JPH1087450A - Hair dye composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hair dye composition having good dyeing property, durability of color, etc., and having high safety to hair and scaep by including an acidic dye and an acidic amino acid resin. SOLUTION: This hair dye composition contains 0.0001-10wt.% acidic dye and 0.01-50wt.% acidic amino acid resin. The acidic dye is a well-known water- soluble dyne having a sulfonic acid salt and red No. 106, etc., is exemplified as the acidic dye. The acidic amino acid resin is a water-soluble resin having 500-500,000 weight average molecular weight and polyaspartic acid, polyaspartic acid derivative are exemplified as the acidic amino acid resin. The acidic amino acid resin is obtained by reacting, e.g. polysuccinic imide with a functional group-containing amino compound as necessary and hydrolyzing the reactant when producing polyaspartic acid and its derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye composition which is excellent in dyeing properties, has good color, can impart a good feel to hair, and is highly safe for hair and skin.

[0002]

2. Description of the Related Art In recent years, oxidative hair dyes, which are widely used, cause hydrogen peroxide to act under alkaline conditions at the time of hair dyeing, which may cause damage to hair and irritation to the skin depending on how they are treated. was there. For this reason, hair dyes using acid dyes having little effect on hair and scalp have been studied. For example, Japanese Unexamined Patent Publication No. Sho 60-228407 and Japanese Patent Application No. 4-69323 propose hair dyes with improved dyeing properties, irritation to hair, and skin. Not always enough.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the above-mentioned technology, to provide excellent dyeability and good color, and to give a good feeling to hair,
It is intended to provide a dye composition having high safety for hair and skin.

[0004]

Means for Solving the Problems The present inventor has conducted intensive studies in view of the above problems, and found that (A) an acid dye and (B)
The present inventors have found that a hair dye composition containing an acidic amino acid resin exhibits good performance as a hair dye, and have reached the present invention. Hereinafter, the present invention will be described specifically.

(A) Acid dyes The acid dyes to be used in the present invention are known water-soluble dyes having a sulfonic acid group, which are used for ordinary hair dyes, and include, for example, nitro dyes and azo dyes. , A nitroso dye, a triphenylmethane dye, a xanthene dye, a quinoline dye, an anthraquinone dye, an indigo dye, and the like.
No., Red No. 104, Red No. 105, Red No. 106, Red No. 201, Red No. 227, Red No. 220, Red No. 230
No., Red No. 231, Red No. 232, Red No. 401, Red No. 501, Red No. 502, Red No. 503, Red No. 504
No., Red No. 506, Yellow No. 4, Yellow No. 5, Yellow 202
No. Yellow No. 203, Yellow No. 402, Yellow No. 403, Yellow No. 406, Yellow No. 407, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Green No. 401, Green No. 402
No., Blue No. 1, Blue No. 2, Blue No. 202, Blue No. 203
No. 205, Orange No. 205, Orange No. 207, Orange No. 402, Brown No. 201, Purple No. 401, Black No. 401 and the like.

[0006] The content of the acid dye is usually 0.0001 to 10% by weight, preferably 0.1 to 10% by weight in the hair dye composition.
001 to 5% by weight. When the content of the acid dye is 0.0
If the amount is less than 001% by weight, it is difficult to obtain sufficient dyeing properties.
I can hardly see it.

(A) Acidic amino acid resin In the present invention, it is essential that an acidic amino acid resin is blended into the hair dye composition. Examples of the acidic amino acid resin include monoaminodicarboxylic acids such as aspartic acid and glutamic acid, and acidic amino acid polymers composed of a mixture thereof and derivatives thereof.
In particular, polyaspartic acid and polyaspartic acid derivatives are preferred. Here, the derivative of the polymer means that a part of the acidic amino acid structure in the polymer molecule is, for example, an alkali metal salt or an alkaline earth metal salt, or a part of the acidic amino acid structure has a sulfonic acid group. , An alkyl group, an amino group, a hydroxyl group and / or an epoxy group. It is particularly preferable to select these functional groups in consideration of reactivity with a functional group such as a sulfonic acid group and an amino group in the acid dye used in combination.
The acidic amino acid resin used in the present invention generally has a weight average molecular weight of 500 to 500,000, and shows high water solubility.

