JPH07285831A - Hair cosmetic composition - Google Patents

Abstract

PURPOSE:To provide a hair cosmetic composition which contains a specific tonic polymer having an unsaturated monomer bearing polyether groups as a constituent and gives flexible touch without strange feeling and has excellent hair-setting properties. CONSTITUTION:The object hair cosmetic contains a cationic or amphoteric polymer which is obtained by copolymerization of (A) an ionic unsaturated monomer selected from amphoteric, anionic and cationic unsaturated monomers (in an amount of 20-60wt.%), (B) an unsaturated monomer bearing polyether groups of the formula (R<1> is H, methyl; R<2> is a 1-4C alkyl, phenyl, H; R<3> is a 1-3C alkyl; m, n, p are 0-30 and m+n+p=3-50) (in an amount of 21-60wt.%), (C) an alkyl (meth)acrylate bearing a 1-24C alkyl (in an amount of 10-59wt.%) and optimally other polymerizable unsaturated monomers (in an amount of 0-20wt.%). The hair cosmetic is used after shampooing, rinsing, treatment or application of the permanent wave-treatment solutions to remove them. Particularly preferably, the cosmetic is not removed by washing after application.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hair cosmetic composition, and more particularly to a hair cosmetic composition containing a specific ionic polymer having a polyether group-containing unsaturated monomer as a constituent. The composition of the present invention, as a hair cosmetic,
It has a soft and comfortable feel and is easy to set.

[0002]

2. Description of the Related Art As a polymer used for hair styling,
Anionic polymer which is a copolymer containing a neutralized product of vinylcarboxylic acid such as acrylic acid, methacrylic acid and crotonic acid as a hydrophilic component (JP-A-49-14647 and JP-A-3-2).
No. 06023), 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). 55-10
4209, JP-A-61-258804, JP-A-2-30
No. 0110, etc.) are known and widely used.

However, since each of the above-mentioned ionic polymers forms a strong film, it has a hard finish,
In addition, there is a problem of uncomfortable feeling at the time of finishing due to the presence of these films. In order to solve these problems, it has been attempted to add flexibility to each of the above-mentioned ionic polymers by adding a plasticizer, oils and fats, silicone oil and derivatives thereof, but the tackiness may be increased. ,
There are problems such as a decrease in the setting power, and satisfactory products are not obtained. Further, an attempt has been made to use a water-soluble nonionic polyether-based acrylic oligomer as a hair styling material (JP-A-59-50912).
There was a problem such as not having sufficient setting power.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of conventional polymers by using a specific polymer having a cationic or zwitterionic property for hair cosmetics, thereby providing a soft and comfortable feeling. An object of the present invention is to provide a hair cosmetic composition having a feel and an excellent setting property.

[0005]

Means for Solving the Problems That is, the hair cosmetic composition of the present invention comprises (A) an ionic unsaturated monomer; 2
0 to 60% by weight, (B) a polyether group-containing unsaturated monomer represented by the following general formula (I); 21 to 60% by weight,
(C) Having an alkyl group having 1 to 24 carbon atoms (meth)
A copolymer of an acrylic acid alkyl ester; 10 to 59% by weight, and (D) another polymerizable unsaturated monomer; 0 to 20% by weight, having a weight average molecular weight of 5,000 to 30.
A hair cosmetic composition comprising a polymer having a cation or zwitterionicity of 10,000.

[0006]

[Chemical 2]

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a saturated alkyl group having 1 to 4 carbon atoms, a phenyl group, or a hydrogen atom, and R ³ is 1 to 3 carbon atoms. Represents a saturated alkyl group having m, n, p is 0 respectively.
The sum of m, n, and p is 3 to 50. )

The cationic or zwitterionic polymer used in the present invention is (A) zwitterionic, anionic,
And an ionic unsaturated monomer selected from unsaturated monomers having a cationic property, (B) a polyether group-containing unsaturated monomer, and (C) (meth) acrylic acid [wherein acrylic acid and meta Acrylic acid is generically referred to as (meth) acrylic acid. ] It can be obtained by copolymerizing an alkyl ester and, as an optional component, a specific amount or less of another polymerizable unsaturated monomer (D).

