JP2003342133A - Polymer composition for hair cosmetic and hair cosmetic using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polymer composition for a hair cosmetic which provides excellent hair dressing properties, improved set retention power and a finish feeling of natural touch. <P>SOLUTION: The polymer composition for the hair cosmetic comprises (a) a block copolymer having 1×10<SP>3</SP>-1×10<SP>6</SP>number-average molecular weight and at least two glass transition temperatures or melting points and (b) an amphoteric ionic polymer in the weight ratio of ((a)/(b)) of 1/10-10/1. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer composition for hair cosmetics, which is a combination of a block copolymer and a zwitterionic polymer, and a hair cosmetics using the same.
INDUSTRIAL APPLICABILITY The composition of the present invention has excellent hair styling properties, gives good flexibility and a good feeling of touch, and is therefore useful for applications such as hair sprays, hair mousses, hair setting lotions and hair gels.

[0002]

2. Description of the Related Art As a method of maintaining hair in a desired shape, it is generally practiced to apply a solution of a film-forming polymer compound in water, a lower alcohol or a mixed solvent thereof to the hair and dry it to prepare the hair. Has been done. As such a film-forming polymer, amphoteric polymer compounds have come to be widely used (JP-A-49-1464).
7, JP-A-51-9732, JP-A-55-1042.
No. 09, etc.) gives a feeling of stiffness due to lack of flexibility, and does not have sufficient hair styling effect to hold the hair in a desired shape under high humidity, and further has sufficient removability by washing. However, I was not satisfied. In order to improve this, in JP-A-10-87443, a hair cosmetic composition comprising a combination of an amphoteric polymer and an amine oxide group-containing resin is a hair styling composition excellent in flexibility and styling power. Is proposed as.

However, in these combinations,
In terms of the hair styling effect, elasticity, combability, etc., a hair styling material that is satisfactory in terms of performance has not yet been obtained.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and solves the problems of the conventional polymer compositions for hair cosmetics using an amphoteric polymer.
It is an object of the present invention to provide a polymer composition for hair cosmetics and a hair cosmetic which have good hair-holding power and good set-holding power due to an elastic film, and give a finished feeling of natural texture without discomfort. .

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that excellent hair styling can be achieved by combining an amphoteric polymer and a specific block copolymer. It has been found that a polymer composition for hair cosmetics having a good elasticity and a good feeling of finish can be obtained, and as a result of further studies based on this finding, the present invention is completed. Came to.

That is, the gist of the present invention is (a) a number average molecular weight of 1 × 10 ³ to 1 × 10 ⁶ and at least two glass transition points (hereinafter sometimes abbreviated as “Tg”) or melting points. For a hair cosmetic, which comprises a block copolymer having (b) and a (b) zwitterionic polymer in a weight ratio ((a) / (b)) of both of 1/10 to 10/1. A combined composition.

Another aspect of the present invention is that (a) the block copolymer comprises an anionic group consisting of a carboxylic acid group, a sulfuric acid group, a phosphoric acid group and salts thereof, an amino group (a quaternary ammonium salt group). Group), a group of cationic groups consisting of a pyridyl group and salts thereof, a hydroxyl group, an alkoxy group, an epoxy group, a group of nonionic groups consisting of an amide group and a cyano group, a group of zwitterionic groups consisting of a carboxybetaine group,
And the above-mentioned polymer composition for hair cosmetics having at least one block composed of a structural unit having at least one hydrophilic group selected from the group of polarizable groups composed of amine oxide groups, and (b) both ions Polymer, a polymer having an unsaturated monomer containing a betaine structural group such as carboxybetaine group, sulfobetaine group, or phosphobetaine group, or a carboxyl group, sulfonic acid group, phosphoric acid group, etc. The above-mentioned hair cosmetic composition, which is a polymer having both an anionic group-containing unsaturated monomer and a quaternary ammonium salt-containing unsaturated monomer as constituent components. .

Another subject matter of the present invention is that the (a) block copolymer has at least one block containing a structural unit represented by any one of the following general formulas (1) to (5). It also exists in a polymer composition for cosmetics.

[0009]

[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 and R ⁴ And R ⁵ each represent 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 represents —COO—, —CONH—, —O— or —NH—, A ⁻ represents an anion, M represents a hydrogen atom, an alkali metal ion or an ammonium ion, and m represents 0 or 1. , N represents an integer of 1 to 50.) Further, another gist of the present invention is that (a) the block copolymer is a diblock copolymer, a triblock copolymer or a multiblock. The above-mentioned polymer composition for hair cosmetics, which is a copolymer, and (a) the block copolymer have 10 to 90% by weight of a constitutional unit derived from an ethylenically unsaturated carboxylic acid, and an ethylenically unsaturated carboxylic acid. The above-mentioned polymer composition for hair cosmetics containing 90 to 10% by weight of the ester-derived unit is also present.

