JPH01213221A - Resin composition for fixing hair dye and hair dye using said resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition having good adhesivity to hair, giving flexible films, having no tackiness and no flaking, having excellent washability, water resistance and abrasion resistance and useful for fixing hair dyes, by copolymerizing four kinds of polymerizable monomers and subsequently neutralizing the resultant copolymer. CONSTITUTION:30-70wt.% of at least one kind of monomer selected from acrylic acid esters and/or methacrylic acid esters of the formula (R1 is H or methyl; R2 is methyl or ethyl; n is 1-10), 5-25wt.% of at least one kind of monomer selected from a group comprising acrylic acid, methacrylic acid and itaconic acid, 5-20wt.% of at least one kind of monomer selected from the 8-18C aliphatic alcohol esters of acrylic acid/or methacrylic acid and 20-50wt.% of other vinylic monomers are copolymerized. The resultant copolymer is subsequently neutralized with a water-soluble organic basic substance (e.g., ammonia water or morpholine).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a resin composition for fixing a hair colorant, particularly a resin composition for fixing a hair colorant such as a pigment in order to temporarily color the hair; This invention relates to a hair coloring agent using the same.

[Prior art] Hair cosmetic coloring agents such as gray hair coloring agents, mascara types, color sprays, color foams, etc., which are made by mixing hair coloring agents and fixing resins for temporarily coloring the hair, are known. ing. mascara type, color spray,
Color spray uses ethanol, water, etc. as a solvent, and color spray and color foam are packed together with a propellant such as chlorofluorocarbon gas in a pressure-resistant aerosol container.

As the above hair coloring fixing resin, vinylpyrrolidone-vinyl acetate copolymer, copolymer of monochloroacetate modified product of N,N'-dimethylaminoethyl methacrylate and methacrylic ester, acrylic ester-methacrylic ester Copolymers and the like are known.

However, the above-mentioned vinylpyrrolidone-vinyl acetate copolymer has a problem in that the formed film is hard before absorbing moisture, and after absorbing moisture, it suddenly becomes soft and sticky. Further, a copolymer of a monochloroacetate modified product of N,N'-dimethylaminoethyl methacrylate and a methacrylic acid ester also had problems such as high hygroscopicity and increased discoloration when touched with a wet finger. Furthermore, acrylic ester-
In the case of a methacrylic acid ester copolymer, there are problems such as a hard film formed, insufficient prevention of flaking, lack of soft feel, and poor hair washability when using a numerical setting agent.

[Problem to be solved by the invention]

Therefore, the object of the present invention is to provide a resin composition for fixing hair colorant that has good adhesion to hair, has a flexible film, is water resistant, does not discolor due to friction, and has good hair washability. An object of the present invention is to provide a hair coloring agent using the same.

[Technical means and effects for solving the problem] The hair colorant fixing resin composition according to the present invention contains the following polymerizable monomers a y d, that is, an acrylic ester represented by the following formula: or at least one monomer consisting of methacrylic acid ester 30 to 70% by weight ■ R2C=C-0-(OCH2CH2) n0R2 (wherein, R1 is a hydrogen atom or a methyl group, R2 is a methyl group or an ethyl group, n is an integer of 1 to 10.) b, 5 to 25% by weight of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid C, carbon of acrylic acid and/or methacrylic acid number 8~1
at least one ester of 8 aliphatic alcohols
It is obtained by copolymerizing 5 to 20% by weight of a seed monomer and 20 to 50% by weight of other vinyl monomers, and neutralizing it with a water-soluble organic basic substance, and also according to the present invention. The hair coloring agent contains the above hair coloring fixing resin composition together with a hair coloring agent and the like.

The above monomer a improves the adhesion and gloss of the resin to the hair, and adjusts the hydrophilicity, hair washability, etc., and the amount used is 30 to 70% of the total polymerizable monomers. % by weight, preferably 35-60% by weight. If the amount used is less than 30% by weight, poor adhesion to the hair, poor gloss, etc. will occur, and hair washability will also be reduced.On the other hand, if it exceeds 70% by weight, the hydrophilicity will be excessive and the water resistance will be reduced. decreases.

Specific examples of monomer a include methoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytetraethylene (meth)acrylate, and methoxypolyethylene glycol $400
(meth)acrylate, ethoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethoxytetraethylene glycol (meth)acrylate, ethoxypolyethylene glycol $400
Examples include (meth)acrylates, and their acrylic esters and methacrylic esters can be used alone or in combination.

It is involved in the tree-philicity and hair washability of the monomeric plum resin, and its usage amount is 5 to 25% by weight, preferably 10 to 25% by weight. If the amount used is less than 5% by weight, the resulting film will be poorly soluble in water and have poor hair washability;
If it exceeds % by weight, the amount of moisture absorbed increases and the stickiness becomes noticeable. As the monomer, unsaturated carboxylic acids selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid mentioned above can be used alone or in combination.