1. Unsaturated Monomer Examples of the ionic unsaturated monomer as the component (A) include the following. (A) Cationic unsaturated monomer As the cationic unsaturated monomer, for example, a derivative of (meth) acrylic acid represented by the following general formula (II) or a diallyldialkylammonium compound which is an ammonium derivative of an allyl compound is used. (However, the number of carbon atoms of the alkyl group is 1 to
Twelve. ) Is mentioned.

[0010]

[Chemical 3]

(In the formula, R ¹ is a hydrogen atom or a methyl group, R ⁴ is an alkylene group having 1 to ⁴ carbon atoms, and R ⁵ and R ⁶ are respectively
An alkyl group having 1 to 4 carbon atoms, R ⁷ is a hydrogen atom, 1 carbon atom
~ 12 alkyl group, benzyl group, or fatty acid ester residue, A represents -O- group or -NH- group. )

Specific examples of the cationic unsaturated monomer include N- (meth) acryloyloxyethyl-N, N,
N-trimethylammonium, N- (meth) acryloylaminopropyl-N, N, N-trimethylammonium, N- (meth) acryloyloxyethyl-N, N-
The fourth such as dimethyl N-ethylammonium, N- (meth) acryloyloxyethyl-N, N-dimethyl N-benzylammonium, N- (meth) acryloyloxyethyl-N, N-diethyl-N-methylcarboxyethylammonium Derivatives of (meth) acrylic acid having a quaternary ammonium as a cation, derivatives of (meth) acrylic acid such as neutralized products of N- (meth) acryloyloxyethyl-N, N-dimethylamine with acids such as hydrochloric acid and lactic acid,
And diallyldimethylammonium and the like.

Instead of the above cationic unsaturated monomer,
Each of the precursors, an amine or amide derivative of (meth) acrylic acid represented by the following formula (III), or a diallyl monoalkylamine compound is used to copolymerize and then neutralize with an acid or react with a cationizing agent. Thus, a cationized polymer can be obtained.
Examples of the cationizing agent include halogenated alkyl compounds such as methyl chloride, ethyl chloride, lauryl chloride, methyl iodide and butyl bromide; halogenated benzyl compounds such as benzyl chloride; methyl monobromacetate, ethyl monochloroacetate and monochloropropionic acid. Examples thereof include monohalogenated fatty acid ester compounds such as ethyl; dialkyl sulfate compounds such as dimethyl sulfate and diethyl sulfate.

[0014]

[Chemical 4]

(In the formula, R ¹ , R ^{4 to} R ⁶ and A have the same meanings as in formula (II).) Specific examples of the unsaturated monomer as the precursor include dimethylaminoethyl ( (Meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth)
Examples thereof include acrylamide and diethylaminopropyl (meth) acrylamide.

(B) Zwitterionic unsaturated monomer The zwitterionic unsaturated monomer is a cationic compound in the same molecule,
It is an unsaturated monomer having an anionic zwitterionic group, and examples thereof include (meth) acrylic acid derivatives represented by the following general formula (IV).

[0017]

[Chemical 5]

(Wherein R ¹ is a hydrogen atom or a methyl group, R ⁴
And R ⁸ are each an alkylene group having 1 to 4 carbon atoms, R ⁵
And R ⁶ are each an alkyl group having 1 to 4 carbon atoms, A
Is -O- group or -NH- group, B is -COO group, PHO ₃ group, or-
An SO ₃ group is shown. )

Specific examples of the zwitterionic unsaturated monomer represented by the formula (IV) include N- (meth) acryloyloxyethyl N, N-dimethylammonium N-methylcarboxylate and N- (meth) acryloyl. Aminopropyl N, N-dimethylammonium N-methylcarboxylate, N- (meth) acryloyloxyethyl N, N-
Diethyl ammonium N-propane sulfonate and the like can be mentioned.

In place of the zwitterionic unsaturated monomer, a copolymer of an amine derivative or amide derivative of (meth) acrylic acid represented by the general formula (III), which is a precursor of the amphoteric agent, is used. Can also be reacted to obtain a zwitterionized polymer. Examples of the amphoteric agent include sodium monobromide acetate, potassium monochloroacetate, lithium monochloropropionate, or neutralized products of monochloroacetic acid and ammonia, 2-amino-2-methyl-1-propanol, triethanolamine, or the like. Salts of monohalogenated fatty acids; lactones such as propiolactone; sultones such as propane sultone; and phosphides such as propiophosphide.