Another subject matter of the present invention is a hair cosmetic composition containing 0.1 to 10% by weight of the above-described polymer composition for hair cosmetic composition, and a hair cosmetic composition further containing a gas or liquid for spraying. It depends on the fee.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The polymer composition for hair cosmetics of the present invention contains (a) a block copolymer and (b) a zwitterionic polymer. The block copolymer (a) used in the present invention has a number average molecular weight of 1 × 10 ³ to 1 × 10 ⁶ and has at least two glass transition points or melting points. Number average molecular weight is 5.0
It is preferably × 10 ^{3 to} 5.0 × 10 ⁵ . If the number average molecular weight is less than 1 × 10 ³ , the film-forming ability tends to decrease. On the other hand, if the number average molecular weight is more than 1 × 10 ⁶ , the viscosity tends to be excessively high, but if it is within the above range, it is easy to mix with other components when used in a hair cosmetic composition. .

The block copolymer 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,
It is more preferably −20 ° C. or lower. All melting points are preferably around room temperature or higher.

The block copolymer preferably has a glass transition point or melting point derived from each block. That is, it preferably has a glass transition point or melting point that is substantially equal to the glass transition point or melting point of a homopolymer composed of monomers constituting one block of the block copolymer. For example, the AB block copolymer has two glass transition points or melting points, and each glass transition point or melting point is substantially equal to the glass transition point or melting point of the homopolymer of A and B respectively. Is preferred. Further, the A-B-C type block copolymer has three glass transition points or melting points, and each glass transition point or melting point is the glass transition point or melting point of the homopolymer of A, B and C, respectively. Is preferably approximately equal to.

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. Be done. Ratio (Mw / M) of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography of the block copolymer.
n) is not particularly limited, but is preferably 2.5 or less, more preferably 2.0 or less,
It is more preferably 1.8 or less. Mw / Mn is 2.
When it exceeds 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.

When the block copolymer has at least one block having a hydrophilic group, when it is used, for example, as a shampoo for hair, it becomes a cosmetic composition with good hair washability that can be easily removed by washing the hair. It is preferable because it can be incorporated into various forms of cosmetics. The hydrophilic group may be any of an anionic group, a cationic group, a nonionic group, a zwitterionic group and a polarizable 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 formed in the block copolymer by polymerizing a monomer having a hydrophilic group or by producing a copolymer and then subjecting the copolymer to a post-treatment such as a hydrolysis treatment. Can be introduced to.

In the present specification, the polarizable group is not a definite ionic group, but a group having an ionic property and a covalent bond property, but having a biased electron distribution. As described above, the block copolymer preferably has at least one block composed of a structural unit having a hydrophilic group, and has a hydrophilic group and a structural unit derived from a compound having an ethylenically unsaturated bond. More preferably, it has at least one block consisting of As the structural unit having a hydrophilic group, the following general formula (1) to
The structural unit represented by any of (5) is preferable.

[0018]

[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 having 7 to 24 carbon atoms or an alkylaryl group consisting of a combination thereof, and X ¹ represents -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. A^-The anion represented by
Examples thereof include anionic groups of acids such as halogen ion.
Ion, sulfate ion, carboxylate ion, etc.
It The alkali metal ion represented by M is Na⁺
And K⁺Is mentioned. Also, the ammoni represented by M
NH derived from ammonia for the um ions_Four ⁺Other
Methylamine, dimethylamine, trimethylamine,
Cylamine, diethylamine, triethylamine, n-
Propylamine, n-butylamine, allylamine, d
Volatile amines such as tolylenediamine, morpholine and pyridine
Mono-, di- or triethanolamine, mono
-, Di- or triisopropanolamine, aminoethyl
Lepropanol, aminoethylpropanediol, lysine
Non-volatile amines such as amines;
Rukylammonium ions are also included.

The block containing the constitutional unit represented by any of the above general formulas (1) to (5) can be produced by polymerizing using a double bond-containing compound corresponding to each constitutional unit 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, the block copolymer having a block composed of the structural unit represented by the general formula (1) uses a (meth) acrylic acid ester as a copolymerization monomer, and synthesizes a copolymer having a block composed of the monomer. After that, the block can be hydrolyzed to produce the same. 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).

