JPH1179945A - Hair cosmetic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hair cosmetic composition imparting a hard feel when applied, hard to cause coated film fracture even in case an external force is applied to the hair, and excellent in maintaining the above hard feel, by using a specific amphoteric polymer. SOLUTION: This hair cosmetic composition contains an amphoteric polymer which is obtained by modifying a copolymer with amphotericizing agent(s) of the formula XR<8> COOE (R<8> is a 1-4C alkylene; X is bromine, chlorine or iodine; E is an alkali metal ion or the like) and/or formula III ((n) is 2 or 3); wherein the copolymer is prepared by copolymerization in a hydrophilic solvent between (A) 20-80 wt.% of an unsaturated monomer of formula I (R<1> is H or methyl; R<2> is a 1-4C alkylene; R<3> and R<4> are each H or a 1-4C alkyl; A is NH or O), (B) 5-70 wt.% of an unsaturated monomer of formula II (R<5> is H or methyl; R<6> and R<7> are each H, a 1-8C alkyl or the like), (C) 5-60 wt.% of a 1-24C aliphatic hydrocarbon group-bearing (meth)acrylic ester, and (D) 0-20 wt.% of another copolymerizable unsaturated monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hair cosmetic composition, and more particularly to a hair cosmetic composition containing a specific zwitterionic polymer having an amide group-containing unsaturated monomer as a constituent component. The composition of the present invention, as a hair cosmetic,
A hard feel is imparted at the time of applying the hair, and at the same time, the applied film is hardly broken even when an external force is applied to the hair, and has excellent performance in maintaining a hard feel.

[0002]

2. Description of the Related Art Polymers used for hair styling include:
Anionic polymers which are copolymers containing a neutralized vinyl carboxylic acid such as acrylic acid, methacrylic acid or crotonic acid as a hydrophilic component (JP-A-49-14647;
No. 206023), a nonionic polymer which is a copolymer having vinylpyrrolidone or the like as a hydrophilic component, and a zwitterionic polymer which is a copolymer having a carboxybetaine moiety as a hydrophilic group (JP-A-51-9732, JP-A-55-
104209, JP-A-61-258804, JP-A-2-300110, etc.) are known and widely used. However, the ionic polymer described above,
Although a film is formed on the hair surface immediately after application, a hard feeling of finish (shape retention) is obtained. However, when an external force is applied to the hair, the applied film is destroyed. there were. In order to solve these problems, a plasticizer,
Attempts have been made to add fats and oils, silicone oils and derivatives thereof, but there have been problems such as an increase in tackiness and a decrease in hard feeling.

JP-A-7-285831 discloses (A) an ionic unsaturated monomer, (B) a polyether group-containing unsaturated monomer, and (C) a (meth) acrylate ester. And (D) a hair cosmetic composition containing a zwitterionic polymer obtained by amphoterating a copolymer obtained by copolymerizing another unsaturated monomer. However, this composition gives a film with a soft feel after hair application and drying, but has low waist (shape retention) of the hair,
Further improvements were needed. Also, JP-A-9-9558
No. 6 discloses a water-soluble hair styling composition containing a copolymer obtained by copolymerizing a betaine monomer and a (meth) acrylate. With this composition, although a film having a hard feel can be obtained at the time of hair application, the film is broken when an external force is applied, and there is a problem in the hard feeling of hair.

[0004]

DISCLOSURE OF THE INVENTION The present invention uses a specific zwitterionic polymer for hair cosmetics to impart a hard feel when applying hair,
An object of the present invention is to provide a hair cosmetic composition which is hardly broken even when an external force is applied to hair and has excellent performance in maintaining a hard feel.

[0005]

That is, the hair cosmetic composition of the present invention comprises (A) 20 to 80% by weight of an unsaturated monomer represented by the following general formula (I), and (B) 5 to 70% by weight of an unsaturated monomer represented by (II), (C) 5 to 60% by weight of a (meth) acrylate having a saturated or unsaturated aliphatic hydrocarbon group having 1 to 24 carbon atoms, And (D) a copolymer obtained by copolymerizing 0 to 20% by weight of another polymerizable unsaturated monomer in a hydrophilic solvent, by the following general formula (III) and / or the following general formula (IV) A hair cosmetic composition containing a zwitterionic polymer obtained by modification with an amphoteric agent represented by the formula:

[0006]

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Wherein R ¹ is a hydrogen atom or a methyl group, R ²
Is an alkylene group having 1 to 4 carbon atoms, R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A is NH or an oxygen atom. )

[0008]

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[0009] (wherein, R ⁵ is a hydrogen atom or a methyl group, R ⁶
And R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a group selected from one C (CH ₃ ) ₂ COCH ₃ , and one CH ₂ OH. XR ⁸ COOE (III) (wherein, R ⁸ is a saturated alkylene group having 1 to 4 carbon atoms, X is a bromine, chlorine or iodine atom, E is an alkali metal ion, ammonium cation or amine cation) .)