(C) Combination of Cationic Unsaturated Monomer and Anionic Unsaturated Monomer As a method for imparting zwitterionicity to the polymer, the above (b) zwitterionic unsaturated monomer is used. , A combination of a cationic unsaturated monomer and an anionic unsaturated monomer,
A method of copolymerization can also be adopted. In this case, the above-mentioned (a) cationic unsaturated monomer is used as the cationic unsaturated monomer.

Examples of the anionic unsaturated monomer used in combination include unsaturated carboxylic acid monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and crotonic acid; unsaturated Half-esters of polybasic acid anhydrides (eg, succinic anhydride, phthalic anhydride, etc.) and hydroxyl group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate; styrenesulfonic acid, sulfoethyl ( Examples include monomers having a sulfonic acid group such as (meth) acrylate; monomers having a phosphoric acid group such as acid phosphooxyethyl (meth) acrylate and 3-chloro-2-acid phosphooxypropyl (meth) acrylate. .

These anionic unsaturated monomers can be used in the form of an acid or partially neutralized or completely neutralized. They are subjected to copolymerization as an acid and then partially neutralized or completely neutralized. You can also Examples of the base used for neutralization include lithium hydroxide, potassium hydroxide, alkali metal hydroxides such as sodium hydroxide, aqueous ammonia,
Mono-, di-, or triethanolamine, triethylamine, morpholine, aminomethylpropanol,
Examples thereof include amine compounds such as aminoethylpropanediol.

The ratio of the cationic unsaturated monomer to the anionic unsaturated monomer used is preferably in the range of 1/10 to 10/1 in terms of molar ratio.

The amount of the ionic unsaturated monomer as the component (A) used is 20 to 60% by weight based on the total amount of the unsaturated monomer,
It is preferably 25 to 55% by weight. If it is less than 20% by weight, the resulting ionic polymer is hardly soluble in a hydrophilic solvent, and it is difficult to remove it by washing when washing hair. 60% by weight
When it exceeds the above range, the moisture resistance of the obtained ionic polymer is lowered, the hair setting force under high temperature and high humidity becomes insufficient, and the obtained polymer film becomes sticky.

Component (B), Polyether Group-Containing Unsaturated Monomer The polyether group-containing unsaturated monomer has the general formula (I) above.
Is a (meth) acrylic unsaturated monomer having a polyether group. When the sum of m, n, and p of the polyether group is less than 3, an ionic polymer obtained by copolymerization,
The advantages of the polyether compound cannot be exhibited. On the other hand, when it exceeds 50, the resulting ionic polymer exhibits a sticky feeling, and the copolymerizability with the unsaturated monomer of the other component decreases, which is not preferable.

The unsaturated monomer containing a polyether group can be obtained by an esterification reaction of a polyether compound and (meth) acrylic acid. Instead of the unsaturated monomer having a polyether group, it is also possible to subject it to copolymerization in the form of its precursor (meth) acrylic acid and then subject the polyether compound to an esterification reaction.

The unsaturated monomer containing a polyether group is also available as a commercial product. Depending on the values of m, n, p of the polyether group, it is a series product under the trade name, for example, NK ester series, M -40G, M-90G, M-23
0G, AMP-60G (manufactured by Shin-Nakamura Chemical Co., Ltd.), MTG-A in the light acrylate series, 130MA in the light ester series, 041MA (manufactured by Kyoeisha Chemical Co., Ltd.), PP-1000 in the Bremmer series.
PP-500, PP-800, PE-200, PE-3
50, 70 PEP-350B, 55 PET-800, P
ME-200, PME-400 (manufactured by NOF CORPORATION) and the like.

The amount of the polyether group-containing unsaturated monomer used is 21 to 60% by weight, preferably 2
5 to 55% by weight. If it is less than 21% by weight, the flexibility of the obtained polymer will be insufficient, and when applied to hair, an uncomfortable feeling will occur. When it exceeds 60% by weight, the resulting polymer becomes sticky and the hair setting power becomes insufficient.

