature under a nitrogen stream for 1 hour, then gradually heated, and heated and stirred at 90 ° C. for 12 hours. The reaction solution was cooled, concentrated under reduced pressure, and the resulting precipitate was washed with ethanol, collected by filtration, and dried under reduced pressure to obtain the desired product.

[Synthesis Example 3] Polydimethylsiloxane
2-acrylamide 2-methylpropanesulfonic acid-2
-Acryloxyethyltrimethylammonium chloride-stearyl acrylate block copolymer 10 g of poly [polydimethylsiloxane-4,4'-azobis (4-cyanopentanoamidopropyl)] (polydimethylsiloxane average molecular weight 10,000) −
Acrylamide 2-methylpropanesulfonic acid 2 g, 2
-1 g of acryloxyethyltrimethylammonium chloride, 1 g of stearyl acrylate and 200 m of toluene
Dissolved in 100 ml of l-dimethylformamide mixed solution,
After stirring at room temperature for 1 hour under a nitrogen stream, the mixture was gradually heated, and heated and stirred at 90 ° C. for 12 hours. Cool the reaction solution,
The precipitate precipitated after concentration under reduced pressure was washed with ethanol, collected by filtration, and dried under reduced pressure to obtain the desired product.

[Synthesis Example 4] Polydimethylsiloxane
2-acrylamide 2-methylpropanesulfonic acid-2
-Methacryloxyethyldimethylammonium α-methylcarboxybetaine-acrylamide lock copolymer poly [polydimethylsiloxane-4,4′-azobis (4-cyanopentanoamidopropyl)] (polydimethylsiloxane part average molecular weight 10,000) 10 g, 2-
Acrylamide 2-methylpropanesulfonic acid 0.5
g, 2-methacryloxyethyldimethylammonium α
-0.5 g of methylcarboxybetaine and 10 g of acrylamide in 200 ml of toluene-dimethylformamide 1
After dissolving in a mixed solution of 00 ml and stirring at room temperature for 1 hour under a nitrogen stream, the mixture was gradually heated and heated and stirred at 90 ° C. for 12 hours. The reaction solution was cooled, concentrated under reduced pressure, and the resulting precipitate was washed with ethanol, collected by filtration, and dried under reduced pressure to obtain the desired product.

Synthesis Example 5 Polydimethylsiloxane
2-acrylamide 2-methylpropanesulfonic acid-3
-Methacryloxypropyl (tristrimethylsiloxy) silane-3-methacryloxypropylpolydimethylsiloxane block copolymer poly [polydimethylsiloxane-4,4'-azobis (4-cyanopentanoamidopropyl)] (polydimethylsiloxane part (Average molecular weight 5,000) 5 g, 2-acrylamide 2-methylpropanesulfonic acid 1 g, 3-methacryloxypropyl (tristrimethylsiloxy) silane 2 g, 3-methacryloxypropyl polydimethylsiloxane (polydimethylsiloxane part average molecular weight 5,000)
00) 5 g was dissolved in a mixed solution of 250 ml of toluene-50 ml of dimethylformamide, and the mixture was stirred at room temperature under a nitrogen stream for 1 hour, then gradually heated, and heated and stirred at 90 ° C. for 12 hours. The reaction solution was cooled, concentrated under reduced pressure, and the deposited precipitate was washed with methanol, collected by filtration, and dried under reduced pressure to obtain the desired product.

Synthesis Example 6 Polydimethylsiloxane
2-acrylamide 2-methylpropanesulfonic acid-N
-Stearylacrylamide-glyceryl methacrylate block copolymer poly [polydimethylsiloxane-4,4'-azobis (4-cyanopentanoamidopropyl)] (polydimethylsiloxane part average molecular weight 5,000) 10 g, 2-acrylamide 2- 1 g of methylpropanesulfonic acid, N-
After dissolving 1 g of stearylacrylamide and 5 g of glyceryl methacrylate in a mixed solution of 250 ml of toluene and 50 ml of dimethylformamide, the mixture was stirred at room temperature under a nitrogen stream for 1 hour, then gradually heated, and heated and stirred at 90 ° C for 12 hours. The reaction solution was cooled, concentrated under reduced pressure, and the resulting precipitate was washed with ethanol, collected by filtration, and dried under reduced pressure to obtain the desired product.