[0010]

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(Where n represents 2 or 3)

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

1. Constituent Components of Copolymer The copolymer constituting the hair cosmetic composition of the present invention comprises (A), (B) and (C) as essential components and (D) as an optional component. And are obtained by copolymerization of these components. Hereinafter, each component will be described. (1) Unsaturated monomer (A) The following general formula (I) used in the present invention:

[0013]

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The unsaturated monomer represented by the formula (hereinafter, referred to as (A) monomer) is acrylic acid or methacrylic acid (hereinafter, both are collectively referred to as (meth) acrylic acid. Acid esters and methacrylic acid esters are referred to as (meth) acrylates). Specifically, for example, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate,
Examples thereof include diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide.

The amount of the monomer (A) used in producing the copolymer of the present invention is determined by the total amount of the monomers [(A) + (B)
+ (C) + (D)] to 20 to 80% by weight, preferably 30 to 75% by weight. If the amount is less than 20% by weight, the resulting zwitterionic polymer becomes poorly soluble in a hydrophilic solvent,
In addition, it is difficult to wash and remove the film from the hair when washing the hair. If the amount exceeds 80% by weight, the resulting zwitterionic polymer will have low moisture resistance, will have insufficient hair setting power under high temperature and high humidity, and will exhibit stickiness.

(2) Unsaturated monomer (B) The following general formula (II) used in the present invention:

[0017]

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The unsaturated monomer (hereinafter referred to as (B) monomer) is a derivative of (meth) acrylic acid. Specifically, for example, (meth) acrylamide, N-
Ethyl (meth) acrylamide, Nn-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nn-octyl (meth) acrylamide, N
-T-octyl (meth) acrylamide, cyclohexyl (meth) acrylamide, lauryl (meth) acrylamide, phenyl (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, diacetone (meth) acrylamide, N-methylolacrylamide And the like.

The amount of the monomer (B) used in producing the copolymer of the present invention is 5 to 70 with respect to all monomers.
%, Preferably 15 to 60% by weight. 5% by weight
When the hair is ungrooved, the resulting copolymer will be damaged by the application of external force when applying hair, and the film will be broken, and the hard feel will be insufficient. If it exceeds 70% by weight, the obtained copolymer will be soft. It becomes insufficient to impart a hard feel to a film obtained by coating and drying on hair.

(3) Unsaturated monomer (C) (Meth) acrylic acid ester having a saturated or unsaturated aliphatic hydrocarbon group having 1 to 24 carbon atoms (hereinafter referred to as (C) Monomer))
Methyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate , Tridecyl (meth) acrylate, cetyl (meth) acrylate, palmityl (meth) acrylate,
Examples include stearyl (meth) acrylate, behenyl (meth) acrylate, and oleyl (meth) acrylate.

The amount of the monomer (C) used in producing the copolymer of the present invention is 5 to 60 with respect to all monomers.
%, Preferably 10 to 55% by weight. 5% by weight
If the groove is not grooved, the obtained copolymer will have a sticky feeling, and it will be insufficient to impart a hard feel to a film obtained by applying it to hair. If the amount exceeds 60% by weight, the resulting copolymer will have a problem in that the film will be broken by the application of external force during hair application, making it impossible to maintain a hard feel.

(4) Unsaturated monomer (D) Other polymerizable unsaturated monomers (hereinafter referred to as (D) monomer) other than (A), (B) and (C) used in the present invention. Body)
Is not an essential component, but can be used in an amount of 0 to 20% by weight, preferably 3 to 15% by weight, based on all monomers.
By appropriately selecting the D monomer to be used (appropriate flexibility and hardness can be imparted to the resulting zwitterionic polymer to adjust the feel and the like. As the monomer, for example, , Hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, methoxyethyl (meth)
Acrylate, ethoxyethyl (meth) acrylate,
(Meth) acrylic derivatives such as butoxyethyl (meth) acrylate, acrylonitrile, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate;
Aromatic unsaturated monomers such as styrene, chlorostyrene and vinyltoluene; vinyl unsaturated monomers such as N-vinylpyrrolidone and vinyl acetate;

2. The amphoteric agent is used to modify the above-mentioned copolymer into a zwitterionic polymer. In the present invention, the amphoteric agent represented by the following general formula (III) and / or (IV) It is. XR ⁸ COOE (III) (wherein, R ⁸ represents a saturated alkylene group having 1 to 4 carbon atoms, X represents a bromine, chlorine or iodine atom, and E represents an alkali metal ion, ammonium cation or amine cation. )