Examples of the alkyl ester of (meth) acrylic acid as the component (C) are as follows:
Methyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, Tridecyl (meth) acrylate, cetyl (meth) acrylate, palmityl (meth) acrylate,
Examples thereof include alkyl (meth) acrylates having a saturated and unsaturated alkyl group having 1 to 24 carbon atoms such as stearyl (meth) acrylate, behenyl (meth) acrylate and oleyl (meth) acrylate.

The amount of alkyl (meth) acrylate used is 10 to 59% by weight, preferably 1
5 to 55% by weight. If it is less than 10% by weight, the resulting polymer will have a sticky feeling and the hair setting power will be insufficient. When it exceeds 59% by weight, the flexibility of the obtained polymer becomes insufficient, and when applied to hair, there is a problem that it causes a feeling of strangeness.

(D) Other Unsaturated Monomers In addition to the monomers of the above-mentioned components (A) to (C), other unsaturated monomers, although not an essential component, are added to all the monomers. 0-2
0% by weight can be used. By appropriately selecting the unsaturated monomer as the component (D) to be used, it is possible to impart appropriate flexibility and hardness to the resulting ionic polymer to control the feel and the like.

Other unsaturated monomers used as the component (D) include, for example, acrylonitrile, hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth). (Meth) acrylic derivatives such as acrylate, tetrahydrofurfuryl (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, diacetone acrylamide; styrene,
Aromatic unsaturated monomers such as chlorostyrene and vinyltoluene; vinyl unsaturated monomers such as N-vinylpyrrolidone and vinyl acetate.

2. Polymer having cationic or zwitterionic The copolymerization reaction using the unsaturated monomer can be carried out by a known radical polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method. The preferred polymerization method is a solution polymerization method, in which a predetermined amount of a polymerizable unsaturated monomer is dissolved in a solvent, a polymerization initiator is added, and the mixture is added under a nitrogen stream at a flow rate of 50-12.
It is carried out by a method of heating and stirring at 0 ° C.

Examples of the polymerization initiator include peroxides such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile.

The solvent is preferably water; alcohols such as methanol, ethanol, isopropanol, ethylene glycol and butyl cellosolve; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; acetic acid esters such as methyl acetate and ethyl acetate. Further, these solvents may be used in a mixture of two or more kinds. The amount of solvent used is such that the polymer concentration of the produced copolymer solution is 10 to 10.
It is preferably 65% by weight.

In the polymerization, the monomer and the polymerization initiator are
It is usual that all kinds and all amounts thereof are present from the beginning of the polymerization, but a divided addition method can be used for those kinds and / or amounts. The weight average molecular weight of the obtained copolymer is 5,000 to 300,000.
Must be within the range. To control the molecular weight, the polymerization temperature, the type and amount of the polymerization initiator, the amount of the chain transfer solvent such as ethanol and isopropanol, the use of the chain transfer agent such as butyl mercaptan and lauryl mercaptan, and the polymerization conditions are appropriately selected. It can be done by

As described above, after copolymerizing in the form of its precursor instead of the ionic unsaturated monomer of the component (A),
When the amphoteric and / or cationizing polymer is used to obtain the zwitterionic and / or cationized polymer, the amount of the amphoteric or cationizing agent used is 70 to 130% of the stoichiometric equimolar amount. Is preferred. Further, in the case of using an amphoteric agent which produces a by-product salt such as sodium monobromide acetate or potassium monochloroacetate in the zwitterionic ionization reaction, the by-product salt is separated and removed by filtration, centrifugation or the like, if necessary. Alternatively, the dissolved salt may be removed by ion exchange treatment (JP-A-55-104209 and JP-A-61-25880).
See Japanese Patent Publication No. 4).

The obtained ionic polymer may be obtained by directly using the produced polymer solution as it is, or by removing the solvent of the produced polymer solution by evaporation or by using a poor solvent to precipitate the polymer. A solid polymer may be used. If necessary, the odor of the ionic polymer obtained can be improved by azeotropic distillation with the solvent of the odor component in a solution state, or by adsorption removal with an adsorbent such as activated carbon, activated clay or zeolite. In the solid state, it can be carried out by heating under reduced pressure and extraction with a solvent such as ethers.