Monomer C is involved in the flexibility and water resistance of the formed film, and its usage amount is 5 to 20% by weight, preferably 5 to 15% by weight.
It is. If the amount used is less than 5% by weight, the film will be hard and have poor water resistance;
If it exceeds 100%, the film becomes excessively soft and sticky, and the hair washability is reduced.

Specific examples of monomer C include 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, balmityl (meth)acrylate, stearyl (meth)acrylate, etc., and acrylic esters thereof, methacrylate Acid esters can be used alone or in combination.

Monomer d imparts appropriate hardness and flexibility to the resulting film, and is used in an amount of 20 to 50% by weight.

Specific examples of monomer d include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, vinyl acetate, vinylpyrrolidone, (meth)acrylate, Acrylamide, diacetone (
Examples include meth)acrylamide, acrylonitrile, styrene, etc., and these vinyl monomers can be used alone or in combination.

Copolymerization of the above monomers a to d is carried out by ordinary solution polymerization in a hydrophilic solvent. For example, each monomer is dissolved in a hydrophilic solvent, a polymerization initiator is added, and the solvent is This can be carried out by stirring at or near the boiling point of . The above-mentioned monomers are copolymerized by making all types and amounts thereof present from the beginning of the polymerization, or by adding them in portions depending on the type and/or amount of the monomers. It is preferable to use the above solvent so that the solid content in the resin solution is 30 to 60% by weight.

Examples of hydrophilic solvents include water-soluble aliphatic alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, hydrous alcohols such as 95% ethyl alcohol, acetone, methyl cellosolve, Ethyl cellosolve, dioxane, methyl acetate, dimethylformamide, etc. can be used alone or in combination. Further, as the polymerization initiator, it is preferable to use, for example, peroxides such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile.

By adding a water-soluble organic basic substance to the resin-containing liquid obtained by the above copolymerization, the copolymerized resin is neutralized and made water-soluble. The neutralization rate is preferably 50 to 100%.

Examples of water-soluble organic basic substances include ammonia water,
Mono-, di- or triethanolamine, mono-, di- or triisopropanolamine, morpholine, aminomethylpropanolamine, aminoethylpropanolamine,
Aminomethylpropanediol, aminoethylpropanediol, etc. can be used alone or in combination. In particular, when an organic amine is used, a water-free resin composition can be obtained, which is suitable for aerosols that avoid moisture.

The resin composition thus obtained has a copolymer molecular weight of about 500 to 200,000, and can be used as a hydrophilic solvent solution obtained by the copolymerization, or as a hair colorant as a water-containing solvent system. For fixation, preferably the ratio (hair colorant/resin composition)=(1/1) to (1/20) (
solid content ratio).

[Examples 1 to 6] The present invention will be described below based on Examples. Note that "%" and "1 part" described below are both based on weight.

<Manufacture of resin composition) 3 to 4,200 parts of a polymerizable monomer, 100 parts of ethanol, and a polymerization initiator are placed in a 12-four-loaf flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution, a dropping funnel, and a stirrer. ~2 parts of O and S are added, and the mixture is heated under reflux at a temperature of 0.degree. C. under a nitrogen stream, and polymerization is carried out for 4 hours. After polymerization, the mixture is cooled, and an ethanol solution of a water-soluble organic basic substance is added at 50° C., and the mixture is diluted with ethanol to a solid content of 50%.

Table 1 shows the compositions of the polymerizable monomers a to d, the types and amounts of the polymerization initiators and water-soluble organic basic substances, etc. for Examples 1 to 6 and Comparative Examples 1 to 6.

(Hereinafter referred to as a blank space) <Preparation of color base> The above resin compositions of each example and comparative example (solid content 50%)
40% carbon black as hair colorant, 10%
A color base is prepared by mixing with 50% ethanol and using a three-stage roll.

<Preparation of color foam> Using the above color base, there are 3 types with the following composition (Type C: defoaming is fast, Type Pro: defoaming is intermediate between Type A and Type C, and Type C: defoaming is slow) A hair coloring agent consisting of a color form was prepared.

Composition (%) Type A Type B
Type C color base 10
10 10 Brulonik type nonionic activator*, -
0,5-Fatty acid jetanolamide *2-1 Cetyl alcohol -10,1 Ethanol 60 59.4 58.
9 Purified water 20 20
20LPG (liquefied petroleum gas) 2
2 2 Freon Gas F-12888 *1 Polyoxyethylene-polyoxybrobylene block copolymer oxypropylene glycol average molecular weight 1
750 Ethylene oxide content in all molecules a,
%*2 Coconut oil fatty acid jetanolamide l: Type 2 <Preparation of color spray> Using the above color base, a hair coloring agent consisting of a color spray with the following composition was prepared.