[0024]

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Examples of the amphoteric agent represented by the general formula (III) include metal salts of monohalogen-substituted fatty acids such as sodium monobromoacetate, potassium monochloroacetate, potassium monochloropropionate, and the like, 2-amino-2-methyl-1-propanol. Tertiary amines such as triethylamine, triethanolamine and 2-amino-2-ethyl-1,3-propanediol, or neutralized products of ammonia and monohard-substituted fatty acids. Examples of the amphoteric agent represented by the general formula (IV) include compounds such as propiolactone and butyrolactone. The amount of the amphoteric agent to be used is 70 to 130 mol%, preferably 80 to 120%, based on the monomer (A).

3. Production of Copolymer (Copolymerization of Monomer) The copolymer of the present invention can be produced by copolymerizing the monomers (A) to (D) in a hydrophilic solvent. The copolymerization reaction can be carried out by a known radical polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.A preferred polymerization method is a solution polymerization method, and a predetermined amount of a monomer is used. It is carried out by a method comprising dissolving in a solvent, adding a polymerization initiator, and heating and stirring at a temperature of 50 to 120 ° C. under a nitrogen stream.

Examples of the polymerization initiator include peroxides such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile, azobisdimethylpareronitrile, and azobismethyl-N-hydroxyethylpropionamide. Can be As the solvent, a hydrophilic solvent is used. For example, water: alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and butyl cellosolve; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate and ethyl acetate Acetates are preferred, and two or more of these solvents may be used as appropriate. The solvent is preferably used in such an amount that the polymer concentration of the resulting copolymer solution becomes 10 to 65% by weight.

In the polymerization, the monomer and the polymerization initiator are:
Normally, all of the types and amounts are present from the beginning of the polymerization, but a split addition method can be used for those types and / or amounts. The molecular weight of the obtained copolymer is preferably in the range of 5,000 to 500,000 in terms of weight average molecular weight. Control of molecular weight depends on polymerization temperature,
The polymerization can be carried out by appropriately selecting polymerization conditions such as the type and amount of a polymerization initiator, the amount of a solvent having a chain transfer property such as ethanol and isopropanol, and the amount of a chain transfer agent such as butyl mercaptan and lauryl mercaptan. .

4. By reacting the amphoteric polymer with the amphoteric polymer,
The copolymer is modified to obtain a zwitterionic polymer. After the above-mentioned copolymerization reaction is completed,
A predetermined amount of an amphoteric agent is added, and the mixture is added under a nitrogen atmosphere at 60 to 120.
It can be carried out with stirring at a temperature of ° C.

In the copolymer obtained by copolymerizing the monomers (A) to (D), the reaction between the portion composed of the monomer (A) and the amphoteric agent results in the following general formula (V) ) Or (V
A zwitterionic polymer having the zwitterionic structure represented by I) is obtained. When the amphoteric agent represented by the general formula (III) is used, a by-product salt represented by the following general formula (VII) is also produced.

[0031]

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(A) Depending on the type of monomer, amphoteric agent and polymerization solvent, by-product salts may precipitate or dissolve. Depending on the purpose of use of hair cosmetics, if necessary,
The precipitated by-product salt may be filtered and separated and removed by a centrifuge, and the dissolved salt may be further removed by ion exchange treatment. (For example, JP-A-55-104209, JP-A-61-258)
No. 804). The weight-average molecular weight of the obtained zwitterionic polymer is 5,000 to 500,000, preferably 10,000 to 400,000. As the obtained zwitterionic polymer, the solution of the produced polymer may be used as it is, or the solvent of the produced polymer solution is removed by evaporation, or the polymer is precipitated using a poor solvent to obtain the obtained solid. Shaped polymers may be used. Also,
If necessary, the odor of the obtained zwitterionic polymer should be improved by azeotropic distillation of the odor component with the solvent in the solution state or by adsorption removal with an adsorbent such as activated carbon, activated clay and zeolite. Can be. In the solid state, the removal can be carried out by heating under reduced pressure, extraction with a solvent such as ethers, or the like.

5. Hair cosmetic composition The hair cosmetic composition of the present invention is a composition in which the amphoteric polymer obtained as described above is contained in a cosmetic medium. Hair cosmetics in the present invention are shampoos, rinses, treatments, hair cosmetics for removing hair after use such as permanent wave liquid, and mascara, aerosol hair spray, pump hair spray, foam hair styling, set lotion, Hair liquid,
It means a well-known hair cosmetic such as a hair setting agent that does not remove hair after use such as a hair gel, a hair cream, a hair oil, etc. A particularly preferable use is a hair styling cosmetic that does not remove hair after use.