(Hair Cosmetic Composition) The hair cosmetic composition of the present invention is a composition in which the ionic polymer obtained as described above is contained in a cosmetic medium. Hair cosmetics used in the composition of the present invention include hair cosmetics that remove hair after use such as shampoo, rinse, treatment, and permanent wave liquid, and mascara, aerosol-type hair spray, pump-type hair spray, foamy hair styling. It means a known hair cosmetic such as a hair setting agent which does not remove hair after use such as a hair lotion, set lotion, hair liquid, hair gel, hair cream, hair oil, etc. is there.

The content of the ionic polymer in the cosmetic medium is preferably 0.1 to 10% by weight. When the content is less than 0.1% by weight, it is insufficient to exert the effect of the polymer of the present invention when used as a hair cosmetic composition, and when it exceeds 10% by weight, the content of the polymer of the present invention for hair is increased. The amount of adhesion increases, which rather impairs the effect of the polymer of the present invention.

The cosmetic medium used in the composition of the present invention refers to a liquefied gas and a gas used as a solvent and a propellant for the above-mentioned various forms of hair cosmetics.
Specifically, the solvent includes water and hydrophilic solvents such as ethyl alcohol, isopropyl alcohol and ethylene glycol, such as monohydric and dihydric alcohols, and hydrophobic solvents such as isoparaffin and cyclic silicone. Liquefied gas includes liquefied petroleum gas, dimethyl ether, halogenated hydrocarbon, etc., and gas includes carbon dioxide gas, nitrogen gas and the like.

Further, known additives may be added to the hair cosmetic composition of the present invention, for example, anionic active agents, cationic active agents, nonionic active agents, zwitterionic active agents and the like. Surfactants and foaming agents, thickening agents, hadrotropes, emulsions, conditioning agents including silicone polymers and their chemical modifications, oils and fats, humectants, plasticizers, dyes, pigments and other coloring agents. , Bactericides, fragrances, etc. In addition, the hair cosmetic composition of the present invention may be used in combination with conventionally used known cationic, anionic, nonionic, etc. natural polymers, natural modified polymers, and synthetic polymers.

[0044]

EXAMPLES The present invention will be described in more detail with reference to experimental examples. The parts and% in the production examples are based on the weight, and the parts and% in the examples are based on the weight of the active ingredient.

<Production Example 1> Dimethylaminoethyl methacrylate: 40 parts, NK ester M-90G (the above-mentioned) was placed in a five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a glass tube for nitrogen substitution, and a stirrer. In the general formula (I), R ¹ = methyl group, R ² = methyl group, m =
9, n = 0, p = 0): 10 parts, NK ester M
-230G (in the general formula (I), R ¹ = methyl group, R ² = methyl group, m = 23, n = 0, p = 0): 25 parts, butyl methacrylate: 25 parts, and Absolute ethanol: 100 parts was added, azobisisobutyronitrile (hereinafter abbreviated as AIBN): 0.6 part was added, the mixture was heated under reflux at 80 ° C. under a nitrogen stream, and after 2 hours, AIBN:
1.0 part was added and the copolymerization was further carried out for 6 hours in a nitrogen stream. Next, a 40% anhydrous ethanol solution of a neutralized aminomethyl propanol of monochloroacetic acid in an equimolar amount to dimethylaminoethyl methacrylate was dropped into a five-necked flask with a dropping funnel, and further heated under reflux at 80 ° C. under a nitrogen stream. The amphoteric reaction was carried out for 8 hours to obtain 310 parts of a polymer solution.

The polymer solution thus obtained was treated with "P
-1 ". In addition, a certain amount of the polymer solution is taken and
The active ingredient concentration was 46% by weight, which was obtained by drying under reduced pressure at 4 ° C. for 4 hours and weighing the amount of the residue after removing the solvent.
Further, the weight average molecular weight of the polymer was 70,000 when measured by gel permeation chromatography (hereinafter abbreviated as GPC) using polystyrene as a standard substance.

<Production Example 2> 50 ml of dimethylaminoethyl methacrylate was added to the same five-necked flask as in Production Example 1.
Light ester 041MA (in the general formula (I), R ¹ = methyl group, R ² = methyl group, m = 30, n = 0,
p = 0): 35 parts, stearyl methacrylate:
Add 15 parts, absolute ethanol: 150 parts, AIBN:
Add 0.6 parts and heat to reflux under a nitrogen stream at 80 ° C. for 2
After the lapse of time, AIBN (1.0 part) was added, and copolymerization was further carried out for 6 hours in a nitrogen stream. Next, a 40% anhydrous ethanol suspension of a neutralized potassium hydroxide solution of monochloroacetic acid in an equimolar amount to dimethylaminoethyl methacrylate was added dropwise to the five-necked flask with a dropping funnel, and heated under reflux at 80 ° C under a nitrogen stream. Then, the amphoteric reaction was carried out for 12 hours.