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)) are shown below. However, the present invention is not limited to the following specific examples. Examples of the nonionic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, -n-propyl (meth) acrylate, and (meth).
Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate Cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, (meth) acrylic acid Decyl, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic acid-2
-Methoxyethyl, (meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl,
2-Hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ-
((Meth) acryloyloxypropyl) trimethoxysilane, γ-((meth) acryloyloxypropyl)
Dimethoxymethylsilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2- (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid diperfluoromethylmethyl, ( (Meth) acrylic acid-2-perfluoromethyl-2-perfluoroethylmethyl, (meth) acrylic acid-2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic acid-2 -(Meth) acrylic acid ester such as perfluorohexadecylethyl Le; styrene, alpha-methyl styrene, p- methyl styrene, p- methoxystyrene aromatic alkenyl compounds such as acrylonitrile, vinyl cyanide compounds such as methacrylonitrile; butadiene,
Conjugated diene compounds such as isoprene; halogen-containing unsaturated compounds such as vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene and vinylidene fluoride; silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; Unsaturated carboxylic acid anhydride such as maleic anhydride; Unsaturated dicarboxylic acid diester such as maleic acid dialkyl ester and fumaric acid dialkyl ester; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc. Ester compounds; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-steary. Maleimide compounds such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; polyethylene glycol (meth) acrylate, methoxypoly (ethylene glycol / propylene glycol) mono (meth) acrylate, polyethylene glycol di (meth) acrylate, N-polyalkylene. Monomers derived from (meth) acrylic acid or (meth) acrylamide such as oxy (meth) acrylamide and an alkylene oxide having 2 to 4 carbon atoms; such as N-vinylpyrrolidone, N- (meth) acryloylmorpholine and acrylamide Hydrophilic nonionic monomers; and the like.

In the present specification, the notation such as "(meth) acrylic" means "acrylic or methacrylic". Examples of the anionic monomer include unsaturated carboxylic acid compounds such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and crotonic acid; unsaturated polybasic acid anhydrides (eg, succinic anhydride). Acid, phthalic anhydride, etc.)
And a partial ester compound of a hydroxyl group-containing (meth) acrylate (for example, hydroxyethyl (meth) acrylate); a compound having a sulfonic acid group such as styrenesulfonic acid, sulfoethyl (meth) acrylate; acid phosphooxyethyl (meth) Compounds having a phosphoric acid group such as acrylate; and the like. These anionic unsaturated monomers can be used as an acid or partially neutralized or completely neutralized, or can be subjected to copolymerization as an acid and then partially neutralized or completely neutralized. it can. Examples of the basic compound used for neutralization include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, ammonia water, amine compounds such as mono-, di-, tri-ethanolamine 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 acting a modifying agent such as sodium or potassium haloacetate on the specific example of the above-mentioned cationic monomer precursor. . 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 any of these two.
Used in combination of two or more species. Among these, from the viewpoint of industrial availability, (meth) acrylic acid ester, aromatic alkenyl compound, vinyl cyanide compound,
It is preferable to use a conjugated diene compound or a halogen-containing unsaturated compound. As a preferred embodiment of the block copolymer, a block copolymer containing at least one block each composed of an ethylenically unsaturated carboxylic acid unit and at least one block composed of an ethylenically unsaturated carboxylic acid ester unit can be mentioned.

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 block copolymer is such that the former is 10 to 90% by weight and the latter is 90 to 10% by weight. Is preferred, more preferably the former is 15 to 80% by weight and the latter is 80 to 15% by weight.
% By weight, more preferably 20 to 50% by weight in the former and 80 to 50% by weight in the latter. 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 elasticity of the resin tends to significantly decrease.

In the present specification, the "structural unit derived from a compound" means not only a structural unit formed as a result of polymerizing the compound as a monomer, but also as described above.
A structural unit derived from the compound in structure, which is generated as a result of post-treatment such as hydrolysis, is also included. The block copolymer may be any of a diblock copolymer, a triblock copolymer, and a multiblock copolymer. For example, when the block copolymer has a hard block A (a block having a high Tg) and a soft block B (a block having a low Tg), an A-B type diblock copolymer or an A-B-A type diblock copolymer is used. Triblock copolymer, BA-
Examples thereof include B type triblock copolymers and (AB) n type multiblock copolymers. Among these, an ABA type triblock copolymer, an (AB) n type multiblock copolymer, or a mixture thereof is preferable in order to impart rubber elasticity to the resin.