The content of the zwitterionic polymer in the composition of the present invention is preferably 0.1 to 10% by weight in the cosmetic. When the content is less than 0.1% by weight, when used as a hair cosmetic, it is insufficient to exert the effect of the polymer, and when it exceeds 10% by weight,
The amount of the polymer adhering to the hair is increased, which may undesirably inhibit the effect.

A cosmetic medium is blended with the cosmetic. The cosmetic medium refers to a solvent constituting the above-described various forms of hair cosmetics, a liquefied gas or a gas used as a propellant, and the like. Specific examples include hydrophilic solvents such as water, ethyl alcohol, isopropyl alcohol, and monohydric or dihydric alcohols such as ethylene glycol; and hydrophobic solvents such as isoparaffin and cyclic silicone. Examples of the liquefied gas or gas include liquefied petroleum gas, dimethyl ether, halogenated hydrocarbon, carbon dioxide gas, nitrogen gas and the like.

Further, the hair cosmetic composition of the present invention may contain known additives such as surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants and zwitterionic surfactants. Agents, foaming agents, thickeners, hadrotropes, emulsifiers, conditioning agents including silicone polymers and their chemically modified products, oils and fats, humectants,
Colorants such as plasticizers, dyes and pigments, bactericides, fragrances and the like can be used.

The composition of each hair cosmetic is illustrated below. (I) Hair mousse that can be sprayed in a foam state: (a) 0.1 to 10% by weight of amphoteric polymer (b) 0.1 to 5% by weight of nonionic surfactant (c) Liquefied gas 3 to 25 % By weight (d) Water-soluble solvent 60% by weight to residue

(Ii) Hair spray: (a) 0.1 to 10% by weight of zwitterionic polymer (e) 30 to 80% by weight of organic solvent or water having a boiling point of 50 to 300 ° C. (f) Propellant 10 to 60 weight%

(Iii) Hair gel: (a) amphoteric polymer 0.1 to 10% by weight (g) gel base 0.1 to 3% by weight (h) water 72% by weight to residue

(Iv) Hair set lotion: (a) 0.1 to 10% by weight of zwitterionic polymer (b) 90% by weight of water-soluble solvent to residue

Further, the hair cosmetic composition of the present invention comprises
A part (1 to 90% by weight) of the component (a) has a conventionally known weight average molecular weight of 5,000 to 500,0.
It may be replaced with a natural polymer such as 00, a cationic polymer, an anionic polymer, a nonionic polymer, a natural modified polymer, or a synthetic polymer.

Specific examples of the cationic polymer include:
As the synthetic cationic polymer, Guffcut 75
N-vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer such as 5N, 755, 734 (manufactured by ISP), Rubicut PQ11 (manufactured by BASF); copolymers 845, 937, 958 (manufactured by IS)
N-vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer such as G.Fix VC-7
N-vinylpyrrolidone / N-vinylcaprolactam / dimethylaminoethyl methacrylate copolymer such as 13 (manufactured by 1SP); N-vinylpyrrolidone / methacrylamidopropyl trimethylammonium chloride copolymer such as Guffcut HS-1100 (manufactured by ISP Welfare) Combined; Rubicut FC370, FC550, FC905, HM-552
N-vinylpyrrolidone / quaternized methylvinylimidazolium copolymer such as (manufactured by BASF); dimethyldiallylammonium chloride polymer such as mercoat 100, 550 (manufactured by Calgon); dimethyldiallylammonium chloride / Acrylamide copolymer: JP-A-4-21623 and JP-A-5-30503
No. 8, quaternized dialkylaminoalkylene methacrylate / (meth) acrylic acid alkyl ester copolymer and the like.

As the cationic polymer modified with natural products,
Hydroxyethyl cellulose / dimethyldiallylammonium chloride copolymer such as Celcut, H-100, L200 (all manufactured by National Starch); Celcut lSC-240, SC-240C, SC-230
M (manufactured by National Starch), Ecare Polymer JR-125, JR-400, JR-30M (manufactured by Amacor), Leogard G (manufactured by Lion), Catinal HC, LC (manufactured by Toho Chemical) Made)
Reaction product of hydroxyethylcellulose with epoxidized trimethylammonium compound; Kitamer KC
(Made by Amacor Co., Ltd.).