The resulting viscous suspension was filtered with a filter to obtain a suspension, and the filtrate was regenerated with a cation exchange resin ("DIAION PK-220" was regenerated and the system was replaced with absolute ethanol). Through a column packed with, then regenerated anion exchange resin (“Diaion PA-416” after regeneration,
The system was replaced with absolute ethanol) and the column was passed through.

Next, the solvent was removed under reduced pressure at 70 ° C. to obtain a solid. The solid matter was crushed, washed well with diethyl ether, and well dried under reduced pressure at 70 ° C. to obtain 100 parts of solid matter. The polymer thus obtained is designated as "P-2". The weight average molecular weight of the polymer was 40,000 when measured by GPC as in Production Example 1.

<Production Example 3> N-methacryloyloxyethyl N, N-dimethylammonium N-propanesulfonate: 40 was placed in the same five-necked flask as in Production Example 1.
Parts, light ester 041MA: 35 parts, butyl methacrylate: 25 parts, and ethyl acetate: 150 parts,
Azobisdimethylvaleronitrile (hereinafter abbreviated as AVN): 1.2 parts was added and heated at 70 ° C. under a nitrogen stream,
After 2 hours, AIBN (1.0 part) was added, and the mixture was further heated under reflux at 78 ° C. under a nitrogen stream for copolymerization for 6 hours.

Next, the solvent was removed under reduced pressure at 70 ° C. to obtain a solid. The solid matter was crushed, washed well with diethyl ether, and well dried under reduced pressure at 70 ° C. to obtain 95 parts of a solid matter. The polymer thus obtained is designated as "P-3". The weight average molecular weight of the polymer was 20,000 when measured by GPC as in Production Example 1.

<Production Example 4> Diethylaminoethyl methacrylate: 30 was placed in the same five-necked flask as in Production Example 1.
Part, Bremmer 55 PET-800 (the above general formula (I)
In the formula, R ¹ = methyl group, R ² = hydrogen atom, m = 10, n
= 0, p = 5): 30 parts, butyl acrylate:
10 parts, butyl methacrylate: 20 parts, diacetone acrylamide: 10 parts, and absolute ethanol: 100
Parts, add AIBN: 0.6 parts, and under nitrogen stream 8
The mixture was heated under reflux at 0 ° C., 2 hours later, AIBN (1.0 part) was added, and the copolymerization was further conducted under a nitrogen stream for 6 hours.

Then, a 40% anhydrous ethanol solution of a neutralized aminomethyl propanol of monochloroacetic acid in an equimolar amount to dimethylaminoethyl methacrylate was dropped into a five-necked flask with a dropping funnel, and further refluxed at 80 ° C. under a nitrogen stream. After heating and conducting amphoteric reaction for 8 hours, the active ingredient concentration is 47
270 parts by weight of polymer solution are obtained. The obtained polymer solution is designated as "P-4". The weight average molecular weight of the polymer was 6 when measured by GPC as in Production Example 1.
It was 5,000.

<Production Example 5> In a five-necked flask similar to Production Example 1, dimethylaminoethyl methacrylate: 30 parts,
NK ester M-230G: 30 parts, tertiary butyl acrylate: 20 parts, isobutyl methacrylate:
20 parts, absolute ethanol: 55 parts, AIBN:
Add 0.2 parts and heat to reflux at 80 ° C under nitrogen flow,
After the lapse of time, AIBN: 1.0 part was added, and the copolymerization was further carried out for 6 hours in a nitrogen stream, and then 45 parts of anhydrous ethanol was added.