The acidic amino acid resin of the present invention can be produced by a known method. For example, in the case of producing polyaspartic acid and its derivatives, polysuccinimide may be optionally used with a functional group-containing amino compound or the like. After the reaction, a typical method is to obtain polyaspartic acid or a derivative thereof by hydrolysis. Less than,
The production of this polyaspartic acid or a derivative thereof will be described.

(Polysuccinimide) The polysuccinimide used in the present invention desirably contains a succinimide unit in a polymer in an amount of 50 mol% or more. As a method for producing this polysuccinimide, for example, a product obtained by reacting maleic acid and ammonia, maleamic acid and / or aspartic acid as a monomer, in a solvent or without a solvent, in the presence or absence of a catalyst, A method of reacting in the presence is mentioned. Among the preferred methods are:
In this method, aspartic acid is used as a monomer and a catalyst is used. The monomeric aspartic acid may be in D-form, L-form or a mixture thereof.

Further, in the polymerization for obtaining polysuccinimide, other copolymerizable monomers can be used within a range not exceeding 50 mol% based on all monomers. Examples of copolymerizable monomers include a) aspartate, b) glutamic acid and its salts, c) alanine, leucine, lysine, and other amino acids other than a) and b), d) glycolic acid, lactic acid, Examples include hydroxycarboxylic acids such as 3-hydroxyacetic acid, and e) compounds having at least one functional group capable of reacting with an amino group and a carboxylic acid such as 2-hydroxyethanol, maleic acid, 6-aminocaproic acid, and aniline.

When a reaction solvent is used, it is usually selected from the group consisting of hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents and aprotic polar solvents, preferably at 100 ° C. or higher. Is 130 ° C
Solvents having the above boiling points, for example, xylene, diethylbenzene, toluene, amylbenzene, cumene, mesitylene, tetralin, chlorotoluene, dichlorobenzene, 1,4-dichlorobutane, chlorobenzene, dichloroethyl ether, butyl ether, diisoamyl Ether, anisole, n-amyl acetate, isoamyl acetate, methyl isoamyl acetate, cyclohexyl acetate, benzyl acetate, n-butyl propionate, isoamyl propionate, isoamyl butyrate, n-butyl butyrate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-
Examples include dimethyl-2-imidazolidinone, tetramethyl urea acid, dimethyl sulfoxide, sulfolane, hexamethyl phosphoroamide, and the like, and mixtures thereof.

The solvent is used in an amount of 1 to 100 parts by weight of the monomer.
It can be used in a proportion of up to 5000 parts by weight, preferably 5 to 4000 parts by weight, more preferably 10 to 3000 parts by weight. A catalyst may not be used, but is preferably used. This catalyst is, for example, an acid catalyst,
Inorganic acids such as sulfuric acid, sulfuric anhydride, phosphoric acid, polyphosphoric acid, metaphosphoric acid, condensed phosphoric acid, phosphoric anhydride, and organic acids such as p-toluenesulfonic acid, trichloroacetic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid. And others, a phosphoric acid monoester, a phosphoric diester, a phosphoric acid triester and the like, but preferably phosphoric acid, polyphosphoric acid, metaphosphoric acid, condensed phosphoric acid, phosphoric anhydride, phosphoric acid monoester, phosphoric acid Diester and phosphoric acid triester. The amount of the catalyst used is usually 0.002 to 0.3 mol, preferably 0.02 to 1 mol of the monomer.
〜0.25 mol.