The nonionic polymer has a carboxyl group,
Or a polymer having an acidic group such as a sulfonic acid group. As specific examples, Gantrez ES-225, ES-42
5, A-425, V-225, V-425 (above, IS
P28); methyl vinyl ether / alkyl maleic anhydride half ester copolymer; resin 28-1310
(National Starch), Rubiset CA (BAS
Vinyl acetate / crotonic acid copolymer such as resin F-2); vinyl acetate / crotonic acid / vinyl neodecanoate copolymer such as resin 28-2930 (National Starch); vinyl acetate such as Lupiset CAP (BASF). / Crotonic acid / vinyl propionate copolymer; Advantage CP
Vinyl acetate / monobutyl maleate / isobornyl acrylate copolymer;
P (BASF), Diamond Hold (Mitsubishi Chemical)
(Meth) acrylic acid / (meth) acrylic acid ester copolymer; Ultrahold; Strong, Ultrahold 8 (above, manufactured by BASF), Persachil 42 (National Starch), plus size L53P (compatible chemical), etc. Acrylic acid / acrylamide derivative copolymer;
Polyvinylpyrrolidone / (meth) acrylic acid / (meth) acrylate copolymer such as Rubiflex VBM35 (manufactured by BASF); diethylene glycol / such as Eastman AQ polymer (manufactured by Eastman Chemical Company);
Cyclohexane dimethanol / dimethyl isophthalate /
Sulfonated dimethyl isophthalate condensate and the like can be mentioned.

The acidic groups in these anionic polymers are preferably used after neutralizing a part or all of the acidic groups with a basic compound from the viewpoint of water solubility. Examples of such a basic compound include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; inorganic basic compounds such as aqueous ammonia; ethanolamine, diethanolamine, triethanolamine, triisopropanolamine; Use of alkanolamines such as 2-amino-2-methyl-11-propanol, 21-amino-21-methyl-1,3-propanediol and aminomercaptopropanediol; basic amino acid compounds such as lysine, arginine and histidine; Can be done. Among these, it is particularly preferable to use 21-amino-21-methyl-1-propanol and potassium hydroxide from the viewpoint of water solubility.

The anionic polymer is a polymer containing an unsaturated monomer having a pyrrolidone ring, a caprolactam ring, an N-alkyl-substituted amide group, a polyether group, or an acetamido group or a formamide group as an essential component. Specific examples of the polymer having a ring include Rubiscol K-7, K-12, K-30, KK60, and K-19.
0 (above, manufactured by BASF), PVPK-15, K-3
Polyvinylpyrrolidone such as 0, K-60, K-90, and K-120 (all manufactured by ISP); Rubiscol VA2
8, VA37, VA55, VA64, VA73 (above,
BASF), PVP / VA-735, PVP / VA
635, PVP / VA-535, PVP / VA-33
5, PVP / VA-235, S-630 (above, 1SP
Vinylpyrrolidone / vinyl acetate copolymers such as those manufactured by Co., Ltd.); vinylpyrrolidone / vinyl acetate / vinyl propionate copolymers such as Rubiscol VAP343 (BASF).

Specific examples of the polymer containing an unsaturated monomer containing an amide group, an N-alkyl-substituted amide group or a polyether group as essential components include (meth) acrylamide and N-octyl (meth) acrylamide. Homoradical polymer of unsaturated monomer such as hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate / polypropylene glycol, or (meth) acrylic acid alkyl (C _l ~C ₂₄₎ esters, may be mentioned radical copolymer of vinyl acetate and the like.
Specific examples of the polymer containing an unsaturated monomer containing an acetamido group and a formamide group as an essential component include a single radical polymer of an unsaturated monostar such as N-vinylacetamide and N-vinylformamide, or (meth) A) radical copolymers with alkyl (C ₁ -C ₂₄ ) acrylates, vinyl acetate and the like.

[0048]

The following non-limiting experimental examples further illustrate the present invention. Parts and percentages in Production Examples are on a weight basis, and parts and percentages in Examples are on a weight basis in terms of active ingredients.

Production Example of Zwitterionic Polymer Production Example 1 30 parts of dimethylaminoethyl methacrylate and diacetone were placed in a five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a glass tube for purging nitrogen, and a stirrer. Acrylamide 20 parts, ethyl methacrylamide 40
Parts, 10 parts of stearyl methacrylate and 100 parts of absolute ethanol, and 0.6 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) were added.
Heat to reflux at a temperature of 0 ° C. and after 2 hours AIBN 1.0
The copolymerization reaction was further performed for 6 hours under a nitrogen stream. Then, a 50% anhydrous ethanol solution of dimethylaminoethyl methacrylate and an equimolar neutralized aminomethylpropanol of monochloroacetic acid was added dropwise to the flask using a dropping funnel, and further heated under reflux at 80 ° C. under a nitrogen stream. For 8 hours to obtain 260 parts of a zwitterionic polymer solution. The polymer thus obtained is referred to as "P-1". The weight average molecular weight of the polymer was 65,000 as measured by gel permeation chromatography (hereinafter abbreviated as GPC) using polystyrene as a standard substance.