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 is 60 ° C. with 1 part by weight of the block copolymer and 99 parts by weight of deionized water (or a deionized water / ethanol (50/50) mixed solution). It can be confirmed by confirming that the resulting solution is uniform without forming a precipitate and the light transmittance at 655 nm is 70% or more after heating and stirring for 2 hours and cooling and allowing to stand at room temperature for 1 day. The term "dispersible" means that the fine particles of the copolymer are dispersed in water and / or a water-ethanol mixed solution without being precipitated to form an emulsion or latex.

The method for producing the block copolymer as the component (a) is not particularly limited, but examples thereof include the following methods (1) to (3). Among them, it is preferable to use living radical polymerization, which is a type of controlled radical polymerization, because the molecular weight and structure of the block copolymer produced can be easily controlled. Living Anion or Living Cationic Polymerization Controlled Radical Polymerization Suspension Polymerization Method Using Polymer Initiator or Chain Transfer Agent Living radical polymerization refers to radical polymerization in which the activity of the polymer terminal 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 of being included and is also used in the present specification in the latter meaning.

Living radical polymerization has been actively studied in various groups in recent years. Examples thereof include those using a chain transfer agent such as polysulfide, cobalt porphyrin complex (J. Am. Chem. Soc. 19).
94, 116, 7943) or a radical scavenger such as a nitroxide compound (Macromolecule)
les, 1994, 27, 7228), an atom transfer radical polymerization using an organic halide as an initiator and a transition metal complex as a catalyst (Atom TransferRadic).
al Polymerization (ATRP) and the like. 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.

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. The block copolymer obtained by the polymerization may be used as it is in the polymer composition for hair cosmetics 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 that can be used here include hydrolysis treatment, quaternization treatment, and amine oxide treatment. For example, by hydrolysis,
From a block composed of (meth) acrylic acid ester,
It is possible to form a block derived from (meth) acrylic acid having a carboxylic acid group which is a hydrophilic group (for example, a block having a structural unit represented by the general formula (1)). 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 carboxylic acid formed may be partially or completely neutralized before use. For neutralization, for example, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; ammonia water, mono-, di-, triethanolamine,
Amine compounds such as trimethylamine; and the like bases are used.

In the present invention, a zwitterionic polymer having an zwitterionic group is used as the component (b) together with the block copolymer as the component (a). The amphoteric polymer as the component (b) that can be used in the present invention includes a heavy monomer containing an unsaturated monomer having a betaine structure group such as a carboxybetaine group, a sulfobetaine group, or a phosphobetaine group as a constituent component. Polymers having a combination or an unsaturated monomer having an anion group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group and an unsaturated monomer having a quaternary ammonium salt group as constituent components are preferable.

Specific examples of the polymer having an unsaturated monomer having a betaine structural group as a constituent component include Yucaformer 205S, SM, AMPHOSET301, R10.
2, R402, 510, 201, W (above, manufactured by Mitsubishi Chemical Co., Ltd.) and the like can be cited as a methacryl-based carboxybetaine polymer which is a monohaloacetic acid salt-modified product of a dimethylaminoethyl methacrylate / alkyl methacrylate ester copolymer. , JP-A-51-9732, JP-A-5
It is described in JP-A 5-104209, JP-A-61-258804, JP-A-7-285832.

Further, a polymer containing both an unsaturated monomer having an anion group such as a carboxyl group, a sulfonic acid group and a phosphoric acid group and an unsaturated monomer having a quaternary ammonium salt group as a constituent component. As a specific example, the former 28
-4910, LV-71, LV-47 (above, manufactured by National Starch) hydroxypropyl acrylate /
A butylaminoethyl methacrylate / octylamide acrylate / acrylic acid copolymer of a polymer containing both a carboxyl group-containing unsaturated monomer and a tertiary amino group-containing unsaturated monomer Quaternary compound; a carboxyl such as diallyldimethylammonium chloride / acrylic acid copolymer such as Mercoat 295 (manufactured by Calgon) and diallyldimethylammonium chloride / acrylic acid / acrylamide copolymer such as Mercoat Plus 3330 (manufactured by Calgon) Examples thereof include polymers having both a group-containing unsaturated monomer and a quaternary ammonium salt-containing unsaturated monomer as constituent components.

The amphoteric polymer as the component (b) preferably contains at least 5% by weight of amphoteric groups.
It is more preferable that the content is 15% by weight or more.
It is more preferable to contain the above. The weight average molecular weight of this amphoteric polymer is 5,000 to 1,000,
000 is preferable, and 10,000 to 500,000 is preferable.
It is more preferably 0, 20,000 to 300,000
It is more preferably 0.

