JP2003081742A - Resin composition for cosmetic and cosmetic using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for cosmetics, enabling a plurality of performances required for cosmetics to be met simultaneously through using a resin having a combination of two or more properties, and to provide cosmetics using the resin composition. SOLUTION: This resin composition for cosmetics includes a block copolymer which has constituent unit derived from a compound bearing an ethylenically unsaturated bond, a number-average molecular weight of 1.0×10<3> to 1.0×10<6> and at least two glass transition points or melting points; wherein it is preferable that the block copolymer has at least one block composed of hydrophilic group-bearing constituent unit. The other objective cosmetics using the above resin composition are provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for cosmetics containing a block copolymer and a cosmetic using the same, and more particularly to a heavy-weight resin having two or more different characteristics in its skeleton. The present invention relates to a resin composition for cosmetics containing a block copolymer in which coalescing units are block-wise introduced, and a cosmetic using the same.

[0002]

2. Description of the Related Art Heretofore, there have been known cosmetics for skin, nails and hair which utilize a resin having a film-forming property. For example, for skin or nails, a film-forming resin is used for cosmetics for improving makeup retention, protecting the skin or nails, or coloring or other decoration on the skin or nails. Has been done. As a cosmetic for hair, a resin having a film-forming property is used for the purpose of maintaining styling due to affinity for hair and adhesiveness between hairs. For example, nonionic, anionic, cationic and amphoteric resins have hitherto been used as cosmetic resins for hair. Polyvinylmethyl ether, polyvinylpyrrolidone, etc. are used as the nonionic resin, but polyvinylipyrrolidone is easily affected by humidity conditions. There is a problem that it is easily affected by. That is, while the film before moisture absorption is hard and easily causes flaking phenomenon, when it is hot and humid, it becomes very flexible and causes a blocking phenomenon, and hairs stick to each other, and combing and brushing tend to be difficult. is there. In polyvinyl methyl ether, such an influence of humidity is more remarkable.

Examples of the anionic resin include copolymers of vinylcarboxylic acid (for example, acrylic acid, methacrylic acid and the like) having a carboxylic acid which is an anionic group, and styrene or alkyl acrylate. Unlike the nonionic resin, the anionic resin is unlikely to be affected by humidity, but has the same anionic property as the hair, and thus has a weak affinity for the hair. In general, an anion-based resin film is hard and has a high hair styling effect, but on the other hand, there is a problem that it is brittle and a flaking phenomenon easily occurs.
Furthermore, the addition of the cationic substance is restricted due to the fact that it is anionic, and there is a concern about a solidification phenomenon due to a rinse agent (cationic) or the like during hair washing. Cationic resins have a greater affinity for hair than the former two, but are susceptible to humidity as well as nonionic resins. In addition, there is concern about toxicity and skin irritation due to being cationic, and addition of an anionic substance is limited, and there is also concern about a solidification phenomenon due to shampoo (anionic) during hair washing.

Also, it can be easily removed by washing the hair,
The resin used is preferably water-soluble, because it is easily diluted with water when preparing a hair cosmetic composition, and alcohol-free hair cosmetic compositions are being demanded from the viewpoint of environmental problems. However, in general, there is a problem that the setting force is lowered when the water solubility of the resin is increased. To improve the drawbacks of hair cosmetics containing these anionic resin, cationic resin and nonionic resin, cosmetics using a zwitterionic polymer which is a copolymer having carboxybetaine or an amine oxide group as a hydrophilic group are used. Fees have been proposed (Japanese Patent Laid-Open Nos. 51-9732, 55-104209, and 10-7232).
No. 3, etc.). However, this zwitterionic polymer has problems such as insufficient compatibility with various cosmetic base materials.

The general-purpose ionic resins as described above have been playing a role of maintaining styling by utilizing their respective characteristics, and by their affinity to hair, film-forming ability and adhesiveness between hairs. However, the styling agents using these general-purpose ionic resins have problems such as stickiness during moisture absorption and stiffness during drying. Therefore, in an actual prescription system, the feel is improved by adding a small amount of an oil agent or the like to the polymer. Addition of an oil agent causes deterioration of polymer performance, and as a result, it becomes difficult to maintain the original high setting force. As one means for solving this, there is a demand for the development of a new polymer having a plurality of performances such as setting property and good touch property, and having easy washing property when washing hair. Based on such a background, in recent years, a thermoplastic elastomer soluble or dispersible in water or alcohol having a water-soluble graft chain in the main chain of a random copolymer has been studied, but stickiness during moisture absorption occurs, It has not been possible to obtain sufficient resin elasticity as a resin composition for cosmetics (Japanese Patent Laid-Open No. 8-512083, JP-A No. 11-1).
No. 81029).

By the way, thermoplastic elastomeric copolymers are well known, and typical ones are styrene-butadiene copolymers, styrene-isoprene copolymers, and hydrogenated polymers thereof (each of which is styrene-ethylene-copolymer).
Butylene copolymer and styrene-ethylene-propylene copolymer) are widely used. These block copolymers have both thermoplastic resin-like properties that impart solubility and strength to the copolymer, and rubber-like elasticity that impart flexibility and shape retention to the copolymer. Further, it is known that these block copolymers can be used as a compatibilizing agent for various general-purpose thermoplastic resins.
However, most thermoplastic elastomeric copolymers are usually soluble in water and / or alcoholic solvents,
It is insoluble or sparingly soluble and is not suitable for cosmetic resin compositions. If a thermoplastic elastomeric copolymer having the above-mentioned properties and having solubility in water and / or alcohol can be provided, it is useful for developing an improved cosmetic resin composition. Further, by using the water-soluble thermoplastic elastomer as a compatibilizing agent for general-purpose resins, the possibility of polymer blending (combination of anion resin and cation resin, etc.), which has hitherto been impossible, is expected.

[0007]

As described above, in the conventional general-purpose resin for hair setting agent, the resin alone cannot obtain a plurality of required performances such as high setting property and good feel, Actually, the performance has been maintained by using a combination system of various resins and addition of an oil agent and the like. However, the addition of these oil agents has a problem that the original resin performance is deteriorated.

The present invention has been made in view of the above problems, and by using a resin having two or more properties, it is possible to simultaneously satisfy a plurality of performances required for a cosmetic. It is an object to provide a resin composition for cosmetics and a cosmetic. Further, the present invention is a cosmetic or a cosmetic which has excellent film-forming properties on hair, skin or nails, has suppleness due to rubber elasticity, and has excellent usability without giving a sticky feeling or a feeling of strangeness due to film-forming. An object of the present invention is to provide a resin composition for cosmetics capable of producing a cosmetic.

[0009]

As a result of various studies to solve the above problems, the present inventor has found that a block copolymer having specific physical properties has, for example, flexibility of a film and shape retention of a film. It is possible to exhibit mutually contradictory characteristics required for a resin for cosmetics, and further, while satisfying these requirements, it also has performance such as hydrophilicity required for preparing a cosmetic or environmentally. Gaining knowledge,
The present invention has been completed through further studies. That is, the cosmetic resin of the present invention has a constitutional unit derived from a compound having an ethylenically unsaturated bond, and has a number average molecular weight of 1.0 × 10 ^3.
1.0 a × 10 ^6, and characterized in that it comprises a block copolymer having at least two or more glass transition point or melting point. The block copolymer may be a diblock copolymer, a triblock copolymer or a multiblock copolymer.

As a preferred embodiment of the present invention, there is provided the above-mentioned cosmetic resin composition, wherein the block copolymer has at least one block composed of a structural unit having a hydrophilic group. The hydrophilic group may be any of an anionic group, a cationic group, a nonionic group, a zwitterionic group and a polarizable group. As a more preferred embodiment of the present invention,
The hydrophilic group is a group of anionic groups consisting of a carboxylic acid group, a sulfuric acid group, a phosphoric acid group and salts thereof, an amino group (including a quaternized ammonium salt group), a pyridyl group and a cationic group consisting of these salts. A group of groups, a group of nonionic groups consisting of a hydroxyl group, an alkoxy group, an epoxy group, an amide group and a cyano group, a group of zwitterionic groups consisting of a carboxybetaine group, and a group of polarizable groups consisting of an amine oxide group. The above-mentioned resin composition for cosmetics is provided.

In a preferred embodiment of the present invention, the block copolymer has at least one block containing a structural unit represented by any one of the following general formulas (1) to (5).
The above-mentioned resin composition for cosmetics is provided.

[0012]

[Chemical 2]

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R ⁶ each represent a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³ , R ⁴ and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or an arylalkyl group or alkylaryl group having 7 to 24 carbon atoms, which is a combination thereof. X ¹ is-
Represents COO-, -CONH-, -O- or -NH-. A ⁻ represents an anion, and M represents a hydrogen atom, an alkali metal ion or an ammonium ion. m represents 0 or 1, and n represents an integer of 1 to 50.

As a preferred embodiment of the present invention, the above-mentioned resin composition for cosmetics, wherein the block copolymer contains a constitutional unit derived from an ethylenically unsaturated carboxylic acid and a constitutional unit derived from an ethylenically unsaturated carboxylic acid ester; The cosmetic resin composition, wherein the block copolymer contains 10 to 90% by weight of the unit derived from the ethylenically unsaturated carboxylic acid and 90 to 10% by weight of the unit derived from the ethylenically unsaturated carboxylic acid ester; The above-mentioned resin composition for cosmetics, wherein the block copolymer has a glass transition point or melting point substantially equal to the glass transition point or melting point of a homopolymer composed of a monomer forming at least one block of the block copolymer. ; Is provided. In the present specification, "substantially equal" includes not only the case where they are completely the same and the case where they are the same within the allowable range of the measurement error, but also the case where the difference between them is within 10 ° C.