Composition (%) Color base 6 ethanol
34 Freon Gas F-1124 Freon Gas F-1236 (However, in Example 3 and Comparative Example 3, it is impossible to prepare a color spray because ammonia water is used as the organic basic substance.) Preparation of mascara type ) Using the above color base, a mascara-type hair coloring agent was prepared with the following composition.

Composition (%) Color base 10 resin composition (
solid content 50%) 4 ethanol
10 purified ice
76 <Performance evaluation> Appropriate amount of the above hair coloring agent was applied to a 10 cm (approximately 1 g) bundle of bleached hair, and after drying with a hair dryer (warm air), the following performance evaluations were performed on the hair. The results are shown in Table 2. .

(1) Adhesiveness Evaluate the stickiness of the hair after drying by touching it with your fingers.

O: No tackiness, Δ: Slight tackiness, ×: High tackiness (2) Comb the hair after flaking and evaluate whether or not the resin has fallen off.

O: No shedding, △: Some shedding, ×: Much shedding (3) Hair washability Make a 1% aqueous solution of a commercially available shampoo, wash the dried hair at 35°C, wash it with water, dry it, and check the degree of shedding. Evaluate.

o2 No residue, △: Small amount of residue, ×: Large amount of residue (4) Water resistance After immersing the dried hair in 40°C water for 30 seconds, take it out and squeeze it with a white cloth. Evaluate the degree of discoloration.

O: No color fading, Δ: Some color fading, ×: A lot of color fading (partial dissolution) (5) Using an abrasion resistance rubbing fastness tester (JIS P-8136), fix the white cotton cloth on the table. At the same time, the dried hair was fixed on the upper part and rubbed 30 times with a load of 300 g. The degree of discoloration on cotton cloth is evaluated on a scale of 1 to 5.

1: Almost no coloring, 5: Fully colored [Effects of the invention] As described above, the present invention has good adhesion to hair, a flexible formed film, no stickiness and flaking, and is easy to wash. It is possible to provide a hair colorant fixing resin composition having excellent properties, water resistance, and abrasion resistance, and a hair colorant using the same.

Patent applicant Goo Chemical Industry Co., Ltd. Agent Atsushi Ando Atsushi Ando Procedural amendment (1 button May 22, 1999 Patent application No. 040245 No. 040245 2, Name of invention Resin composition for fixing hair colorant) Product and hair coloring agent 3 using the same, relationship with the case of the person making the amendment Patent applicant address Kyoto Prefecture 44-7pbMiir'43g5a Address Name IkuF7ISVYKarishiki Company Representative Director ”=”1WW 4, Agent 603 5. Date of amendment order (voluntary) 6. Subject of amendment “Claims” and “Claims” of the specification
Each column of "Detailed Description of the Invention" (attached sheet) Contents of amendment (1) The scope of claims will be amended as shown in the attached sheet.

(2) Page 4 lines 16-18 of the specification “R1 R2C=C-0-(OCH2CH2) n0R2J, and correct it.

(3) “Ethanol” on page 14, lines 17-18 of the specification
60 59.4 58.9
Seisui 20 20
20 J, ``Ethanol 20 20
20 Purified water 60
59.4 Corrected to 58.9J.

(Attachment) Amended claims (1) A resin composition for fixing a hair coloring agent obtained by copolymerizing the following polymerizable monomers a''-/d and neutralizing it with a water-soluble organic basic substance. .

a, at least one monomer consisting of acrylic ester and/or methacrylic ester represented by the following formula
30 to 70% by weight (in the formula, R1 is a hydrogen atom or a methyl group, R2 is a methyl group or an ethyl group, n is 1
~10 integer. ) b. 5 to 25% by weight of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid; C. acrylic acid and/or methacrylic acid having 8 to 1 carbon atoms;
at least one ester of 8 aliphatic alcohols
5 to 20% by weight of seed monomer d, and 20 to 50% by weight of other vinyl monomers (2) A hair coloring agent comprising the hair coloring agent fixing resin composition according to claim 1.

that's all Agent Patent Attorney Atsushi Yasufuji

Claims (2)

[Claims] (1) A resin composition for fixing a hair coloring agent, which is obtained by copolymerizing the following polymerizable monomers a to d and neutralizing it with a water-soluble organic basic substance. a, at least one monomer 30 consisting of an acrylic ester and/or a methacrylic ester represented by the following formula;
~70% by weight ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is a hydrogen atom or a methyl group, R_2 is a methyl group or an ethyl group, and n is an integer from 1 to 10.) b, acrylic acid, 5 to 25% by weight of at least one monomer selected from the group consisting of methacrylic acid and itaconic acid; c, acrylic acid and/or methacrylic acid having 8 to 1 carbon atoms;
at least one ester of 8 aliphatic alcohols
Seed monomer 5-20% by weight d, other vinyl monomers 20-50% by weight (2) A hair coloring agent comprising the hair coloring fixing resin composition according to claim 1.