[Synthesis Example 7] Polydimethylsiloxane
2-acrylamide 2-methylpropanesulfonic acid-1
H, 1H, 2H, 2H-heptadecafluorodecyl acrylate block copolymer poly [polydimethylsiloxane-4,4′-azobis (4-cyanopentanoamidopropyl)] (polydimethylsiloxane part average molecular weight 5,000) 10 g, 2-acrylamide 2-methylpropanesulfonic acid 1 g, 1 g
1 g of H, 1H, 2H, 2H-heptadecafluorodecyl acrylate was dissolved in a mixed solution of 250 ml of toluene and 50 ml of dimethylformamide, and the mixture was stirred at room temperature under a nitrogen stream for 1 hour, then gradually heated, and heated and stirred at 90 ° C. for 12 hours. did. The reaction solution was cooled, concentrated under reduced pressure, and the resulting precipitate was washed with ethanol, collected by filtration, and dried under reduced pressure to obtain the desired product.

As the block copolymer synthesized by the method described above, only one kind may be used as a dispersant, or two or more kinds may be used as a mixture.

The block copolymer according to the present invention is a compound capable of uniformly dispersing an aqueous pigment. According to the present invention, the pigment dispersion efficiency and the dispersion stability are improved.

Examples 1 to 7 and Comparative Examples 1 to 6 The block copolymers obtained in the above Synthesis Examples 1 to 7 were evaluated for pigment dispersibility by the following method. The results are shown in Tables 1 and 2.

[Pigment Dispersibility] One hour after the sample was prepared and allowed to stand, the appearance was visually observed. (Evaluation criteria) ○: Uniformly dispersed ×: Pigment aggregated

[0096]

[Table 1]

[0097]

[Table 2]

As is clear from the results shown in Tables 1 and 2, the block copolymer of the present invention has excellent pigment dispersibility.

(Example 8, Comparative Example 7) As shown in Table 3, for a sunscreen cosmetic containing titanium oxide dispersed using the block copolymer of the present invention and a sunscreen cosmetic prepared by a conventional method, A comparison was made by a UV protection effect evaluation test.

[0100]

[Table 3]

The UV protection evaluation was performed by the following method.

[UV protection effect] Example 8 and Comparative Example 7
1 g of each sample was applied to a 3 × 3 cm inner part of the forearm of a specialized panel (40 persons), and an ultraviolet lamp (color si
mulator model 600, UV irradiation 1.56 MEDs / m
in) for 1 minute, and the panel itself evaluated the condition of the skin on the next day. (Evaluation results) As a result, 35 out of 40 persons answered that the UV protection effect of the sunscreen of Example 8 was superior to Comparative Example 7, and the remaining 5 persons were Examples 8 and 7 Both responded equally. This is considered to be because in Example 8, the amount of titanium dioxide dispersed was improved by the addition of the block copolymer (Synthesis Example 1), and the UV protection effect was also improved.

(Example 9, Comparative Example 8) As shown in Table 4, a solid eye shadow prepared using the block copolymer of the present invention and a solid eye shadow prepared by a conventional method were subjected to a usability evaluation test. A comparison was made.

[0104]

[Table 4]

The usage test was performed in the following manner.

[Usability (Coloring)] Forty panelists used the eye shadows of Example 9 and Comparative Example 8, and evaluated their coloring ability comparatively. (Evaluation Results) As a result, 36 out of 40 persons answered that the color development of the eye shadow of Example 9 was superior to that of Comparative Example 8, and the remaining four persons were equal to both Example 9 and Comparative Example 8. answered. This is considered to be because in Example 9, the dispersibility of various pigments was improved by blending the block copolymer (Synthesis Example 5).

(Example 10, Comparative Example 9) As shown in Table 5, a comparison was made between a powdery foundation prepared using the block copolymer of the present invention and a powdery foundation by a conventional method in a usability evaluation test. went.

[0108]

[Table 5]

The use test was performed in the following manner.

[Usability (Coloring)] Forty panelists used the powdery foundations of Example 10 and Comparative Example 9 to compare and evaluate the coloring ability. (Evaluation Results) As a result, 34 out of 40 persons were in Example 10.
Of the powdery foundation of Comparative Example 9 was superior to that of Comparative Example 9, and the remaining six persons answered that both Examples 10 and Comparative Example 9 were equivalent. This is probably because in Example 10, the dispersibility of various pigments was improved by the addition of the block copolymer (Synthesis Example 7).