In the polymer composition for hair cosmetics of the present invention, the weight ratio ((a) / (b)) of the (a) block copolymer to the (b) zwitterionic polymer is 1/10. -10/1
And preferably 1/5 to 10/1. (A) /
When the ratio of (b) is less than 1/10, the hair styling effect is insufficient, the desired hair shape cannot be maintained, and the elasticity of the hair becomes insufficient under high humidity. On the other hand, if this ratio exceeds 10/1, there is a problem in that the slipperiness when applying the cosmetic to hair is insufficient and a squeaky feeling occurs.

The polymer composition for hair cosmetics of the present invention comprises
The component (a) and the component (b) are combined, and the total amount of the composition is 0.
It is preferable to contain 1 to 10% by weight, and 0.5 to
It is more preferably 8% by weight. If the total amount is less than 0.1% by weight, the hair styling power tends to be insufficient, and if it exceeds 10% by weight, the feeling of stiffness may be increased and the feel may be deteriorated.

The polymer composition for hair cosmetics of the present invention contains, in addition to the above-mentioned essential components (a) and (b), components used in ordinary cosmetics such as castor oil and cacao. Oil, mink oil, avocado oil, jojoba oil, macadamian nut oil, olive oil, and other glycerides; beeswax, lanolin, and other waxes; liquid paraffin, solid paraffin, isoparaffin, squalane, and other hydrocarbons; cetyl alcohol, oleyl alcohol, Linear and branched higher alcohols such as stearyl alcohol, isostearyl alcohol, lauryl alcohol and 2-octyldodecanol; polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin and sorbitol; polyoxy ethylene Ethylene oxide and / or propylene oxide adducts of higher alcohols such as uryl ether, polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene stearyl ether; isopropyl myristate, octyldodecyl myristate, hexyl laurate, cetyl lactate, etc. Esters;
Amides such as oleic acid diethanolamide and lauric acid diethanolamide; silicone derivatives such as dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone, amino-modified silicone; stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryltrimethylammonium Nonionic surfactants such as chlorides; anionic surfactants such as polyoxyethylene lauryl ether sulfates and polyoxyethylene lauryl sulfosuccinates; amphoteric surfactants such as lauryl hydroxysulfobetaine and lauryl dimethylcarboxybetaine;
Collagen hydrolysates, keratin hydrolysates, protein derivatives such as polyamino acids, amino acid derivatives; plant extracts,
UV absorbers such as crude drugs, vitamins and oxybenzene,
Chelating agent such as EDTA-Na, preservative such as paraben,
Antioxidants, dyes, pigments, fragrances and the like may be appropriately added within a range not impairing the effects of the present invention.

The use and form of the hair cosmetic composition of the present invention is not particularly limited, and examples thereof include aerosol hair spray, pump hair spray, foam hair spray, hair mist,
It can be used as a set lotion, hair gel, hair cream, hair oil. The hair cosmetic composition of the present invention comprises the components (a) and (b) above.
It can be produced by dissolving or dispersing in water and / or a solvent of alcohols such as ethanol and isopropanol according to a conventional method.

Further, for example, as a gas or liquid for spraying, chlorofluoroalkanes such as trichloromonofluoromethane and dichlorodifluoromethane; liquefied petroleum gas composed of alkanes; dimethyl ether; compressed gas such as carbon dioxide gas and nitrogen gas Alternatively, or by using a mixed gas thereof, an aerosol formulation can be prepared by a conventional method.

[0044]