Production Example 2 70 parts of dimethylaminoethylacrylamide and t-butylacrylamide 1 were placed in the same five-necked flask as in Production Example 1.
5 parts, 15 parts of lauryl methacrylate and 100 parts of absolute ethanol were added, and 3.0 parts of azobismethyl-N-hydroxyethylpropionamide was added.
The mixture was heated at reflux at 0 ° C. and the copolymerization reaction was carried out for 40 hours. Then, a 50% anhydrous ethanol solution of 0.8 mol of dimethylaminoethylacrylamide neutralized with aminomethylpropanol of monochloroacetic acid was added by a dropping funnel. The mixture was added dropwise to the flask, and heated under reflux at 80 ° C. under a nitrogen stream to carry out an amphoteric reaction for 8 hours to obtain 340 parts of a polymer solution. The obtained polymer was designated as “P-2”
And The weight average molecular weight of the obtained polymer is
When measured by GPC in the same manner as in Production Example 1, 120,0
00.

Preparation Example 3 In the same five-necked flask as in Preparation Example 1, dimethylaminoethyl methacrylate 40 parts and dimethylacrylamide 30 were added.
Parts, 15 parts of normal butyl methacrylate, 15 parts of stearyl methacrylate and 100 parts of absolute ethanol, 0.1 part of azobisdimethyl valeronitrile (hereinafter abbreviated as AVN) was added, and the mixture was refluxed at 65 ° C. under a nitrogen stream. After 4 hours, 1.0 part of AIBN was added, and the mixture was refluxed and heated at 80 ° C. under a nitrogen stream to carry out copolymerization for 6 hours. Next, a 40% anhydrous ethanol suspension of dimethylaminoethyl methacrylate and equimolar potassium hydroxide neutralized monochloroacetic acid was added dropwise to the five-necked flask with a dropping funnel. And heated under reflux for 12 hours to carry out an amphoteric reaction. The resulting viscous suspension was filtered through a filter to remove the suspension, and the filtrate was filled with a regenerated cation exchange resin ("Diaion PK-220" was regenerated and the system was replaced with anhydrous ethanol). The solution was passed through a column, and then passed through a column packed with a regenerated anion exchange resin ("Diaion PA-416", the system of which was replaced with anhydrous ethanol after regeneration). Subsequently, the solvent was removed at a temperature of 70 ° C. under reduced pressure to obtain a solid. After pulverizing the solid, it is thoroughly washed with diethyl ether, and dried under reduced pressure for 7 hours.
Drying well at a temperature of 0 ° C. gave 100 parts of solid.
The polymer thus obtained is referred to as "P-3". The weight average molecular weight of the obtained polymer was 160,000 as measured by GPC in the same manner as in Production Example 1.

Production Example 4 30 parts of diethylaminoethyl methacrylate, 15 parts of acrylamide, 10 parts of methyl methacrylate, 30 parts of isobutyl methacrylate, 15 parts of tridecyl methacrylate, and 230 parts of anhydrous ethanol were placed in the same five-necked flask as in Production Example 1. And add 1.2 parts of AVN
Reflux heating was performed at a temperature of 80 ° C. under a nitrogen stream.
1.0 part of IBN was added, and the mixture was refluxed and heated at 80 ° C. under a nitrogen stream to carry out a copolymerization reaction for 6 hours. Then
50 of aminoethylpropanediol neutralized product of monochloroacetic acid equimolar to diethylaminoethyl methacrylate
% Ethanol suspension was dropped into a five-necked flask with a dropping funnel, and further heated under reflux at a temperature of 80 ° C. under a nitrogen stream to carry out an amphoteric reaction for 12 hours. Then, under reduced pressure 70
The solvent was removed at a temperature of ° C. to obtain a solid. The solid was pulverized, washed well with diethyl ether, and thoroughly dried under reduced pressure at a temperature of 70 ° C. to obtain 390 parts of a solid. The polymer thus obtained is referred to as "P-4". The weight average molecular weight of the polymer was 30,000 as measured by GPC in the same manner as in Production Example 1.