Then, after cooling to room temperature, a 50% absolute ethanol solution of 80% diethyl sulfuric acid in an equimolar amount to dimethylaminoethyl methacrylate was added dropwise to the five-necked flask with a dropping funnel, and further under a nitrogen stream at 50 ° C. Heat to 3
The cationization reaction is carried out for an hour, and the active ingredient concentration is 50%
235 parts of a polymer solution of The polymer solution thus obtained is designated as "P-5". The weight average molecular weight of the polymer was 150,000 when measured by GPC as in Production Example 1.

<Production Example 6> In a five-necked flask similar to Production Example 1, dimethylaminoethyl methacrylate: 5 parts,
Acrylic acid: 20 parts, Bremmer 70PEP-350B
(In the general formula (I), R ¹ = methyl group, R ² = hydrogen atom, R ³ = methyl group, m = 7, n = 3, p = 0): 50 parts, tertiary butyl Acrylate: 15
Parts, lauryl methacrylate: 10 parts, and absolute ethanol: 100 parts, and AIBN: 0.4 parts,
Reflux heating at 80 ° C. under a nitrogen stream, and after 2 hours AIBN:
1.0 part was added and the copolymerization was further carried out for 6 hours in a nitrogen stream.

Next, a 50% anhydrous ethanol solution of 70% aminomethyl propanol equimolar to acrylic acid was added dropwise to the five-necked flask with a dropping funnel to carry out a neutralization reaction under a nitrogen stream to obtain an active ingredient concentration of 50. 220 parts by weight of polymer solution are obtained. The obtained polymer solution is designated as "P-6". The weight average molecular weight of the polymer was 100,000 when measured by GPC as in Production Example 1.

<Production Example 7> Unsaturated monomer was added to dimethylaminoethyl methacrylate: 10 parts, NK ester M-
Polymerization operation was performed in the same manner as in Production Example 1 except that 90 G: 70 parts and butyl acrylate: 20 parts were used, and then, in the same manner as in Production Example 1, an amphoteric reaction was carried out with an aminomethyl propanol neutralized product of monochloroacetic acid. , Active ingredient concentration 48
220 parts by weight of polymer solution are obtained. The obtained polymer solution is designated as "P-7". The weight average molecular weight of the polymer was 7 when measured by GPC as in Production Example 1.
It was 10,000.

<Production Example 8> Unsaturated monomer was added to dimethylaminoethyl methacrylate: 70 parts, NK ester M-
Polymerization operation was performed in the same manner as in Production Example 1 except that 230 G: 10 parts and butyl methacrylate: 20 parts were used, and then,
In the same manner as in Production Example 1, an amphoteric reaction was carried out with an aminomethyl propanol neutralized product of monochloroacetic acid to obtain 390 parts of a polymer solution having an active ingredient concentration of 45% by weight. The obtained polymer solution is designated as "P-8". The weight average molecular weight of the polymer, when measured by GPC in the same manner as in Production Example 1,
It was 70,000.

<Production Example 9> Unsaturated monomer was mixed with N-methacryloyloxyethyl N, N-dimethylammonium.
N-methylcarboxylate: 15 parts, NK ester M
Polymerization operation was performed in the same manner as in Production Example 1 except that -230G: 15 parts and butyl methacrylate: 70 parts were used to obtain 195 parts of a polymer solution having an active ingredient concentration of 50% by weight. The obtained polymer solution is designated as "P-9". The weight average molecular weight of the polymer was 60,000 when measured by GPC as in Production Example 1.

<Example 1>"P- obtained in Production Example 1"
When "1" was spray-applied to the hair in the form of an aerosol spray or a pump spray having the following formulation, it had a soft finished feel and a good feeling of use without discomfort.
It also showed good setting power and good hair washability. Furthermore, it showed good flexibility when measuring the hardness of the hair.
(Table 1) Each evaluation method will be described later.

(1) Aerosol spray (parts by weight) Polymer (as an active ingredient) 3 Petroleum liquefied gas 20 Ethanol balance (total) 100 (2) Pump spray (parts by weight) Polymer (as an active ingredient) 5, 3, or 0 .5 Water 20 Ethanol balance (total) 100

<Examples 2 to 6>"P-2","P-"
3 "," P-4 "," P-5 ", and" P-6 "were evaluated in the spray form in the same manner as in Example 1, and similar to" P-1 ", they were good as hair cosmetics. The performance was shown (Table 1).