EXAMPLES The present invention will be described in more detail below with reference to production examples and examples. However, the present invention is limited by these production examples and examples as long as the gist of the invention is not exceeded. is not. The parts and% in the production examples and examples are
Unless otherwise specified, they are expressed on a weight basis. (1) Production of Polymer [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 the atmosphere was replaced with nitrogen, followed by copper bromide. 165 mg of (I) was put and it heated up at 80 degreeC. Next, while maintaining the nitrogen atmosphere in the reaction vessel,
While stirring at 250 rpm, a mixed solution of 692 mg of dimethyl 2,6-dibromoheptanedioate, 184 g of 2-ethylhexyl acrylate, 398 mg of pentamethyldiethylenetriamine and 88 g of dimethylformamide was added to 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. Conversion rate of 2-ethylhexyl acrylate is 50%
Met. Obtained polymer (hereinafter may be referred to as "polyethyl acrylate 2-ethylhexyl polymer initiator")
Has a weight average molecular weight (Mw) of 33,000, a number average molecular weight (Mn) of 24,000, and a molecular weight distribution (Mw / M
n) 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 128g, pentamethyldiethylenetriamine 7
A mixture of 9.7 mg and dimethylformamide 53 g was added. After stirring for 2 hours, quench the reaction vessel in an ice bath,
The reaction was stopped. A mixed solution of tetrahydrofuran and water was added to the system to cause phase separation into a polymer phase and a catalyst phase,
The polymer layer was passed through a column packed with aluminum silicate (Kyowa Chemical Co., Ltd., "Kyoward 700SN"),
After completely removing copper bromide, 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 (M
w) is 56,000 and the number average molecular weight (Mn) is 39,8.
00, 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 40% by weight, respectively. Also, ¹ H-NM
By R, the weight fraction of 2-ethylhexyl acrylate and t-butyl acrylate in the copolymer was confirmed. The block copolymer obtained was poly (t-BA) / poly (2E).
It was a triblock copolymer having a constitution of HA) / poly (t-BA).

21 g of a 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, 1
The mixture was heated under reflux in an oil bath at 20 ° C 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 a block copolymer P-1.

The hydrolysis rate of the block copolymer P-1 was
When confirmed by neutralization titration using a 0.1 mol / L potassium hydroxide aqueous solution, the hydrolysis rate was 61%. In addition, 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 weight average molecular weight (Mw) of the obtained poly (2-ethylhexyl acrylate) polymer initiator was 22,600, the number average molecular weight (Mn) was 12,000, and the molecular weight distribution (Mw /
Mn) was 1.87.

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, 250
While stirring at rpm, 30 g of the obtained poly (2-ethylhexyl acrylate) polymer initiator, 151 g of t-butyl acrylate, 1 g of pentamethyldiethylenetriamine and 66 g of dimethylformamide were added. Three
After stirring for an hour, the reaction vessel was rapidly cooled in an ice bath to stop the reaction. After that, a copolymer was obtained by the same operation as in Example 1. The weight average molecular weight (Mw) of this copolymer was 45,000,
Number average molecular weight (Mn) is 25,400, molecular weight distribution (M
w / 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. Moreover, the weight fraction of 2-ethylhexyl acrylate and t-butyl acrylate in the copolymer was confirmed by ¹ H-NMR. The obtained copolymer 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, the mixture was heated under reflux in an oil bath at 120 ° 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-2.

The hydrolysis rate of the block copolymer P-2 was
When confirmed by neutralization titration using a 0.1 mol / L potassium hydroxide aqueous solution, the hydrolysis rate was 50%. Moreover, the glass transition temperature (Tg) measured by the method shown below is −50 ° C. derived from the 2-ethylhexyl acrylate block, 43 ° C. derived from the t-butyl acrylate block, and 107 derived from the acrylic acid. It was ℃. 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 carrying out GPC measurement using a polystyrene gel column with tetrahydrofuran as a mobile phase. Further, the glass transition temperature (Tg) was measured at a temperature rising rate of 20 ° C./min using DSC (differential scanning calorimetry) according to JIS K7121. The same applies hereinafter. Example 3 (Production of Random Copolymer Having Amine Oxide Group) 50 parts of N, N-dimethylaminoethyl methacrylate in a reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas introducing pipe and a stirring device. 30 parts of methyl methacrylate,
After 20 parts of isobutyl methacrylate and 150 parts of absolute ethanol were added and 0.6 part of 2,2′-azobisisobutyronitrile was added, the mixture was reacted at 80 ° C. for 8 hours in a nitrogen atmosphere and then cooled to 60 ° C.

Then, a 31% aqueous solution of N, N-dimethylaminoethylmethacrylate and equimolar hydrogen peroxide was added dropwise to the polymerization solution by a dropping funnel in 1 hour, and stirring was continued for 20 hours to obtain a dimethylamino group. Oxidation of the polymer and adding absolute ethanol to increase the polymer concentration to 30
Adjusted to%. The completion of the oxidation reaction was confirmed by measuring the amine value of the reaction solution. The obtained polymer was designated as "P-
3 ”. The weight average molecular weight of the obtained polymer was 1
It was 10,000. In addition, the absorption of N—O was recognized from the infrared absorption spectrum, and the generation of amine oxide groups was confirmed. (2) Preparation and Evaluation of Hair Cosmetics [Examples 1 to 6 and Comparative Examples 1 to 8] Hair cosmetics (pump sprays) having a composition shown in Table 1 and combined with an ionic polymer were prepared by a conventional method. The hair styling power (setting power) when these were applied to hair, the elasticity of the hair under high humidity, the firmness / tension of the hair, flaking, and the hair wash removability were tested and evaluated by the following methods. The results are also shown in Table 1.