In a preferred embodiment of the present invention, at least one block constituting the block copolymer is a block formed by post-treatment after polymerization; The above-mentioned resin composition for cosmetics in which the number average molecular weight of the block units constituting the coalescence is 10 ³ to 10 ⁵ ; the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the block copolymer ( M
The above resin composition for cosmetics having a w / Mn) of 2.5 or less is provided. The post-treatment includes quaternization treatment of nitrogen, amine oxide treatment, ester bond hydrolysis treatment, and the like.

In a preferred embodiment of the present invention, the block copolymer is a resin composition for cosmetics which is dispersible or soluble in water and / or alcohol; the block copolymer is 50 MPa or more (more preferably, Has a Young's modulus of 100 MPa or more) and is capable of forming a coating film having an elongation of 150% or more (more preferably 200% or more); the block copolymer is At least one of block copolymers
There is provided the above-mentioned cosmetic resin composition, which has a glass transition point or melting point substantially equal to the glass transition point or melting point of a homopolymer consisting of monomers constituting one block.

In a preferred embodiment of the present invention, the block copolymer is produced by controlled radical polymerization, wherein the resin for cosmetics comprises the block copolymer with an organic halide as an initiator. 8th group of the table,
The resin composition for cosmetics prepared by controlled radical polymerization using at least a metal complex having a metal selected from Group 9, 10 and 11 elements as a central metal, as a catalyst; The above-mentioned resin composition for cosmetics is characterized by being produced by controlled radical polymerization using a metal complex obtained from a copper halide and an amine compound as a catalyst; and the block copolymer is ethylenically unsaturated. A second compound having an ethylenically unsaturated bond is polymerized using a polymer initiator composed of a homopolymer of a first compound having a bond, and a first block composed of a constitutional unit derived from the first compound. A polymerization step for producing a copolymer containing a second block composed of a constitutional unit derived from the second compound, and the first and / or second block The cosmetic resin composition characterized in that a third block co serious condition produced blocks from the post-treatment step of generating and processing; is provided.

From another point of view, there is provided a cosmetic characterized by using the above-mentioned resin composition for cosmetics; the aforementioned cosmetic characterized by being for hair, nail and skin.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. In addition, in this specification, "-" shows the range which includes the numerical value described before and after that as a minimum value and a maximum value, respectively.

The cosmetic resin composition of the present invention contains a block copolymer. The block copolymer is a copolymer having a constitutional unit derived from a compound having an ethylenically unsaturated bond and having a number average molecular weight of 1.0 × 10 ^{3 to} 1.0 × 10 ⁶ . The number average molecular weight of the block copolymer is 1.0 ×
When it exceeds 10 ⁶ , problems such as high solution viscosity may occur when used as a cosmetic. On the other hand, when the number average molecular weight is less than 1.0 × 10 ³ , the film-forming ability is lowered, and there is a problem that sufficient performance cannot be obtained when the number average molecular weight is applied to a cosmetic. The preferred range of the weight average molecular weight of the block copolymer varies depending on the use, but when it is used as a hair cosmetic, particularly as a hair setting agent, it is preferably 5.0 × 10 ^{3 to} 3.0 × 10 ^5. ,
When used as a conditioning function-imparting agent, it is preferably 2.0 × 10 ^{4 to} 1.5 × 10 ⁵ . When used for cosmetics for skin and nails, 1.0 x 1
0 ^{4 to} 5 × 10 ⁵ are preferable, and 2.0 × 10 ^{4 to} 1.0 ×
10 ⁶ is more preferable.

The weight average molecular weight of the block copolymer measured by gel permeation chromatography (M
The ratio (Mw / Mn) of w) to the number average molecular weight (Mn) is not particularly limited, but is preferably 2.5 or less, more preferably 2.0 or less, and 1.8 or less. Is more preferable, and 1.5 or less is particularly preferable. When Mw / Mn exceeds 2.5, the homogeneity of the block copolymer tends to decrease. By utilizing the controlled radical polymerization method described later, a uniform block copolymer having a small Mw / Mn can be obtained.

The number average molecular weight of each block composition of the block copolymer is not particularly limited, but 1.0 ×
10 ^{3 to} 1.0 × 10 ⁵ is preferable and 5.0 × 10 ³ to
1.0 × 10 ⁵ is more preferable. Number average molecular weight is 1.0
It × tend to 10 ³ smaller than the viscosity from being too slow, whereas, the number-average molecular weight tends to 1.0 × 10 ⁵ greater than the viscosity becomes excessively high, depending on the resin performance in need It is preferably set within the above range.

The block copolymer of the present invention has a glass transition point or melting point of 2 or more. Of the two glass transition points, the one on the high temperature side is preferably 25 ° C. or higher,
40 ° C. or higher is more preferable, and 50 ° C. or higher is further preferable. Of the two glass transition points, the one on the low temperature side is preferably less than 25 ° C, more preferably 0 ° C or less,
-20 ° C or lower is more preferable. All melting points are preferably around room temperature or higher. It is preferable that the block copolymer has a glass transition point or a melting point derived from each block, that is, a glass transition of a homopolymer composed of monomers constituting one block of the block copolymer. It preferably has a glass transition point or melting point that is approximately equal to the point or melting point. For example, in the embodiment of the AB block copolymer, it has two glass transition points or melting points, and each glass transition point or melting point is approximately the same as the glass transition point or melting point of the homopolymer of A and B. Equal to is preferred. Also,
In the embodiment of the A-B-C type block copolymer, it has three glass transition points or melting points, and each glass transition point or melting point has a glass transition point or melting point which the homopolymer of A, B and C respectively has. Is preferably approximately equal to.

Glass transition point (Tg) and melting point (Tm)
The term “temperature” at which a polymer or a part thereof transforms from a brittle substance or solid to a rubber-like substance or liquid.
For example, it can be measured by a differential scanning calorimetry (DSC) method. The glass transition phenomenon of polymer is Introduc
ion to Polymer Science an
d Technology: An SPE Text
books (eds.HS Kaufman and JJ Falcetta), (John Wi.
ley & Sons: 1977).

When the block copolymer has at least one block having a hydrophilic group, for example, when used as a cosmetic for hair, the cosmetic has good hair washability and can be easily removed by washing the hair. Therefore, it is preferable. In addition, a block having a hydrophilic group is preferable because it can be incorporated into various types of cosmetics. The hydrophilic group may be any of an anionic group, a cationic group, a nonionic group and a zwitterionic group. Anionic groups include carboxylic acid groups, sulfuric acid groups, phosphoric acid groups and salts thereof; cationic groups include amino groups (including quaternary ammonium groups), pyridyl groups and salts thereof; nonionic groups As a hydroxyl group, an alkoxy group, an epoxy group, an amide group, a cyano group and the like; and as an amphoteric group, a carboxybetaine group, a sulfobetaine group, a phosphobetaine group and the like; Is mentioned. These hydrophilic groups can be obtained by polymerizing a monomer originally having a hydrophilic group or by producing a copolymer and then subjecting the copolymer to a post-treatment such as hydrolysis treatment. Can be introduced inside. In the present specification, the polarizable group is not a definite ionic group, but a group having a biased electron distribution while using both ionicity and covalent bond.

The block copolymer has a constitutional unit derived from a compound having an ethylenically unsaturated bond. As mentioned above, at least one block of the block copolymer preferably has a hydrophilic group. As the structural unit having a hydrophilic group, a structural unit represented by any of the following general formulas (1) to (5) is preferable.

[0027]

[Chemical 3]

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R ⁶ each represent a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³ , R ⁴ and R ⁵ represents an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or an arylalkyl group or alkylaryl group having 7 to 24 carbon atoms, which is a combination thereof; and X ¹ is -COO-,
Represents -CONH-, -O- or -NH-. A ⁻ represents an anion, and M represents a hydrogen atom, an alkali metal ion or an ammonium ion. m represents 0 or 1,
n represents an integer of 1 to 50.

R³, R^FourAnd R^FiveThe carbon source that each represents
Alkyl groups having 1 to 24 children include linear, branched, and
And cyclic alkyl groups are also included. R³, R^FourAnd
And R ^FiveAlkyl groups of arylalkyl groups represented by
Part, and the alkyl group part of the alkylaryl group.
The same is true.

[0030] A ^- as the anion represented by the include anionic groups of an acid, for example, a halogen ion, sulfate ion, COO ^-, and the like. Examples of the alkali metal ion represented by M include Na ⁺ and K ⁺ .
In addition to NH ₄ ⁺ derived from ammonia, the ammonium ion represented by M includes methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, n-butylamine, allylamine, ethylenediamine, morpholine. And volatile amines such as pyridine; non-volatile amines such as mono-, di- or triethanolamine, mono-, di- or triisopropanolamine, aminoethylpropanol, aminoethylpropanediol and lysine; amines such as Also included are alkyl ammonium ions derived from

The block containing the constitutional unit represented by any one of the above general formulas (1) to (5) is represented by the above general formulas (1) to (5).
It can be produced by polymerizing using a double bond-containing compound corresponding to the structural unit represented by (5) as a monomer. Even when the compound corresponding to the constitutional unit represented by the general formulas (1) to (5) is not used as a monomer, the resulting block is hydrolyzed after polymerization using another monomer. It can be manufactured by subjecting to post-treatment. For example, a block copolymer having a block composed of the structural unit represented by the general formula (1) uses (meth) acrylic acid ester as a copolymerization monomer,
It can also be produced by synthesizing a copolymer having a block composed of the monomer and then hydrolyzing the block. The block copolymer may be a block copolymer having two or more types of blocks composed of the structural units represented by any of the general formulas (1) to (5).