From the above results, the dispersibility of the pigment was improved by blending the copolymer of the present invention, and as a result, a high UV protection effect or a good coloring property was exhibited, and the function was excellent even when applied to products. It was confirmed that. In addition, due to the structure of the copolymer of the present invention, the miscibility with the silicone oil, which has conventionally been incompatible with the pigment, is also improved. With this base, the UV protection effect of the sunscreen agent can be improved, and the coloring property of the makeup product can be improved.

Examples of the formulation are shown below.

[Formulation Example 1] Oil-based lipstick (combination component) blended amount (% by weight) titanium dioxide 5 candelilla wax 9 solid paraffin 8 beeswax 5 carnauba wax 5 polydimethylsiloxane (6 mPa · s) 26.5 decamethyl Cyclopentasiloxane 20 Lanolin 11 Isopropyl myristate 10 Block copolymer (Synthesis example 6) 0.5 Perfume Appropriate amount Oxidative preservatives Appropriate amount (Production method) Titanium dioxide and components other than perfume are mixed, heated and melted, Add titanium and fragrance and disperse uniformly with a homomixer. Pour into a mold, quench and stick.
Get an oily type lipstick.

Formulation Example 2 Solid blusher (combination component) Compounding amount (% by weight) Talc 80 Kaolin 9 Vaseline 3 Dimethylpolysiloxane (6 mPa · s) 3 Zinc myristate 4.5 Block copolymer (Synthesis example) 3) 0.5 Oxidizing preservatives Appropriate amount Perfume Appropriate amount (Preparation method) The components other than the perfume are mixed well with a blender, added with the perfume, treated with a pulverizer, and then compression molded to obtain a solid rouge.

[Formulation Example 3] Pencil-type eyebrow ink (combination component) Compounding amount (% by weight) Black iron oxide 20 Titanium oxide 5 Talc 10 Kaolin 15 Mokurou 20 Stearic acid 10 Beeswax 5 Vaseline 4 Polydimethylsiloxane (20 mPa · s) 10.5 Block copolymer (Synthesis example 4) 0.5 Oxidizing preservatives Appropriate amount (Production method) Titanium dioxide, iron oxide and talc are mixed with a blender. The other components are mixed, heated and melted, uniformly added to the powder portion, processed by a pulverizer and then compression-molded to obtain a pencil-type eyebrow ink.

[Formulation Example 4] Sunscreen (combination component) blending amount (% by weight) purified water residue 1,3-butylene glycol 5 titanium dioxide 5 zinc oxide 5 octyl paramethoxycinnamate 5 oxybenzone 3 block Copolymer (Synthesis Example 1) 1 Squalane 30 Glycerin diisostearate 2 Organically modified montmorillonite 1.5 Preservatives Appropriate amount Flavors Appropriate amount (Production method) A water-soluble component and a lipophilic component are each heated and dissolved at 70 ° C. The lipophilic component is gradually added together with the aqueous phase homogenizer treatment to obtain a sunscreen agent.

[Formulation Example 5] Deodorant stick (combination component) Compounding amount (% by weight) Aluminum chlorohydrate 23 Talc 15 Solid paraffin wax 2 Stearyl alcohol 8 Block copolymer (Synthesis Example 2) 1 Liquid paraffin 13. 5 Decamethylcyclopentasiloxane 36.5 Sorbitan fatty acid ester 1 Fragrance appropriate amount (Preparation method) Solid paraffin, stearyl alcohol, sorbitan fatty acid ester, and block copolymer (Synthesis Example 2) are dissolved in liquid paraffin by heating and mixed. The remaining powder is added, uniformly dispersed and mixed using a homomixer, poured into a mold and cooled and solidified to obtain a deodorant stick.

[Formulation Example 6] W / O emulsified foundation (combination component) blending amount (% by weight) sericite 5.4 kaolin 4 titanium dioxide 9.3 bengara 0.4 yellow iron oxide 0.8 black oxide Iron 0.2 Block copolymer (Synthesis example 5) 0.5 Liquid paraffin 4.5 Decamethylcyclopentasiloxane 12 POE-modified dimethylpolysiloxane 4 Purified water Residue 1,3-butylene glycol 5 Preservatives Appropriate amount Stabilization Agent 2.1 Appropriate amount of perfume (Preparation method) Heat and stir the aqueous phase at 70 ° C, add the powder part, treat with a homomixer, and add a stabilizer. 70 ° C
The heated oiliness is added to the mixture, and a homomixer treatment is performed. Stir and cool, add perfume at 45 ° C, cool to room temperature, W / O
An emulsified foundation is obtained.