Production Example 5 In the same five-necked flask as in Production Example 1, 45 parts of dimethylaminoethyl methacrylate and dimethylacrylamide 2 were added.
0 parts, 15 parts of t-butyl acrylate, 10 parts of penyl methacrylate, 10 parts of N-vinylpyrrolidone and 100 parts of anhydrous ethanol, 0.6 parts of AIBN were added, and the mixture was refluxed and heated at 80 ° C. under a nitrogen stream. After 2 hours, 1.0 part of AIBN was added, and a copolymerization reaction was further performed under a nitrogen stream for 6 hours. Then, a 50% anhydrous ethanol solution of a neutralized aminomethylpropanol solution of monochloroacetic acid and dimethylaminoethyl methacrylate in an equimolar amount was dropped into a five-necked flask with a dropping funnel, and further added with nitrogen stream.
Reflux heating at a temperature of 0 ° C. to carry out an amphoteric reaction for 10 hours,
300 parts of a polymer solution were obtained. The obtained polymer is designated as "P-5". The weight average molecular weight of the polymer was measured by GPC in the same manner as in Production Example 1, and was found to be 90,
000.

Production Example 6 50 parts of dimethylaminoethyl acrylamide, 30 parts of diacetone acrylamide, 10 parts of methyl methacrylate, 10 parts of lauryl methacrylate and 100 parts of absolute ethanol were placed in the same five-necked flask as in Production Example 1. After adding 1.6 parts, reflux heating was performed at a temperature of 80 ° C. under a nitrogen stream, and after 2 hours, 1.0 part of AIBN was added, and a copolymerization reaction was further performed under a nitrogen stream for 6 hours. Then, 50% of an aminomethylpropanol neutralized product of monochloroacetic acid in an equimolar amount with dimethylaminoethylacrylamide was used.
% Anhydrous ethanol solution was dropped into a five-necked flask using a dropping funnel, and further, the mixture was refluxed and heated at a temperature of 80 ° C. under a nitrogen stream to carry out an amphoteric reaction for 10 hours to obtain 310 parts of a polymer solution. The obtained polymer is designated as "P-6". The weight average molecular weight of the polymer was measured by GPC in the same manner as in Production Example 1 and found to be 70,000.

Production Example 7 A polymerization operation was carried out in the same manner as in Production Example 1 except that the unsaturated monomer was changed to 10 parts of dimethylaminoethyl methacrylate, 80 parts of diacetone acrylamide and 10 parts of lauryl acrylate. In the same manner as in 1, amphoteric reaction was carried out using a neutralized product of monochloroacetic acid with aminomethylpropanol to obtain 120 parts of a polymer solution. The obtained polymer is set to "P-7". The weight average molecular weight of the polymer was measured by GPC in the same manner as in Production Example 1, and found to be 70,000.

Production Example 8 A polymerization operation was carried out in the same manner as in Production Example 1 except that the unsaturated monomer was changed to 85 parts of dimethylaminoethyl methacrylate, 1 part of acrylamide and 14 parts of n-butyl methacrylate. In the same manner as in 1, amphoteric reaction was carried out with the aminomethylpropanol neutralized product of monochloroacetic acid,
380 parts of a polymer solution were obtained. The obtained polymer is set to "P-8". The weight average molecular weight of the polymer was measured by GPC in the same manner as in Production Example 1, and was found to be 70,
000.

Production Example 9 Unsaturated monomers were prepared as follows: dimethylaminoethyl acrylamide (10 parts), diacetone acrylamide (10 parts), methyl methacrylate (20 parts), isobutyl methacrylate (40)
Parts and stearyl methacrylate 20 parts, and the same polymerization operation as in Production Example 1 was carried out. Then, as in Production Example 1, an amphoteric reaction was carried out with an aminomethylpropanol-neutralized product of monochloroacetic acid to give 210 parts. Was obtained. The obtained polymer is designated as "P-9". The weight average molecular weight of the polymer was measured by GPC in the same manner as in Production Example 1 and found to be 65,000.

Example 1 When the amphoteric polymer "P-1" obtained in Production Example 1 was spray-applied to hair in the form of an aerosol spray or a pump spray having the following formulation, a hard feel was imparted. At the same time, even when an external force was applied to the hair, the applied film was hardly broken and exhibited excellent performance in maintaining a hard feel. In addition, good hair washability was exhibited.
(See Table 1).

(I) aerosol spray part by weight zwitterionic polymer (as active ingredient) 3 petroleum liquefied gas 20 ethanol balance (total) 100

(Ii) Pump spray parts by weight Zwitterionic polymer (as active ingredient) 0.5, 3.0 or 5.0 Water 20 Ethanol Balance (Total) 100

Before compounding the above formulation, the polymer content in the “P-1” solution obtained in Production Example 1 was determined in advance, and the calculated value was used to convert the concentration to obtain the amount of the polymer solution. Were determined. The polymer content in the solution was determined by drying under reduced pressure at a temperature of 80 ° C. for 4 hours and weighing the residual amount after removing the solvent.