Hereinafter, examples of compounds having an ethylenically unsaturated bond capable of forming the block copolymer (including examples of compounds capable of forming the units represented by the general formulas (1) to (5)) will be given. However, the present invention is not limited to the following specific examples. Examples of nonionic monomers include unsaturated methyl acrylate, ethyl acrylate, -n-propyl acrylate, isopropyl acrylate, -n-butyl acrylate, isobutyl acrylate, -t-butyl acrylate, and acrylic. Acid-n-pentyl, acrylate-n-hexyl, cyclohexyl acrylate, acrylate-n-heptyl, acrylate-n-octyl, acrylate-2-ethylhexyl, acrylate nonyl, decyl acrylate, dodecyl acrylate, Phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, acrylate-2
-Hydroxyethyl, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate,
2-Aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoroacrylic acid Methyl ethyl, 2-perfluoroethyl ethyl acrylate,
2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroacrylate Acrylic acid esters such as ethylmethyl, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate; styrene, α
-Aromatic alkenyl compounds such as methylstyrene, p-methylstyrene and p-methoxystyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;

Conjugated diene compounds such as butadiene and isoprene; halogen-containing unsaturated compounds such as vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene and vinylidene fluoride; silicon such as vinyltrimethoxysilane and vinyltriethoxysilane. Unsaturated compounds containing; unsaturated dicarboxylic acid compounds such as maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid; vinyl acetate, vinyl propionate, pivalin Vinyl ester compounds such as vinyl acrylate, vinyl benzoate and vinyl cinnamate;
Maleimide compounds such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; methylmethacrylate, ethylmethacrylate, methacrylic acid -N
-Propyl, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -tert-butyl methacrylate, -n-pentyl methacrylate, -n-hexyl methacrylate, cyclohexyl methacrylate, Methacrylic acid-n-heptyl, methacrylic acid-n-octyl, methacrylic acid-2-ethylhexyl, nonylmethacrylate, decylmethacrylate, dodecylmethacrylate, phenylmethacrylate, toluylmethacrylate, meta Benzyl acrylate, isobornyl methacrylate, methacrylic acid-2
-Methoxyethyl, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, methacrylic acid 2
-Aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethylmethacrylate, methacrylic acid-2-tri Fluoromethyl ethyl, methacrylic acid-2-perfluoroethyl ethyl, methacrylic acid-2-perfluoroethyl-2
-Perfluorobutylethyl, 2-perfluoroethylmethacrylate, perfluoromethylmethacrylate, diperfluoromethylmethylmethacrylate, -2-perfluoromethyl-2-perfluoroethylmethylmethacrylate, meta Methacrylic acid esters such as 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl methacrylate and 2-perfluorohexadecylethyl methacrylate;

Hydroxyethyl (meth) acrylate,
Polyethylene glycol (meth) acrylate, methoxy poly (ethylene glycol / propylene glycol)
Monomers derived from (meth) acrylic acid or (meth) acrylamide such as mono (meth) acrylate, polyethylene glycol di (meth) acrylate, N-polyalkyleneoxy (meth) acrylamide and alkylene oxide having 2 to 4 carbon atoms. And hydrophilic nonionic monomers such as N-cyclohexylmaleimide, N-phenylmaleimide, N-vinylpyrrolidone, N- (meth) acryloylmorpholine and acrylamide;

As an example of the anionic monomer, (meth)
Unsaturated carboxylic acid compounds such as acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, crotonic acid; unsaturated polybasic acid anhydrides (eg succinic anhydride, phthalic anhydride, etc.) and hydroxyl group-containing ( Half-ester compounds with (meth) acrylate (for example, hydroxyethyl (meth) acrylate, etc.); styrene sulfonic acid,
Examples thereof include compounds having a sulfonic acid group such as sulfoethyl (meth) acrylate; compounds having a phosphoric acid group such as acid phosphooxyethyl (meth) acrylate; These anionic unsaturated monomers can be used as an acid or partially neutralized or completely neutralized,
Alternatively, the acid may be subjected to copolymerization as it is and then partially or completely neutralized. Examples of the base used for the neutralization include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, ammonia water, amine compounds such as mono-, di-, triethanolamine and trimethylamine.

Examples of the cationic monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate and N, N. −
Diethylaminopropyl (meth) acrylate, N, N
-Dimethylaminoethyl (meth) acrylamide, N,
N-diethylaminoethyl (meth) acrylamide,
N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, p-dimethylaminomethylstyrene, p-dimethylaminoethylstyrene, p-diethylaminomethylstyrene, p-diethylaminoethylstyrene, etc. , Cationizing agents (for example, alkyl halides such as methyl chloride, methyl bromide and methyl iodide, dialkyl sulfates such as dimethylsulfate, N- (3-chloro-2-hydroxypropyl) -N, N, N -Cationized with an epichlorohydrin adduct of a tertiary amine mineral salt such as trimethylammonium chloride, an inorganic salt such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, or a carboxylic acid such as formic acid, acetic acid or propionic acid) Cationic monomers are mentioned.

Specific examples of the zwitterionic monomer include compounds obtained by reacting the above-mentioned specific examples of the cationic monomer precursor with a modifying agent such as sodium or potassium haloacetate. . In addition, specific examples of the polarizable monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (Meth) acrylamide, vinyl N, N-dimethylaminopropionate, p-dimethylaminomethylstyrene, p-dimethylaminoethylstyrene, p
-Amine oxide compounds such as diethylaminomethylstyrene and p-diethylaminoethylstyrene; and the like. These monomers may be used alone or in combination of two or more.

Among these, acrylic ester, methacrylic ester, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound or halogen-containing unsaturated compound is preferably used from the viewpoint of industrial availability. .

A preferred embodiment of the block copolymer is a block copolymer containing at least one type of block composed of ethylenically unsaturated carboxylic acid units and at least one type of block composed of ethylenically unsaturated carboxylic acid ester units. . The ethylenically unsaturated carboxylic acid unit is preferably a unit derived from a monomer having a high Tg and exhibiting hydrophilicity, for example, a unit derived from acrylic acid or methacrylic acid. On the other hand, as the ethylenically unsaturated carboxylic acid ester unit, a unit derived from a monomer having a low Tg and exhibiting hydrophobicity is preferable, and for example, a unit derived from an acrylic acid ester or a methacrylic acid ester is preferable. The composition ratio of the ethylenically unsaturated carboxylic acid block and the ethylenically unsaturated carboxylic acid ester block constituting the polymer is preferably 10 to 90% by weight for the former and 90 to 10% by weight for the latter, and more preferably The former is 15 ~
80% by weight, the latter is 80 to 15% by weight, more preferably the former is 20 to 50% by weight and the latter is 80 to 50% by weight. When the proportion of the ethylenically unsaturated carboxylic acid block is less than 10% by weight, the block copolymer tends to be insoluble in water, and when the proportion of the ethylenically unsaturated carboxylic acid ester block is less than 10% by weight. The film-forming property tends to deteriorate, and the rubber elasticity of the resin significantly decreases. In the present specification, the “structural unit derived from a compound” means not only a structural unit formed as a result of polymerization using the compound as a monomer, but also a result of post-treatment such as hydrolysis as described above. A structural unit that is derived from the compound structurally is also included.

The block copolymer may be in the form of a diblock copolymer, a triblock copolymer or a multiblock copolymer. For example, the block copolymer is a hard block A (a block having a high Tg).
And a soft block B (low Tg block), an AB diblock copolymer, an ABA triblock copolymer, and a BAB triblock copolymer. Examples thereof include a combination and an (AB) _n type multi-block copolymer. Among these, in order to impart rubber elasticity to the resin, an ABBA type triblock copolymer, (AB)
_N- type multiblock copolymers or mixtures thereof are preferred.

The structure of the block copolymer is a linear block copolymer or a branched (star) block copolymer, and may be a mixture thereof. The structure of such a block copolymer may be properly used according to the required characteristics.

The block copolymer is preferably dispersible or soluble in water and / or alcohol. The water solubility (or alcohol solubility) of the block copolymer means that 1 part by weight of the block copolymer and 99 parts by weight of a mixed solution of deionized water and / or ethanol are heated and stirred at 60 ° C. for 2 hours, and after cooling, 1 After being left at room temperature for a day, the aqueous solution was homogeneous without forming a precipitate,
It can be confirmed by the fact that the transmittance at 55 nm is 70% or more. Further, "dispersible" means that the fine particles of the above copolymer are dispersed in water and / or alcohol without precipitation and become an emulsion or latex.

The block copolymer preferably has a Young's modulus of 50 MPa or more and can form a coating film having an elongation of 150% or more, and has a Young's modulus of 100 MPa or more and 200%. More preferably, it is possible to form a coating film having the above elongation rate. The Young's modulus and elongation can be measured by a film tensile test based on JIS K7161. When the block copolymer is capable of forming a film having Young's modulus and elongation in the above range,
When the resin composition for cosmetics of the present invention is used for cosmetics for hair, it is preferable because the cosmetics for hair have good setting power and excellent touch.

The method for producing the block copolymer is not particularly limited, but it is preferable to use controlled polymerization. Examples of the controlled polymerization include living anionic polymerization and radical polymerization using a chain transfer agent, and living radical polymerization developed in recent years. Among them, a living radical polymerization, which is one of the controlled radical polymerization, is used to produce a block. It is preferable because the molecular weight and structure of the copolymer can be easily controlled.

Living radical polymerization refers to radical polymerization in which the activity at the polymerization end is maintained without loss.
In a narrow sense, living polymerization refers to polymerization in which the terminals always have activity, but in general, pseudo-living polymerization in which the terminals are inactivated and activated are in equilibrium It is used in the meaning included and is also used in the latter meaning in the present specification. Living radical polymerization has been actively studied in various groups in recent years. For example,
Those using a chain transfer agent such as polysulfide, cobalt porphyrin complex (J. Am. Chem. Soc. 1)
994, 116, 7943) or a radical scavenger such as a nitroxide compound (Macromolec)
ules, 1994, 27, 7228), atom transfer radical polymerization using an organic halide as an initiator and a transition metal complex as a catalyst (Atom Transfer Rad).
(ICal Polymerization: ATRP)
And so on. In the present invention, the block copolymer may be produced by any method, but it is preferable to use atom transfer radical polymerization for ease of control.