As is clear from Table 1, the hair cosmetic compositions of Examples 1 to 6 have excellent hair styling power and set-holding power, and can retain the shape of curled hair even under hot and humid conditions. It was found that the hair has a good elasticity, has no flaking, and has excellent performance of removing hair by washing. On the other hand, the hair cosmetics of Comparative Examples 1 to 8 are insufficient in hair styling power and set holding power, cannot give tension to hair, cause flaking, and have insufficient washability. However, it was not satisfactory in terms of performance as a hair cosmetic.

[0055]

[Table 1]

(Same in the table below) P-1: Block copolymer prepared in Preparation Example 1 P-2: Block copolymer prepared in Preparation Example 2 P-3: Amine oxide prepared in Preparation Example 3 Group-containing copolymer Amphoteric polymer 1: Yucaformer AMPHOSET (manufactured by Mitsubishi Chemical Co., Ltd.) (methacryloyl carboxybetaine / methacrylic acid alkyl ester copolymer) Amphoteric polymer 2: Yukaformer SM (manufactured by Mitsubishi Chemical Corporation) (methacryloyl) Carboxybetaine / methacrylic acid alkyl ester copolymer) Zwitterionic polymer 3: Unformer 28-4910 (manufactured by National Starch) (Acrylic acid octylamide / butyl aminoethyl methacrylate / acrylic acid copolymer) (Acid Neutralize 100% of equivalent weight with 2-amino-2-methyl-1-propanol) Amphoteric polymer 4: Mercoat Plus 3330 GON Co., Ltd.) (diallyldimethylammonium chloride / acrylic acid / acrylamide copolymer) [Examples 7 to 10 and Comparative Examples 9 to 12] Hair cosmetics (aerosol) having a composition shown in Table 2 and combined with an amphoteric polymer. Was prepared by a conventional method and evaluated in the same manner as in Example 1. The results are also shown in Table 2.

As is clear from Table 2, Examples 7-10
The hair cosmetic of No. 1 has excellent hair styling power and set holding power, can hold the shape of curled hair even under high temperature and high humidity conditions, has no flaking, and has excellent performance of removing hair by washing. It turned out to have. On the other hand, Comparative Example 9-
12 Hair cosmetics have poor performance as hair cosmetics, such as insufficient hair styling and set holding power, inability to give tension to hair, flaking, and insufficient washability. In terms of aspect, I was not satisfied.

[0058]

[Table 2]

(3) Test evaluation method (a) Hair styling power (curl holding power) 23 cm, 2 g of habit-free hair was dispensed with a dispenser (or in the form of an aerosol), and a fixed amount of hair cosmetic was applied to the hair. Then, it is immediately wound in a curler having a diameter of 1.2 cm and dried. Next, remove the hair from the curler at 30 ° C.
The hair is hung in a constant temperature / humidity machine of / 90% RH, the elongation of the hair after 3 hours is measured, and the curl retention force (%) is obtained by substituting it in the following curl retention evaluation formula.

Curl retention evaluation formula Curl retention force (%) = [(23−L) / (23−L ₀ )]
× 100 (In the formula, L ₀ is the length of the curled hair bundle immediately after being removed from the curler (cm), and L is the length of the curled hair bundle after 3 hours (cm)) ⊚: Curl holding power Value was 81% or more.

◯: The value of the curl holding force was 61 to 80%. (Triangle | delta): The value of curl holding power was 40-60%. X: The value of curl retention was less than 40%. (B) Elasticity of hair Curled hair obtained by operating in the same manner as the above hair styling power (curl holding power) is allowed to stand overnight under constant temperature and humidity conditions of 23 ° C./50% RH and then curled. Evaluate the elasticity and elasticity of hair when crushed with.

◯: There was good tension and elasticity. Δ: There is tension, but it is elastic but weak. X: There is little or no tension and elasticity. (C) Flaking The hair applied in the same manner as the above hair styling power (curl holding power) is leveled with fingers immediately after application to prepare a flat hair bundle, which is then dried at 23 ° C./60% RH. After standing overnight under constant temperature and humidity conditions, combing is performed, and the amount of the peeled polymer pieces present on the hair is observed with a stereoscopic microscope (20 times).