Examples 2 to 6 "P-2", "P-3", "P-4", "P-5" and "P-6" were evaluated in the same manner as in Example 1. −
As in the case of "1", the composition exhibited good performance as a hair cosmetic (see Table 1).

Comparative Examples 1 to 3 When "P-7", "P-8" and "P-9" were evaluated in the same manner as in Example 1, a hard feel and a hard feel when an external force was applied to the applied hair. Performance was insufficient or problematic in any of the evaluation items of the feeling retention and the hair washability. (See Table 1).

The evaluation of the hair cosmetic composition was also performed by the following evaluation method. 1) Hard feeling (feel) Spray a certain amount of the active ingredient in the form of a pump spray of 0.5 and 3.0% by weight on a 23 cm, 2 g non-habited hair as an active ingredient, and immediately wind it on a curler having a diameter of 2 cm. dry. Then, the hair removed from the curler was left under the condition of constant temperature and humidity of 23 ° C./60% RH,
Touch with your finger and evaluate the hard feeling. ：: Hard feeling is excellent. ：: There is a hard feeling. Δ: Hard feeling is inferior. ×: No hard feeling.

2) Retention of hard feeling (when an external force is applied) To 15 cm, 1.3 g of uncurled hair, 3.0 and 5.0 wt% of a pump spray as an active ingredient, and 3 as an active ingredient A fixed amount is sprayed on the hair in the form of an aerosol spray of 0.0% by weight, and the hair is immediately adjusted to a width of 2 cm and dried. Then, after standing overnight at 23 ° C./60% RH, using a rheometer (manufactured by Fudo Kogyo Co., Ltd.), the stress (g) generated when both ends of the test piece were used as fulcrums and the center part was pressed and bent 2 cm. ) Is measured on the same sample at the initial and second times. The retention ratio of the hard feeling was calculated by the following equation. Retention (%) = [Second stress / initial stress] × 100

As the evaluation results, the measured values obtained were indicated by the following ranks. (Initial stress and second stress) 50 or less (g): 1 51 to 75: 2 76 to 100: 3 101 to 125: 4 126 to 150: 5 151 to 175: 6 176 to 200: 7

(Retention) 100 to 81 (%): A 80 to 61: B 60 to 41: C 40 to 21: D

3) Hair washability The curled hair obtained using a pump spray containing 3% by weight of polymer as the active ingredient and operated in the same manner as in the measurement of hard feeling was used to obtain dodecyl alcohol maintained at a temperature of 40 ° C. Ethylene oxide 3
Washed with a 10% by weight aqueous solution of the sulfate of the molar adduct,
Rinse well with warm water at ℃. After air-drying, the polymer remaining on the hair is visually and visually evaluated. ：: The polymer has been removed △: The polymer slightly remains ×: The polymer remains

[0069]

[Table 1]

[0070]

Industrial Applicability The hair cosmetic composition of the present invention provides a film which is excellent in hard feeling and easy to wash.

Claims (3)

[Claims] (A) 20 to 80% by weight of an unsaturated monomer represented by the following general formula (I); (B) an unsaturated monomer represented by the following general formula (II):
70% by weight, (C) a (meth) acrylate ester having a saturated or unsaturated aliphatic hydrocarbon group having 1 to 24 carbon atoms
0% by weight, and (D) a copolymer obtained by copolymerizing 0 to 20% by weight of another polymerizable unsaturated monomer in a hydrophilic solvent, to obtain a copolymer represented by the following general formula (III) and / or A hair cosmetic composition containing a zwitterionic polymer obtained by modification with an amphoteric agent represented by the formula (IV). Embedded image (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 4 carbon atoms, and R ³ and R ⁴ are each independently a hydrogen atom or 1 to 4 carbon atoms. The alkyl group, A represents NH or an oxygen atom.) (Wherein R ⁵ is a hydrogen atom or a methyl group, R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, one C (CH ₃ ) ₂ COCH ₃ , CH ₂ OH
Represents a group selected from XR ⁸ COOE (III) (wherein, R ⁸ is a saturated alkylene group having 1 to 4 carbon atoms, X is a bromine, chlorine or iodine atom, E is an alkali metal ion, ammonium cation or amine cation) ). (Where n represents 2 or 3) 2. The hair cosmetic composition according to claim 1, wherein the zwitterionic polymer has a weight average molecular weight of 5,000 to 500,000. 3. The method according to claim 1, wherein the zwitterionic polymer is 0.1 to 10%.
The hair cosmetic composition according to claim 1, which is contained by weight%.