In the atom transfer radical polymerization, an organic halide or a sulfonyl halide compound is used as an initiator, and a metal having a metal selected from the elements of Group 8, 9, 10 or 11 of the periodic table as a central metal is used. The complex can be used as a catalyst. For example, Matyjaszew
ski et al. Am. Chem. Soc. 1995, 1
17, 5614; Macromolecules, 19
95, 28, 7901; Science, 1996, 2
72,866; or Sawamoto et al., Macr.
OMolecules, 1995, 28, 1721 ;, an example of the atom transfer radical polymerization method is described, and it is preferably used in the present invention. According to these methods, in general, the polymerization rate is very high, and although the radical polymerization system is apt to cause termination reaction such as coupling of radicals, the polymerization proceeds in a living manner and the molecular weight distribution A polymer having a narrow Mw / Mn of about 1.1 to 1.5 can be obtained. Further, the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

In the atom transfer radical polymerization method, a monofunctional, difunctional or polyfunctional organic halide or a sulfonyl halide compound can be used as an initiator. These may be properly used depending on the purpose, but when a diblock copolymer is produced, it is preferable to use a monofunctional compound as an initiator, and when a triblock copolymer is produced, a bifunctional copolymer is used. It is preferable to use a polyfunctional compound, and in the case of producing a branched block copolymer, it is preferable to use a polyfunctional compound.

Examples of the monofunctional compound usable as the initiator include compounds represented by the following formula. _{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) -C
_{H 3, C 6 H 5 -C} (X) (CH 3) 2, R 11 -C (H)
(X) -COOR ¹² , R ¹¹ -C (CH ₃ ) (X) -CO
OR ¹² , R ¹¹ -C (H) (X) -CO-R ¹² , R ¹¹ -C
_{(CH 3) (X) -CO} -R 12, R 11 -C 6 H 4 -SO
₂ X, in the formula, C ₆ H ₄ represents a phenylene group (which may be ortho-substituted, meta-substituted or para-substituted). R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. X represents chlorine, bromine or iodine. R ¹² represents a monovalent organic group having 1 to 20 carbon atoms.

Examples of the bifunctional compound that can be used as the initiator include compounds represented by the following formula. _{X-CH 2 -C 6 H 4} -CH 2 -X, X-CH (C
_{H 3) -C 6 H 4 -CH} (CH 3) -X, X-C (CH 3) 2
_{-C 6 H 4 -C (CH 3} ) 2 -X, X-CH (COOR 13)
_{- (CH 2) n -CH (} COOR 13) -X, X-C (CH
^{_{3) (COOR 13) - (}} CH 2) n -C (CH 3) (COO
^{R 13) -X, X-CH} (COR 13) - (CH 2) n -CH
(COR ¹³ ) -X, X-C (CH ₃ ) (COR ¹³ )-
_{(CH 2) n -C (CH} 3) (COR 13) -X, X-CH 2
_{-CO-CH 2 -X, X-} CH (CH 3) -CO-CH
_{(CH 3) -X, X-} C (CH 3) 2 -CO-C (CH 3)
_{2 -X, X-CH (C} 6 H 5) -CO-CH (C 6 H 5) -
_{X, X-CH 2 -COO- (} CH 2) n -OCO-CH 2 -
_{X, X-CH (CH 3} ) -COO- (CH 2) n -OCO
_{-CH (CH 3) -X, X} -C (CH 3) 2 -COO-
_{(CH 2) n -OCO-C} (CH 3) 2 -X, X-CH 2 -
_{CO-CO-CH 2 -X,} X-CH (CH 3) -CO-C
_{O-CH (CH 3) -X} , X-C (CH 3) 2 -CO-C
_{O-C (CH 3) 2} -X, X-CH 2 -COO-C 6 H 4 -
_{OCO-CH 2 -X, X-} CH (CH 3) -COO-C 6
_{H 4 -OCO-CH (CH 3} ) -X, X-C (CH 3) 2 -
_{COO-C 6 H 4 -OCO-} C (CH 3) 2 -X, X-SO
During ₂ -C ₆ H ₄ -SO ₂ -X formula, R ¹³ is an alkyl group having 1 to 20 carbon atoms, 7 to number 6 to 20 aryl group or the number of carbon-carbon
It represents 20 aralkyl groups, and when two or more R ^13's are present in one molecule, the two or more R ^13's may be the same or different. C ₆ H ₄ represents a phenylene group (which may be ortho-substituted, meta-substituted or para-substituted). C ₆ H ₅ represents a phenyl group. n represents an integer of 0 to 20. X represents chlorine, bromine or iodine.

Examples of the polyfunctional compound that can be used as the initiator include compounds represented by the following formula. _{C 6 H 3 - (CH 2} -X) 3, C 6 H 3 - (CH (C
_{H 3) -X) 3, C} 6 H 3 - (C (CH 3) 2 -X) 3, C 6 H
_{3 - (OCO-CH 2 -X} ) 3, C 6 H 3 - (OCO-CH
_{(CH 3) -X) 3,} C 6 H 3 - (OCO-C (CH 3) 2 -
_{X) 3, C 6 H 3} - represents a (SO ₂ -X) ₃ wherein, C ₆ H ₃ is the position of the trisubstituted phenyl group (the substituent may be any of 1-position to 6-position). X represents chlorine, bromine or iodine.

If an organic halide or a sulfonyl halide compound having a functional group other than the one that initiates the polymerization is used, a polymer having a functional group introduced at the terminal can be easily obtained. As such a functional group, an alkenyl group,
Examples thereof include a hydroxyl group, an epoxy group, an amino group, an amide group and a silyl group.

The organic halide or sulfonyl halide compound which can be used as these initiators has a carbon to which a halogen is bonded bonded to a carbonyl group or a phenyl group, and the carbon-halogen bond is activated. A compound that initiates polymerization. The amount of the initiator used is adjusted to the required molecular weight of the block copolymer,
It may be determined from the ratio with the monomer. That is, the initiator 1
The molecular weight of the block copolymer can be controlled depending on the number of monomers used per molecule.

The transition metal catalyst used as the catalyst for the atom transfer radical polymerization is not particularly limited, but preferred are monovalent and zerovalent copper, divalent ruthenium, divalent iron and divalent iron. A nickel complex is mentioned. Among these, it is preferable to use a copper complex from the viewpoint of cost and reaction control. When a complex is used as the metal catalyst, a complex synthesized in advance may be added to the polymerization system, or a metal salt and a ligand which forms a complex by coordinate-bonding to the metal are each added to the polymerization system. To form a complex in the system. Above all, it is preferable to use copper halide and an amine compound capable of coordinatively binding to copper as the metal catalyst, and to add each of them into the polymerization system.

Examples of the monovalent copper compound usable as the catalyst for the atom transfer radical polymerization include, for example, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and cuprous oxide. Examples include copper and cuprous perchlorate. When a copper compound is used, 2,2′-bipyridyl and its derivative, 1,10-phenanthroline and its derivative, tetramethylethylenetriamine (T
MEDA), pentamethyldiethylenetriamine, polyamines such as hexamethyl (2-aminoethyl) amine, and the like can be added as ligands. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also preferable as the catalyst. When using a ruthenium compound as a catalyst, you may add aluminum alkoxide as an activator. Further, a bivalent iron bistriphenylphosphine complex (F
eCl ₂ (PPh ₃ ) ₂ , a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ) and a divalent nickel bistributylphosphine complex (NiBr ₂ (PBu ₃ ) ₂ ) are also used as catalysts. preferable. The amounts of the catalyst, ligand and activator used are not particularly limited, but may be appropriately determined depending on the relationship between the amounts of the initiator, monomer and solvent used and the required reaction rate.

The atom transfer radical polymerization can be carried out without solvent (bulk polymerization) or in various solvents. Examples of the solvent to be used include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Solvents; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; ester solvents such as ethyl acetate, butyl acetate; ethylene Carbonate,
Carbonate-based solvents such as propylene carbonate; dimethylformamide, dimethylsulfoxide,
Examples thereof include N-methylpyrrolidone and water. These may be used alone or in combination of two or more. As described above, when the polymerization is carried out without a solvent, bulk polymerization is performed. On the other hand, when a solvent is used, the amount to be used may be appropriately determined from the relationship between the viscosity of the entire system and the required stirring efficiency (that is, reaction rate).

The polymerization can be carried out at room temperature to 200 ° C., preferably 50 to 150 ° C.

To produce a block copolymer by the above-mentioned polymerization, a method of sequentially adding monomers, a method of polymerizing the next block by using a polymer synthesized beforehand as a polymer initiator, and a method of polymerizing separately Examples include a method of binding the coalesced product by a reaction. These methods may be used properly according to the purpose, but from the viewpoint of simplicity of the production process, the method of sequentially adding monomers or using a polymer initiator is preferable.

The method for producing the block polymer is not particularly limited, but the block produced by controlled radical polymerization using copper halide as a catalyst and sequential addition of monomers using an amine ligand. It is preferable because the molecular weight of the polymer can be easily controlled. In particular, the use of dimethylformamide as the reaction solvent is more preferable because the reaction rate is improved due to the chelating effect on the catalyst.

The block copolymer obtained by the polymerization is
It may be used as it is in the cosmetic resin composition of the present invention, or may be used after being subjected to a post-treatment such as hydrolysis.
By controlling the modification ratio by the post-treatment, various properties such as water solubility and film-forming ability of the resulting block copolymer can be set within a desired range according to the application. Examples of the post-treatment include hydrolysis treatment, quaternization treatment, amine oxide treatment and the like. For example, a block derived from acrylic acid or methacrylic acid having a carboxylic acid group that is a hydrophilic group (for example, represented by the general formula (1) by a hydrolysis treatment) Block having a structural unit that is formed). The hydrolysis treatment of the ester can be performed using an acid catalyst such as hydrochloric acid or p-toluenesulfonic acid, or an alkali catalyst such as sodium hydroxide. The hydrolysis rate can be controlled by the amount of catalyst and the reaction time. After hydrolysis, the produced carboxylic acid may be partially or completely neutralized before use. For the neutralization, for example, a base such as an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide; an ammonia water, an amine compound such as mono-, di-, triethanolamine or trimethylamine; or the like is used.