◯: Polymer pieces are not observed or slightly observed Δ: Polymer pieces are observed ×: A large amount of polymer pieces are observed (d) Hair wash removability (film solubility) Adjusted hair cosmetic (If a propellant is contained, the liquid from which the propellant has been removed) is applied to a glass plate using a 100 μm applicator and dried. Next 23 ° C / 60% R
After being left under constant temperature and humidity conditions of H overnight, it is immersed in warm water of 40 ° C. and the time required for dissolving the polymer film on the glass plate is measured.

○: Dissolve within 1 minute △: Dissolve within 1 to 5 minutes ×: Requires 5 minutes or more for dissolution (e) Setting force (hair bundle bending strength) 0 for a hair bundle having a length of 15 cm Apply 7g of each sample,
Immediately, it was adjusted to a width of 2 cm, dried, and left in a thermo-hygrostat at 23 ° C./60% RH for 1 hour. Then, the maximum load was measured when the plate was placed on a support table at 65 mm intervals and the center part was bent at a constant speed, and evaluated according to the following criteria.

○: The maximum load was 200 g or more, the resin did not feel uncomfortable, and the flexibility was good. Δ: The maximum load was 100 g or more and less than 200 g, the resin remained uncomfortable with the pliability ×: Maximum load 100 g Below, there was a feeling of discomfort in the resin and the flexibility was poor. (F) Set holding force test (hair bundle bending test) After the above set force test, the maximum load after breaking the hair bundle was determined according to the following criteria. evaluated.

[0066] ○: 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

[0067]

As described above, according to the present invention,
It solves the problems of conventional hair cosmetic polymer compositions that use amphoteric polymer compounds, has excellent hair styling properties and good set retention due to elasticity, and gives a feeling of natural texture with no discomfort. A polymer composition for hair cosmetics and hair cosmetics (various hair cosmetics such as hair spray, hair mousse, hair setting lotion, hair gel, etc.) are provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4C083 AC012 AC102 AC172 AD011                       AD012 AD071 AD072 AD091                       AD092 CC31 CC32 DD08                       EE06 EE21 EE28                 4J002 BG01X BG05X BG07X BG13X                       BP01W BP03W FD200 GB00

Claims (9)

[Claims] 1. (a) Number average molecular weight 1 × 10 ³ to 1 × 1
0 is ^6, and 1/10 block copolymer having at least two glass transition or melting point, and (b) amphoteric polymers, as the weight ratio of both ((a) / (b) ) A polymer composition for hair cosmetics, which is contained in a ratio of 10/1. 2. The (a) block copolymer comprises 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 quaternary ammonium salt group), a pyridyl group and Consists of a group of cationic groups consisting of these salts, a group of hydroxyl groups, alkoxy groups, epoxy groups, amide groups and nonionic groups consisting of cyano groups, a group of amphoteric groups consisting of carboxybetaine groups, and amine oxide groups The polymer composition for hair cosmetics according to claim 1, having at least one block composed of a structural unit having at least one hydrophilic group selected from the group of polarizable groups. 3. The amphoteric polymer as the component (b) is a polymer containing an unsaturated monomer having a betaine structure group such as a carboxybetaine group, a sulfobetaine group, or a phosphobetaine group as a constituent component. The polymer composition for hair cosmetics according to claim 1 or 2. 4. An unsaturated monomer having an anionic group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group, and an unsaturated monomer having a quaternary ammonium salt group. The polymer composition for hair cosmetics according to claim 1 or 2, which is a polymer having both the body and the constituent components. 5. The block copolymer (a) having at least one block containing a structural unit represented by any one of the following general formulas (1) to (5): Item 7. A polymer composition for hair cosmetics according to Item. [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. ) 6. The hair cosmetic composition according to any one of claims 1 to 5, wherein the block copolymer (a) is a diblock copolymer, a triblock copolymer or a multiblock copolymer. Polymer composition. 7. The (a) block copolymer comprises 10 to 90% by weight of a structural unit derived from an ethylenically unsaturated carboxylic acid,
And a polymer composition for hair cosmetics according to any one of claims 1 to 6, which comprises 90 to 10% by weight of a unit derived from an ethylenically unsaturated carboxylic acid ester. 8. A hair cosmetic containing 0.1 to 10% by weight of the polymer composition for hair cosmetics according to claim 1. 9. The hair cosmetic composition according to claim 8, further comprising a spraying gas or liquid.