<Comparative Examples 1 to 4>"P-7","P-"
8 "," P-9 ", and G, which is the current anionic commercial product.
Sprayed in the same manner as in Example 1 using Antrez ES-225 (anionic polymer sold by ISP, USA; 20% of theoretical amount was neutralized with aminomethyl propanol and used as an ethanol solution having an active ingredient concentration of 50% by weight). When evaluated in terms of form, there was a problem in terms of performance, or a problem with respect to any of the evaluation items such as a soft finished feel, a good feeling of use without discomfort, setting power, and hair washability. (Table 1).

[0065]

[Table 1]

<Evaluation method> 1) Softness / feel 23 cm, 2 g of straight hair was spray-applied in a fixed amount in the form of pump spray, and immediately 2 c in diameter
Wrap in m curler and dry. Next, the hair removed from the curler is allowed to stand under conditions of constant temperature and humidity of 23 ° C./60% RH, and is touched with a finger to evaluate flexibility and feel. ○ −− Good flexibility and little polymer discomfort Δ−− Insufficient flexibility and some polymer discomfort × −− No flexibility and polymer discomfort ×× − Sticky I have a feeling

2) Setting power 23 cm, 2 g of straight hair is spray-applied in a fixed amount in the form of aerosol spray or pump spray, and immediately wound on a curler having a diameter of 1.2 cm to dry. Next, remove the hair removed from the curler at 30 ° C /
The hair is hung in a thermo-hygrostat at 70% RH, the hair elongation after 8 hours is measured, and the curl retention (%) is calculated by substituting it into the curl retention formula.

3) Hair Washability A curled hair obtained by using a pump spray containing 5% by weight of polymer as an active ingredient was operated in the same manner as the setting force, and the dodecyl alcohol / ethoxylate (3EO) kept at 40 ° C. was kept warm. ) / Sulfate salt 10% by weight in water and rinsed well with warm water at 40 ° C. After air-drying, the polymer remaining on the hair is evaluated visually and visually. ○ --The polymer has been removed .---- Some of the polymer remains .---- The polymer remains.

4) Hardness of hair 23 cm, 2 g of straight hair was dipped and applied in an ethanol diluted solution of 3% by weight in terms of active ingredient, and immediately after that, a diameter of 5
Wrap in a cm curler and dry. Next, the hair removed from the curler is left under constant temperature and humidity conditions of 23 ° C./60% RH, and a rheometer (made by Fudo Kogyo Co., Ltd.) is used to apply the weight (g) required to crush the curled hair. taking measurement.

[0070]

EFFECTS OF THE INVENTION The hair cosmetic composition according to the present invention has a soft feeling and an excellent setting property by using a polymer having a specific cationic or zwitterionic property.

Claims (6)

[Claims] 1. (A) an unsaturated monomer having ionicity;
20 to 60% by weight, (B) a polyether group-containing unsaturated monomer represented by the following general formula (I); 21 to 60% by weight,
(C) Having an alkyl group having 1 to 24 carbon atoms (meth)
A copolymer of an acrylic acid alkyl ester; 10 to 59% by weight, and (D) another polymerizable unsaturated monomer; 0 to 20% by weight, having a weight average molecular weight of 5,000 to 30.
A hair cosmetic composition comprising a polymer having a cation or zwitterionicity of 10,000. [Chemical 1] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a saturated alkyl group having 1 to 4 carbon atoms, a phenyl group, or a hydrogen atom, and R ³ is a saturated alkyl group having 1 to 3 carbon atoms. Represents an alkyl group, and m, n and p each represent an integer of 0 to 30, and the sum of m, n and p is 3 to 50.) 2. The composition according to claim 1, wherein the unsaturated monomer as the component (A) is a cationic unsaturated monomer. 3. The composition according to claim 1, wherein the unsaturated monomer as the component (A) is a zwitterionic unsaturated monomer. 4. The composition according to claim 1, wherein the unsaturated monomer as the component (A) comprises an anionic unsaturated monomer and a cationic unsaturated monomer. 5. The unsaturated monomer as the component (A) comprises a zwitterionic unsaturated monomer, an anionic unsaturated monomer, and a cationic unsaturated monomer. The composition as described. 6. The composition according to claim 3, wherein the zwitterionic unsaturated monomer is selected from (meth) acrylates having a carboxybetaine structure or a sulfobetaine structure.