A block having a quaternary ammonium group which is a cationic group (for example, represented by the above general formula (2)) is obtained by quaternizing a block made of (meth) acrylate having an amino group. Blocks) can be formed. The quaternization treatment includes alkyl halides such as methyl chloride, methyl bromide and methyl iodide; dialkyl sulfates such as dimethylsulfate and N- (3-chloro-2).
-Hydroxypropyl) -N, N, N-trimethylammonium chloride and other tertiary amine mineral salt epichlorohydrin adducts; inorganic salts such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid; formic acid, acetic acid, propionic acid Carboxylic acid such as; and cationizing agent such as. Further, by subjecting a block composed of (meth) acrylate having an amino group to an amine oxide treatment, a block having an amine oxide group which is a polarizable group (for example,
The block represented by the general formula (3) can be formed. The amine oxide treatment is carried out using a peroxide such as hydrogen peroxide, ammonium persulfate, sodium persulfate, peracetic acid, metachloroperbenzoic acid, benzoyl peroxide, t-butyl hydroperoxide or an oxidizing agent such as ozone. be able to.

The resin composition for cosmetics of the present invention can be used for cosmetics for various purposes. Above all, it is preferably used for hair cosmetics, skin cosmetics, and nail cosmetics.
The block copolymer is a resin exhibiting various properties required for various cosmetics by determining the composition of each block in consideration of the hard / soft balance and the hydrophilic / hydrophobic balance. be able to. For example, in a cosmetic containing the block copolymer composed of a hydrophilic segment, a high-strength segment and a high-elasticity segment, with a settability, there is no stickiness when absorbing moisture and no stiffness when drying, and moreover it is easy to wash with water. It becomes a cosmetic composition for hair that can be easily removed and has good hair washability. Also, similarly,
By appropriately setting the composition of the segments constituting the block copolymer and the composition in each segment, the composition can be easily and uniformly spread on the skin, feels pleasant on the skin, and has high penetration of the pharmaceutically active agent and the like. It is possible to provide a skin cosmetic that is capable of penetrating through the skin. Further, similarly, by appropriately setting the composition of the segment constituting the block copolymer and the composition in each segment, the composition easily and uniformly spreads over the nail, and a film is easily formed, and It is possible to obtain a nail cosmetic with high retention.

Each cosmetic will be described in detail below. (Hair Cosmetics) The resin composition for cosmetics of the present invention can be used for hair cosmetics for various purposes such as shampoo, rinse, treatment, setting agent and permanent wave liquid. Also, liquids, creams, emulsions,
It can be used for hair cosmetics in any form such as gel and mousse. For example, the block copolymer, known shampoo, rinse, treatment, setting agent,
It may be added in place of a known resin in hair cosmetics such as a permanent wave liquid. At this time, you may use together with the well-known resin conventionally used. The preferred range of the content of the block copolymer in the hair cosmetic composition depends on the form and purpose of the hair cosmetic composition and the type and amount of other materials used in combination, but the block copolymer is for hair. 0.01 to 1 in cosmetics
It is preferably contained in an amount of 0% by weight.

The embodiments in which the present invention is applied to hair cosmetics will be described in detail below. (1) Setting Agent In the present specification, the term “setting agent” is used as a broad concept including all hair cosmetics used for the purpose of setting hair. Aerosol hair sprays, pump hair sprays, foam hair sprays, hair mists, set lotions, hair creams, hair oils and other forms are also included. The setting agent is usually prepared by dissolving and / or dispersing a resin having a setting ability using water and / or alcohols such as ethanol and isopropanol as a solvent.
As the resin having setting ability, the block copolymer can be used alone or together with a known cationic, anionic, nonionic or amphoteric known setting polymer.

As a known polymer for setting which can be used in combination, as a cationic polymer, for example, an ether of hydroxycellulose and glycidyltrimethylammonium chloride (trade name: Rhogard G (manufactured by Lion Corporation)), trade name: Polymer JR- 30M-125 and -400 (manufactured by Union Carbide Co.), a quaternized product of vinylpyrrolidone-dimethylaminoethyl methacrylate copolymer (trade name: GAFQUAT 734 and 7).
55 (manufactured by GAF), dimethyl diallyl ammonium chloride polymer (trade name: MERQUAT 100 (manufactured by Merck)), dimethyl diallyl ammonium chloride acryloamide copolymer (trade name: MERQUAT).
550 (manufactured by Merck) and the like. Examples of the anionic polymer include a copolymer of (meth) acrylic acid and alkyl methacrylate (trade name: Diahold (manufactured by Mitsubishi Chemical Co., Ltd.), trade name: Plus Size (manufactured by Mutual Chemical Co., Ltd.), maleic acid. Monoalkyl ester and methyl vinyl ether copolymer (trade name: GANTREZ (I
SP company)) and the like. Examples of the nonionic polymer include a polyvinylpyrrolidone polymer (trade name: PVP (manufactured by ISP)) vinylpyrrolidone and a vinyl acetate copolymer (trade name: LUVISKOL (manufactured by BASF)). In amphoteric polymers, for example,
Examples thereof include methacrylic acid ester copolymer (trade name: Yukaforma-AM-75W (manufactured by Mitsubishi Chemical Corporation)).

In a mode of a hair cosmetic (mousse) for a set which can be jetted in a foam state, the composition of the block copolymer is 0.01 to 10% by weight, and the known set polymer is 0 to 15% by weight. % By weight, 0.1 nonionic surfactant
˜5 wt%, liquefied gas 3 to 25 wt%, and water-based water-soluble solvent 60 wt% to the balance. However, it is preferable to prepare water such that water is contained in the hair cosmetic in an amount of 60% by weight or more. In the gel embodiment, the composition of the block copolymer is 0.01 to 10% by weight, a known set polymer is 0 to 15% by weight, a gel base is 0.1 to 3% by weight, and water is 72% by weight. % To the balance is preferable. In a hair spray embodiment, the composition of the block copolymer is 0.01 to 10% by weight, a known set polymer is 0 to 15% by weight, and a solvent is 30 to 30% by weight.
It is preferably 80% by weight and the propellant content is 10 to 70% by weight.

Examples of nonionic surfactants usable in mousses include sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether. , Polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamides and the like. Examples of propellants that can be used in the spray or mousse include liquefied petroleum gas, liquefied gas such as dimethyl ether and halogenated hydrocarbon, and compressed gas such as air, carbon dioxide gas and nitrogen gas.

(2) Conditioning function-imparting agent In the present specification, "conditioning function-imparting agent"
The term is used as a broad concept including all hair cosmetics used for the purpose of conditioning the condition of hair. Any form of shampoo, conditioner, permanent liquid, etc. is included. These hair cosmetics include water and / or ethanol such as shampoo, rinse, permanent and the like, and alcohol containing alcohol such as isopropanol, and water and / or ethanol, isopropanol such as hair treatment. Alcohols such as, or alcohols and / or boiling point 5
Included are hair cosmetics using hydrocarbons at 0 ° C to 300 ° C as a solvent. Like the set agent described above, in the present invention,
As the resin having conditioning ability, the block copolymer can be used alone or together with a conventional cationic, anionic, nonionic or amphoteric conditioning polymer.

The shampoo mode is prepared by adding the block copolymer to a known anionic, amphoteric or nonionic surfactant base material. Examples of the anionic surfactant base material include N-coconoyl-N-methyl-
β-alanine sodium, N-myristoyl-N-methyl-β-alanine sodium and other N-fatty acid acyl-
N-methyl-β-alanine salt and the like; as the amphoteric surfactant base material, cocoaside propyl betaine, dimethyl lauryl betaine, bis (2-hydroxyethyl) lauryl betaine, cyclohexyl lauryl amine oxide, dimethyl lauryl amine oxide, bis (2-Hydroxyethyl) laurylamine oxide and the like; Examples of the nonionic surfactant base material include stearic acid diethanolamide, coconut oil fatty acid diethanolamide, sorbitan sesquioleate, polyoxyethylene stearyl ether and the like.

The rinse mode is prepared by adding the block copolymer to a known cationic surfactant.
Examples of the cationic surfactant base material include stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and stearyl dimethyl benzyl ammonium chloride. In the form of permanent liquid,
The block copolymer is added to a known oxidizing agent such as bromate, perboric acid, etc., and reducing agent such as thioglycolic acid and its salt, cysteine, etc. to prepare.

In the hair treatment embodiment, the above-mentioned block is used in combination with or in the form of a known cationic surfactant base material and / or a cationized polymer such as a cationic polypeptide, a cationic cellulose or a cationic polysiloxane. Prepare by adding the copolymer. As the cationic surfactant base material, those exemplified as being usable for rinsing can be used for hair treatment.