[Formulation Example 7] Nail enamel (combination component) blending amount (% by weight) nitrocellulose 10 alkyd resin 10 acetyltributyl citrate 5 ethyl acetate 20 butyl acetate 10 ethanol 5 toluene 32 pearling agent 5 block copolymer (Synthesis Example 1) 3 (Production method) A pearl agent and a block copolymer (Synthesis Example 1) are added to a part of the alkyd resin and a part of the acetyltributyl citrate, and mixed well. The other components are mixed, added and uniformly dispersed to obtain a nail enamel.

[Formulation Example 8] Hair dye (color stick) (combination component) blending amount (% by weight) carbon black 2 beeswax 15 mokurou 10 block copolymer (synthesis example 4) 1 liquid paraffin 65.8 POE (20) Sesquioleic acid ester 1.2 Fragrance 5 Oxidation preservatives Appropriate amount (Preparation method) After heating and melting the oily components and mixing uniformly, add carbon black, mix and cool to obtain a hair dye (color stick) .

[0121]

The block copolymer according to the present invention has excellent pigment dispersibility. Therefore, the solvent dispersibility can be improved without particularly treating the pigment. In addition, by using the copolymer of the present invention in a cosmetic, a makeup cosmetic having particularly excellent coloring properties, a sunscreen agent having an excellent UV protection effect, and the like can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) A61K 7/032 A61K 7/032 7/043 7/043 7/13 7/13 7/38 7/38 7 / 42 7/42 (72) Inventor Toshio Yanagi 1050 Nippa-cho, Kohoku-ku, Yokohama-shi, Kanagawa Prefecture F-term in Shiseido Daiichi Research Center (reference) 4C083 AA122 AB132 AB212 AB222 AB232 AB242 AB432 AB442 AC012 AC022 AC032 AC072 AC102 AC122 AC242 AC342 AC352 AC372 AC392 AC402 AC422 AC442 AC472 AC532 AC542 AD072 AD092 AD152 AD161 AD162 AD172 AD262 AD512 CC12 CC13 CC14 CC17 CC19 CC28 CC36 DD11 DD17 DD21 DD23 DD27 DD32 EE01 EE07 EE17 FF01 FF05 4J035 BA02 CA02 GB02 GB02 GB02 GB

Claims (8)

[Claims] 1. A polysiloxane part containing at least one of the repeating units represented by the following general formulas (I) and (II) and a hydrophilic part containing at least a sulfonic acid group (—SO ₃ H). A block copolymer contained as a constituent unit. Embedded image Embedded image In the general formulas (I) and (II), each symbol has the following meaning. R ¹ : independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group; R ² : a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ³ : a C 1 to C 6 atom; An alkyl group or a cyano group; CO-Y-CO: a dibasic acid residue; A: -NH- or -O-: B: an alkylene group having 1 to 6 carbon atoms which may be via an oxygen atom; : A number from 1 to 10,000; p: a number from 0 to 6. 2. The amide group (-CON) is further added to the hydrophilic portion.
H ₂ ), a quaternary ammonium group [—N (R) ₃ ⁺ (R: each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)], carboxybetaine [R ′ (R ″) ₂ N ⁺ CH
^{_{2 COO - (R ', R}} '': -C 1 each independently
To 6), a carboxyl group (—COO)
H), a phosphate group [—O—PO (OH) ₂ ], a hydroxyl group (−
OH) and one or more hydrophilic groups selected from nitrogen-containing heterocyclic groups having a vinyl group.
The copolymer as described in the above. 3. The copolymer according to claim 1, wherein the polysiloxane moiety is derived from an azo group-containing polysiloxane compound. 4. The method according to claim 1, further comprising a hydrophobic part.
4. The copolymer according to any one of 3. 5. A (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 22 carbon atoms which may contain fluorine, wherein the hydrophobic portion has 1 to 22 carbon atoms. Substituted or unsubstituted alkyl (meth) acrylamide having a linear or branched alkyl group, a substituted or unsubstituted aromatic hydrocarbon having 6 to 12 carbon atoms, and a polysiloxane optionally containing fluorine The copolymer according to claim 4, wherein the copolymer is one or more selected from monomers. 6. The block copolymer according to claim 1, which is a pigment dispersant. 7. A cosmetic comprising the copolymer according to any one of claims 1 to 6. 8. The cosmetic according to claim 7, which contains a pigment.