In the hair cosmetic composition of any of the setting agent and the conditioning function-imparting agent, in addition to the above-mentioned various components, other optional components may be added, if necessary, within a range that does not affect the effects of the present invention. Can be blended. Examples of the optional component include hydrocarbons such as liquid paraffin, petrolatum, solid paraffin, squalane, and olefin oligomers; ethanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, and the like. Chain alcohols; alcohols such as monostearyl glycerin ether, 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterols, hexyldecanol, isostearyl alcohol, octyldodecanol and other branched alcohols; lauric acid, myristic acid, palmitin Acid, stearic acid, behenic acid, oleic acid, 1,2-hydroxystearic acid, undecylenic acid, tallic acid Lanolin fatty acids, isostearic acid, linoleic acid, linolenic acid, .gamma.-linolenic acid, higher fatty acids and their derivatives, such as eicosapentaenoic acid;

Carrageenan, pectin, agar, quince seed (quince), arge colloid (duck extract), starch (rice, corn, potato,
Wheat), plant-based polymers such as glycyrrhizinic acid; microbial-based polymers such as xanthan gum, dextran, pullulan; natural water-soluble polymers such as collagen- and gelatin-based animal-based polymers; methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, Cellulose polymers such as hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, sodium carboxymethyl cellulose (CMC), crystalline cellulose, and cellulose powder; semisynthetic water-soluble polymers such as sodium alginate and propylene glycol alginate-based alginate polymers. molecule;

Vinyl-based polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer (Carbopol); polyethylene glycol 20,000, 4,000,000,
Polyoxyethylene-based polymers such as 600,000; Synthetic water-soluble polymers such as polyethyleneimine; Inorganic water-soluble polymers such as bentonite, AlMg silicate (veegum), lavonite, hectorite, silicic anhydride; Volatile Silicones such as silicone oil, silicone resin, silicone gum, and alkyl-modified silicone; N-lauryl-L-glutamate monosodium, N-coconut oil fatty acid-L-glutamate monotriethanolamine, N-myristyl acyl-L-glutamic acid Monosodium,
N-fatty acid acyl-L-glutamates such as N-mixed fatty acid acyl-L-glutamate monosodium;

N-fatty acid-N-methyl taurine salts such as sodium methyl taurine laurate and coconut oil fatty acid methyl taurine sodium; salts of N-fatty acid sarcosine condensates such as lauroyl sarcosine sodium and cocoyl sarcosine sodium; acyl sarcosine sodium,
Surfactants such as acyl glutamate, sodium acyl-β-alanine, acyl taurate, lauryl sulfate, betaine lauryl dimethylaminoacetate, alkyl trimethyl ammonium chloride, polyoxyethylene hydrogenated castor oil, and the like;

1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, edetate disodium, edetate trisodium, edetate tetrasodium, sodium citrate, polyline Sequestering agents such as sodium acidate, sodium metaphosphate, gluconic acid; 3- (4'-methylbenzylidene) -d, 1-camphor, 3-benzylidene-d, 1-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2- (2'-hydroxy-5'-t
-Octylphenyl) benzotriazole, 2- (2 '
-Hydroxy-5'-methylphenylbenzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5- (3,
3-Dimethyl-2-norbornylidene) -3-pentan-2-one, various benzoic acid-based, anthranilic acid-based, salicylic acid-based, cinnamic acid-based, benzophenone-based, and other UV absorbers;

Emulsifiers such as glyceryl monostearate, sorbitan monopalmitate, polyoxyethylene cetyl ether, polyoxyethylene sorbitan monolaurate; (poly) ethylene glycol, (poly) propylene glycol, glycerin, 1,3-butylene glycol , Maltitol, sorbitol, chondroitin sulfate, hyaluronic acid, atelocollagen, cholesteryl-1,2-hydroxystearate, sodium lactate,
Moisturizers such as bile salts, dl-pyrrolidone carboxylate and short-chain soluble collagen; antibacterial agents such as hinokitiol, hexachlorophene, benzalkonium chloride, trichlorocarbanilide and pithionol; vasodilators such as carpronium chloride; menthol Sensitizers such as benzyl nicotinate; vitamins such as vitamins A, B, C, D and E; bactericidal preservatives such as chlorhexidine gluconate, isopropylmethylphenol and paraoxybenzoate ;

Chelating agents such as protein hydrolysates, amino acids, plant extracts, EDTA-Na; pH adjusting agents such as succinic acid, sodium succinate and triethanolamine; foaming agents; foaming agents; foam stabilizers; In the case of aerosol products, propellants such as liquefied petroleum gas and dimethyl ether; metal ion scavengers; antifungal agents; bactericides; emulsions; conditioning agents; thickeners; antioxidants; solubilizers; rosins; hydrotropes Hair restorer; crude drug; pigment; fragrance;
And so on.

(Cosmetics for skin and nails) The form of the cosmetics for skin and nails is not particularly limited, but as the cosmetics for skin, basic cosmetics such as cream and emulsion, and Makeup cosmetics such as foundation, white powder, blusher, eye shadow, lipstick and the like can be mentioned.
Examples of nail cosmetics include nail color, cream for nail care, nail enamel, nail enamel base coat, nail enamel overcoat and the like.

In the form of cosmetics for skin and nails, it is preferable that the block copolymer is contained in the cosmetic in an amount of 1 to 30% by weight. The skin and nail cosmetics are prepared by blending components including the block copolymer with water, an alcohol solvent such as ethanol, an ester solvent such as ethyl acetate, a ketone solvent such as methyl ethyl ketone, liquid paraffin, and petrolatum. It can be produced by dissolving, emulsifying or dispersing in hydrocarbons such as.

[0080]

EXAMPLES The present invention will be described in more detail based on examples, but the present invention is not limited to the following examples. [Example 1] (Production of 2-ethylhexyl acrylate-t-butyl acrylate block copolymer) A thermocouple and a stirring blade were attached to a reaction vessel, and after substituting with nitrogen, 165 mg of copper (I) bromide was added. The temperature was raised to 80 ° C. Next, while maintaining the nitrogen atmosphere in the reaction vessel,
While stirring at 250 rpm, 692 mg of dimethyl 2,6-dibromoheptanedioate, 184 g of 2-ethylhexyl acrylate, 398 mg of pentamethyldiethylenetriamine and dimethylformamide 88.
g mixture was added into the reaction vessel. After stirring for 3 hours, the reaction vessel was rapidly cooled in an ice bath to stop the reaction. A mixed solution of tetrahydrofuran and water is added to separate the polymer layer and the catalyst layer, copper bromide is removed, the polymer layer is dropped into a large amount of methanol to reprecipitate the polymer, and the solvent is filtered off. I removed it. The conversion rate of 2-ethylhexyl acrylate was 50%. The obtained polymer (hereinafter sometimes referred to as “polyethyl acrylate 2-ethylhexyl polymer initiator”) has a weight average molecular weight (Mw) of 33,000,
Number average molecular weight (Mn) is 24,000, molecular weight distribution (M
w / Mn) was 1.38.

A thermocouple and a stirring blade were attached to another reaction vessel, the atmosphere was replaced with nitrogen, and then 28.6 mg of copper (I) bromide was added.
9.33 mg of copper (II) bromide was added and the temperature was raised to 80 ° C. Next, while maintaining a nitrogen atmosphere in the reaction vessel, 2
Polyacrylic acid 2 obtained while stirring at 50 rpm
-Ethylhexyl polymer initiator 48 g, acrylic acid t
-Butyl 128 g, pentamethyldiethylenetriamine 79.7 mg and dimethylformamide 53 g
Was added. After stirring for 2 hours, the reaction container was rapidly cooled in an ice bath to stop the reaction. A mixed solution of tetrahydrofuran and water was added to separate the polymer layer and the catalyst layer into layers, and the polymer layer was made of aluminum silicate (manufactured by Kyowa Chemical Co., Ltd.,
After completely removing copper bromide through a column filled with "Kyoward 700SN"), the solution was dropped into a large amount of methanol to reprecipitate the polymer, and the solvent was removed by filtration. The weight average molecular weight (Mw) of the obtained copolymer was 56,000.
0, the number average molecular weight (Mn) was 39,800, and the molecular weight distribution (Mw / Mn) was 1.41. The weight fractions of 2-ethylhexyl acrylate and t-butyl acrylate in the copolymer calculated from the Mn value were 60% by weight and 4% by weight, respectively.
It was 0% by weight. In addition, by ¹ H-NMR, 2-ethylhexyl acrylate and t-acrylic acid in the copolymer were analyzed.
The weight fraction of butyl was confirmed. The obtained block copolymer is poly (t-BA) / poly (2EHA) / poly (t
It was a triblock copolymer having a constitution of -BA).

21 g of the triblock copolymer of 2-ethylhexyl acrylate and t-butyl acrylate obtained in Example 1 was dissolved in 480 mL of 1,4-dioxane. After adding 33 mL of 6 mol / L hydrochloric acid, 120
The mixture was heated to reflux in an oil bath at ℃ for 6 hours. After cooling
The solvent was concentrated under reduced pressure, reprecipitated with a large amount of hexane, and the solvent was removed by filtration. The obtained polymer was washed with a large amount of water and then dried under reduced pressure to obtain the block copolymer P-1.
Got The hydrolysis rate of the block copolymer P-1 was set to 0.
When confirmed by oxidative titration using a 1 mol / L potassium hydroxide aqueous solution, the hydrolysis rate was 61%.
Further, the glass transition temperature (T
g) was −50 ° C. derived from 2-ethylhexyl acrylate block, 43 ° C. derived from t-butyl acrylate block, and 107 ° C. derived from acrylic acid. These glass transition points were almost in agreement with the values of each homopolymer.

Example 2 (Production of 2-ethylhexyl acrylate-t-butyl acrylate block copolymer) In the same manner as in Example 1, a poly (2-ethylhexyl acrylate) polymer initiator was produced. However, the amount of copper (I) bromide used was 173 mg, the amount of dimethyl 2,6-dibromoheptanedioate was 697 mg, 2-ethylhexyl acrylate was 184 g, and the amount of pentamethyldiethylenetriamine was 419 mg. I changed to 2 hours. The conversion rate of 2-ethylhexyl acrylate was 50%. The obtained poly (2-ethylhexyl acrylate) polymer initiator had a weight average molecular weight (Mw) of 23,300, a number average molecular weight (Mn) of 16,400, and a molecular weight distribution (Mw /
Mn) was 1.41.

A thermocouple and a stirring blade were attached to the reaction vessel, and after substituting with nitrogen, 717 mg of copper (I) bromide and 58.3 mg of copper (II) bromide were added, and the temperature was raised to 80 ° C. Next, while maintaining the nitrogen atmosphere in the reaction vessel,
While stirring at pm, 30 g of obtained poly (2-ethylhexyl acrylate) polymer initiator, 151 g of t-butyl acrylate, pentamethyldiethylenetriamine 1
g and 66 g of dimethylformamide were added. After stirring for 3 hours, the reaction vessel was rapidly cooled in an ice bath to stop the reaction. Thereafter, the same operation as in Example 1 was carried out to obtain a copolymer. The weight average molecular weight (Mw) of this copolymer was 45,0.
00, the number average molecular weight (Mn) was 25,400, and the molecular weight distribution (Mw / Mn) was 1.77. The weight fractions of 2-ethylhexyl acrylate and t-butyl acrylate in the copolymer calculated from the Mn value were 47% by weight and 53% by weight, respectively. In addition, by ¹ H-NMR, 2-ethylhexyl acrylate and t-acrylate in the copolymer were analyzed.
-The weight fraction of butyl was confirmed. The obtained copolymer is
It was a triblock copolymer.

18 g of the triblock copolymer of 2-ethylhexyl acrylate and t-butyl acrylate obtained in Example 2 was dissolved in 500 mL of 1,4-dioxane. After adding 36 mL of 6 mol / L hydrochloric acid, 120
The mixture was refluxed by heating in an oil bath at ℃ for 20 hours. After cooling, the solvent was concentrated under reduced pressure, reprecipitated with a large amount of hexane, and the solvent was removed by filtration. The obtained polymer was washed with a large amount of water and then dried under reduced pressure to obtain a block copolymer P-2. When the hydrolysis rate of the block copolymer P-2 was confirmed by oxidative titration using a 0.1 mol / L potassium hydroxide aqueous solution, the hydrolysis rate was 50%. Further, the glass transition temperature (Tg) measured by the method shown below is derived from 2-ethylhexyl acrylate block, -50 ° C., derived from t-butyl acrylate block, 43 ° C., and derived from acrylic acid. 107 ° C
Met. These glass transition points were almost in agreement with the values of each homopolymer.

Separately, 17 g of the triblock polymer of 2-ethylhexyl acrylate and t-butyl acrylate obtained in Example 2 was dissolved in 450 mL of 1,4-dioxane. After adding 6 mL of 6 mol / L hydrochloric acid, 1
The mixture was heated under reflux in an oil bath at 20 ° C for 20 hours. After cooling, the solvent was concentrated under reduced pressure, reprecipitated with a large amount of hexane, and the solvent was removed by filtration. The obtained polymer was washed with a large amount of water and then dried under reduced pressure to obtain a block copolymer P-3. When the hydrolysis rate of the block copolymer P-3 was confirmed by oxidative titration using a 0.1 mol / L potassium hydroxide aqueous solution, the hydrolysis rate was 26%. Further, the glass transition temperature (Tg) measured by the method shown below is derived from 2-ethylhexyl acrylate block, -50 ° C., derived from t-butyl acrylate block, 43 ° C., and derived from acrylic acid. 107 ° C
Met. These glass transition points were almost in agreement with the values of each homopolymer.

The molecular weight and the molecular weight distribution were determined in terms of polystyrene by performing GPC measurement using a polystyrene gel column with tetrahydrofuran as the mobile phase. Further, the glass transition temperature is D according to JIS K7121.
Using SC (Differential Scanning Calorimetry), it was measured at a temperature rising rate of 20 ° C./min. The same applies hereinafter.

Example 3 (Production of Random Copolymer) A five-necked flask was equipped with a reflux condenser, a dropping funnel, and a reaction vessel.
After attaching a thermometer, a nitrogen-substituted glass tube and a stirrer, 60 parts by weight of 2-ethylhexyl acrylate, 40 parts by weight of acrylic acid and 100 parts by weight of ethyl alcohol were added, and α, α'-azobisisovaleronitrile was added.
1.0 part by weight was added, and the mixture was heated under reflux at 80 ° C. under nitrogen substitution to carry out polymerization for 10 hours. The obtained copolymer is 20% K
It was neutralized 25% with an aqueous OH solution. The glass transition point of the obtained copolymer was -6 ° C. This random copolymer is
It was set to -4.

The compositions of the copolymers obtained in Examples 1, 2 and 3 were such that the block copolymer P-1 was E by weight ratio.
HA / TBA / AA = 60/16/24, the block copolymer P-2 is EHA / TBA / AA = 47.2 / 26.
3 / 26.5, block copolymer P-3 is EHA / TB
A / AA = 47.2 / 39.3 / 13.5, and the random copolymer P-4 had EHA / AA = 60/40. EHA is 2-ethylhexyl acrylate, TBA is t-butyl acrylate, and AA is acrylic acid. Further, a commercially available anionic random copolymer resin (monoalkyl maleic acid ester and methyl vinyl ether copolymer (trade name: GANTREZ A-425 (ISP
Company)) was used as P-5.

The film physical properties (Young's modulus and elongation) of the films P-1 to P-5 were measured by the following methods. As a test piece, a strip-shaped film made of each resin and having a thickness of 90 ± 15 μm, a width of 10 mm and a length of 20 mm was used. The film was naturally dried for 1 week. This film is pulled at a speed of 20 mm / min
Then, a tensile test was conducted based on JIS K7161 to measure Young's modulus and elongation at break. The results are shown in Table 1.

Each of P-1 to P-5 was neutralized with 20% potassium hydroxide and then mixed with a mixed solution of water and ethanol at a concentration of 3% by weight to prepare pump-type hair spray compositions. Each of the obtained hair spray compositions was applied to hair, and the setting power on the hair, the set holding property, the stickiness, the flaking property, the touch, and the hair washing property were evaluated according to the following criteria. The results are shown in Table 1. [Set holding power (hair styling power)] Hair bundle with a length of 23 cm 2.
After immersing 0 g in a 3% polymer solution, it was pulled out, lightly squeezed, wound on a rod having a diameter of 1 cm, and dried. Then, it was taken out from the rod and a curled product was obtained (length L ₀ ). This hair bundle was previously heated to a temperature of 20 ° C. and a relative humidity of 9
After hanging vertically in a thermo-hygrostat at 0% for 3 hours, the hair bundle length (L ₂ ) was measured, and the retention rate (%) was calculated from the following formula. It evaluated by the standard of. Curl retention rate (%) = {(23−L ₂ ) / (23−
L ₀ )} × 100 ◎: The curl retention rate was 85% or more and 100%. Good: The curl retention rate was 60% or more and less than 85%. Δ: The curl retention rate was 30% or more and less than 60%. X: The curl retention rate was 0% or more and less than 30%.

[Hair-washing property] The curled hair obtained was operated in the same manner as the above set-holding power, and the obtained curled hair was allowed to stand at a temperature of 23 ° C and a constant humidity of 60% relative humidity. Immerse in an aqueous solution of 10% activator (sodium polyoxyethylene lauryl sulfate) for 1 hour, rinse with warm water at 40 ° C., and after drying, visually and feel to see if the resin remains in the hair bundle according to the following criteria. did. ◯: No residual resin was visually or tactually confirmed. Δ: Some residual was visually confirmed. X: Remaining was visually confirmed.

[Evaluation of Stickiness of Hair] About 2 g of each sample was applied to 10 g of a hair bundle having a length of 15 cm, and left at room temperature after application. After being left for 30 minutes, a sticky feeling was sensory-evaluated according to the following criteria by a panel composed of 10 persons. ⊚: All 10 persons did not feel sticky. ◯: 1-2 out of 10 people recognized sticky feeling. (Triangle | delta): 3-6 people among 10 people recognized the sticky feeling. X: 7 or more out of 10 persons felt sticky.

[Evaluation of Feeling of Hair Feeling] About 2 g of each sample was applied to 10 g of a hair bundle having a length of 15 cm, and left at room temperature after application. After a lapse of 30 minutes, the finger-passing feeling was sensory-evaluated according to the following criteria by a panel composed of 10 persons. ⊚: All 10 persons recognized good touch. ◯: More than 8 out of 10 people recognized that the touch was good. (Triangle | delta): Only 4-7 persons among 10 persons recognized the favorable touch. X: Only 1 to 3 out of 10 people recognized the good touch.

[Setting force test (hair bundle bending strength)] Length 1
0.7 g of each sample was applied to a hair bundle of 5 cm, immediately adjusted to a width of 2 cm and dried, and the temperature was 23 ° C. and the relative humidity was 6
It was left for 1 hour in a 0% thermo-hygrostat. Then 65mm
The maximum load was measured when the plate was placed on a support stand with a space and the center was bent at a constant speed, and evaluated according to the following criteria. ◯: The maximum load was 200 g or more, there was no discomfort in the resin, and the flexibility was good. Δ: The maximum load was 100 g or more and less than 200 g, and although the resin was supple, the discomfort of the resin remained. X: The maximum load was 100 g or less, the resin was uncomfortable, and the flexibility was poor.

[Set holding power test (hair bundle bending test)] After the completion of the above set power test, the maximum load after breaking the hair bundle was evaluated according to the following criteria. ◯: The maximum load was 15 g or more. Δ: The maximum load was 10 g or more and less than 15 g. X: The maximum load was less than 10 g.

[Flaking] A fixed amount of each sample was sprayed onto a hair bundle, and after completely drying, a comb was passed through and the amount of flaked polymer pieces present on the hair (flaking state) was measured using a stereomicroscope ( 20 times). The evaluation criteria are as follows. ◯: No peeled polymer was observed and the flaking state was not observed. (Triangle | delta): The polymer which peeled was confirmed a little and it was in the flaking state a little. X: A large amount of peeled polymer was confirmed, and was markedly in flaking state.

[0098]

[Table 1]

From the results shown in Table 1, the block copolymer P
Compared with the random copolymer P-4 and the conventional anionic resin, -1 to 3 were excellent in all properties such as hair washability, setting property, moisture resistance and good feel. In addition, the coating properties of the block copolymers P-1 to P-3 differ from each other, and the hard (t-butyl acrylate) and soft segment (2-ethylhexyl acrylate) ratios in the polymer are particularly high. It was found that the physical properties drastically change at 50%. It was also suggested that the elongation and curl retention of the film changed depending on the acrylic acid content.

Polymer weight% used in the actual formulation system below
Is the solid content value. Example 4 The following shampoo composition was prepared. (Wt%) Sodium polyoxyethylene lauryl sulfate (3EO adduct) 16% Lauroyldiethanolamide 2% "P-1" 1.5% Perfume 0.2% Preservative 0.1% Pigment Trace amount Pure water Balance 100% in total

When this composition was used as a shampoo, the hair after washing could be easily combed,
The dried hair had excellent gloss and luster, and was able to give a smooth and firm feel. Also, repeated shampoos did not have a bad effect such as stickiness. Further, the same results as above were obtained with the composition using the block copolymers P-2 and P-3.

Example 5 The following rinse composition was prepared.                                                               (weight%)   Stearyl trimethyl ammonium chloride 1.5%   Cetanol 2%   "P-2" 1.5%   Fragrance 0.2%   Pure water balance   Total 100%

When this composition was used for rinsing, the hair after rinsing could be easily combed, and the hair after drying had excellent gloss and luster, and was easily combed with a smooth feel. I was able to Moreover, even after repeated rinsing, there was no adverse effect such as stickiness. Further, the same results as above were obtained with the composition using the block copolymers P-1 and P-3.

Example 6 A hair spray composition was prepared by placing the following diluted stock solution in a spray can and filling it with liquefied petroleum gas. Diluted stock solution (wt%) "P-2" 1% absolute ethanol 49% total of 50% liquefied petroleum gas ^{(3kg / cm 2, G,} 20 ℃) 50%

When this composition was spray applied to hair and used, it gave an excellent set-holding power to the hair even when the amount of the polymer used was small, and furthermore, the hair had an excellent gloss and luster, and a smooth feel. Gave. Further, the same results as above were obtained with the composition using the block copolymers P-1 and P-3.

Example 7 Random Copolymers P-4 and P
When a composition similar to that of Example 6 was spray-applied using -5, the amount of resin used was small, and the set holding power for hair was weak. Furthermore, the hair after application had gloss, It did not give a glossy, smooth feel.

Example 8 A foam aerosol composition was prepared in the same manner as in Example 6. Undiluted solution (% by weight) "P-2" 2% Polyoxyethylene cetyl ether (10EO adduct) 0.3% Polyoxyethylene cetyl ether (2EO adduct) 0.1% Pure water 85.6% Total 88% Liquefied petroleum gas (3 kg / cm ² · G, 20 ° C) 12%

When this composition was used on hair, Example 6
Similar excellent results were obtained. Further, the same results as above were obtained with the composition using the block copolymers P-1 and P-3.

Example 9 The following set lotion composition was prepared. (Wt%) "P-2" 3% Pure water 60% Absolute ethanol 37% Total 100%

When this composition was applied to hair and used,
The same excellent results as in Example 9 were obtained. Further, the same results as above were obtained with the composition using the block copolymers P-1 and P-3.

[Example 10] A composition similar to that of Example 9 was used as a set lotion using the random copolymers P-4 and P-5. It did not give a gloss, luster or smooth feel.

Example 11 The following gel composition was prepared. (Wt%) "P-3" 1% "Carbopol 940 ^* " 0.5% (adjusted to pH 7.5 with KOH aqueous solution) Pure water 98.5% 100% ^* B. F. Made by Goodrich Chemical

When this composition was used as a gel on hair, it imparted an excellent set-holding power to the hair and also imparted an excellent gloss and luster to the hair and a smooth feel. Further, when the gel composition was repeatedly applied and washed and the hair was washed, there was no adverse effect such as stickiness and discomfort due to accumulation. Also, the same results as above were obtained with the composition using the block copolymers P-1 and P-2.

[Example 12 (Cosmetic for skin)] A cosmetic for skin 1 having the composition shown in Table 2 below was prepared.

When the obtained cosmetic 1 for skin was applied to the skin, a smooth and good-feeling film was obtained without feeling discomfort or stickiness even after drying.

Example 12 except that a 6% ethanol solution of a cationic polymer (“JR-400” manufactured by Union Carbide Co.) was used in the composition shown in Table 2 in place of the block copolymer P-1. In the same manner, a skin cosmetic 2 was prepared.
When this skin cosmetic composition 2 was applied to the skin, it was highly sticky and a smooth feel was not obtained. A cosmetic for skin was prepared in the same manner as in Example 12 except that a 6% ethanol solution of an anionic polymer (“Gantretz A425” manufactured by ISP) was used in the composition shown in Table 2 instead of the block copolymer P-1. 3 was prepared, and when this skin cosmetic 3 was applied to the skin, it became sticky and a smooth feel was not obtained, and it peeled off after rubbing several times.

[0117]

[Table 2]

[Example 13 (Cosmetic for nails)] The ingredients of the following formulation were dispersed and mixed for 1 hour in a bead mill to prepare a cosmetic 1 for nails. (Wt%) "P-3" 40.0% (10.0% as solid content) Isopropanol 10.0% Red 226 No. 0.1% Titanium oxide 4.9% Ethanol 40.0% (as total amount of ethanol 65.0%) Bentonite 5.0% ("BENTON EW" manufactured by National Lead)

When this composition was used for nails, it dried quickly and did not easily peel off after drying, and it had a good durability. Also,
The same results as above were obtained with the composition using the block copolymers P-1 and P-2.

[0120]

As described above, according to the present invention,
By using a resin that has two or more properties,
It is possible to provide a resin composition for cosmetics and a cosmetic that can simultaneously satisfy a plurality of performances required for the cosmetic.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) A61K 7/11 A61K 7/11 7/48 7/48 C08F 4/06 C08F 4/06 4/40 4 / 40 295/00 295/00 (72) Inventor Risa Nishizawa 1st Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Co., Ltd. (72) Inventor Yasushi Kitani 1st Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Co., Ltd. 72) Inventor Masato Onoue 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Co., Ltd. F-term within the company (reference) 4C083 AB242 AB442 AC012 AC072 AC102 AC182 AC692 AC782 AC862 AD021 AD022 AD071 AD091 AD092 AD131 CC01 CC02 CC28 CC31 CC33 CC38 CC39 DD08 DD23 DD27 DD41 EE06 EE07 4J015 CA04 4J026 HA06 HA09 HA10 HA11 HA12 HA15 HA16 HA19 HA24 HA32 HA39 HB06 HB09 HB10 HB11 HB12 HB15 HB16 HB19 HB24 HB32 HB39 HB45 HB47 HE02

Claims (17)

[Claims] 1. A constitutional unit derived from a compound having an ethylenically unsaturated bond, having a number average molecular weight of 1.0 × 10 ³ to.
A resin composition for cosmetics, which comprises a block copolymer having a glass transition point or a melting point of at least two, which is 1.0 × 10 ⁶ . 2. The resin composition for cosmetics according to claim 1, wherein the block copolymer has at least one block composed of a structural unit having a hydrophilic group. 3. The group of anionic groups, wherein the hydrophilic group is a carboxylic acid group, a sulfuric acid group, a phosphoric acid group and salts thereof, an amino group (including a quaternary ammonium salt group), a pyridyl group and salts thereof. The group of cationic groups consisting of, a group of nonionic groups consisting of a hydroxyl group, an alkoxy group, an epoxy group, an amide group and a cyano group, a zwitterionic group consisting of a carboxybetaine group, and a group of polarizable groups consisting of an amine oxide group. The resin composition for cosmetics according to claim 2, which is at least one selected from the group consisting of: 4. The block copolymer according to claim 1, wherein the block copolymer has at least one block containing a structural unit represented by any one of the following general formulas (1) to (5). The resin composition for cosmetics as described. [Chemical 1] (In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R ⁶ each represent a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³ , R ⁴ and R ⁵ Each represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or an arylalkyl group having 7 to 24 carbon atoms or an alkylaryl group consisting of a combination thereof, X ¹ Is -COO-,
Represents -CONH-, -O- or -NH-. A ⁻ represents an anion, and M represents a hydrogen atom, an alkali metal ion or an ammonium ion. m represents 0 or 1,
n represents an integer of 1 to 50. ) 5. The resin composition for cosmetics according to claim 1, wherein the block copolymer is a diblock copolymer, a triblock copolymer or a multiblock copolymer. .. 6. The block copolymer comprises a structural unit derived from an ethylenically unsaturated carboxylic acid and a structural unit derived from an ethylenically unsaturated carboxylic acid ester.
The resin composition for cosmetics according to any one of 1. 7. The block copolymer contains 10 to 90% by weight of the unit derived from the ethylenically unsaturated carboxylic acid and 90 to 10% by weight of a unit derived from the ethylenically unsaturated carboxylic acid ester. The resin composition for cosmetics according to. 8. The resin composition for cosmetics according to claim 1, wherein at least one block constituting the block copolymer is a block formed by post-treatment after polymerization. object. 9. The resin composition for cosmetics according to claim 8, wherein the post-treatment is a hydrolysis treatment. 10. The block copolymer has a glass transition point or melting point substantially equal to the glass transition point or melting point of a homopolymer composed of monomers constituting at least one block of the block copolymer. 1
The resin composition for cosmetics according to claim 1. 11. The resin composition for cosmetics according to claim 1, wherein the block unit constituting the block copolymer has a number average molecular weight of 10 ³ to 10 ⁵ . 12. The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the block copolymer.
Is 2.5 or less, The resin composition for cosmetics according to any one of claims 1 to 11. 13. The block copolymer is water and / or
Alternatively, the resin composition for cosmetics according to any one of claims 1 to 12, which is dispersible or soluble in alcohol. 14. A catalyst in which the block copolymer is at least a metal complex having an organic halide as an initiator and a metal selected from the elements of Groups 8, 9, 10 and 11 of the periodic table as a central metal. The resin composition for cosmetics according to any one of claims 1 to 13, which is produced by controlled radical polymerization used as. 15. The block copolymer according to claim 1, wherein the block copolymer is produced by controlled radical polymerization using a metal complex obtained from copper halide and an amine compound as a catalyst. The resin composition for cosmetics according to. 16. A cosmetic comprising the resin composition for cosmetics according to any one of claims 1 to 15. 17. The cosmetic according to claim 16, which is a cosmetic for hair, skin or nails.