[0013] The reaction temperature is usually in the range of 100 to 300 ° C, preferably 130 to 280 ° C. The reaction pressure may be normal pressure, reduced pressure or increased pressure, but is preferably normal pressure or reduced pressure. The reaction time is 1 second to 100 hours, preferably 10 seconds to 50 hours, most preferably 20 seconds to 1 hour.
0 hours. Further, the substantial end point of the reaction is a point at which the generation of water by-produced during the reaction has ceased.

An amine or the like may coexist for the purpose of controlling the molecular weight during the polycondensation reaction. The post-treatment step can be appropriately selected according to the use of the polymer. For example, it can be carried out by a conventional method such as a method of removing the solvent by centrifugation or a method of washing with water or a low boiling point solvent after centrifugation. Examples of these polycondensation reactions are described in JP-B-48-2038, US Pat. No. 4,839,461.
Gazette, US 5,057,597 gazette, US 5,21
No. 9,986, EP 578,449 and the like. The molecular weight of the polysuccinimide used in the present invention is preferably 500 to 50,000 in weight average molecular weight.
0, more preferably 500 to 150,000.

(Hydrolysis) The hydrolysis of the polysuccinimide can be carried out according to a conventional method. Am. Chem. Soc. 80, 33
61 (1958); Org. Chem. 26,10
84 (1961), U.S. Pat. No. 5,221,733, U.S. Pat. No. 5,288,783, and JP-A-60-203636. For example,
50 to 50 parts by weight of the above polysuccinimide
1000 parts by weight of water and 0.7 to 3 moles of an alkali metal hydroxide per mole of the polysuccinimide,
The reaction is preferably performed at a temperature of 0 to 50 ° C for 10 minutes to 8 hours. This hydrolysis almost opens the imide ring in the polymer.

(Polyaspartic acid derivative) The polyaspartic acid derivative in the present invention is not particularly limited as long as it has a polyaspartic acid structure even in a part of the polymer molecule. Examples thereof include alkali metal salts and alkaline earth metal salts of acids, and polyaspartic acids into which functional groups such as a sulfonic acid group, an alkyl group, an amino group, a hydroxyl group and an epoxy group are introduced alone or in combination of two or more. The production method is not particularly limited, for example, to introduce a sulfonic acid group, taurine, an alkali metal salt of taurine, to introduce a hydroxyl group, 2-aminoethanol, to introduce an alkyl group, To introduce butylamine, laurylamine and amino groups, hexamethylenediamine, N, N-diethyl-
It can be synthesized by using an amino compound having a functional group to be introduced, such as 1,3-propanediamine, and reacting the compound with polysuccinimide. A production method for introducing a sodium sulfonic acid salt by this method is exemplified below.

A) Aminosulfonate The aminosulfonate used in the present invention has 1
The amino group is not particularly limited as long as it has at least one primary or secondary amino group and at least one sulfonic acid group.
Primary is more preferable, and specific examples include 2-aminoethylsulfonate, aminomethanesulfonate, and aminobenzenesulfonate. The salt is not particularly limited as long as it is a sulfonate, and may be a mixture of one or more salts.
Particularly preferred are lithium, sodium and potassium salts.

B) Reaction between polysuccinimide and aminosulfonate The reaction between polysuccinimide and aminosulfonate is usually carried out in the presence or absence of a solvent. The reaction temperature is usually from 0 to 150 ° C, preferably from 5 to 150 ° C.
120 ° C. The reaction time is 1 minute to 30 days, preferably 5 minutes to 20 days. When a solvent is used, for example, aprotic polar solvents such as N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, N-methylpyrrolidone, and sulfolane are exemplified. The amount of the solvent is usually from 10 to 10,000 parts by weight, preferably from 20 to 50 parts by weight, per 100 parts by weight of the polymer.
00 parts by weight. The product can be isolated by a conventional method, and examples thereof include a method of distilling off the solvent and a method of crystallizing with a poor solvent for the polymer.

C) Hydrolysis Hydrolysis can be carried out in the same manner as in the above-mentioned method for producing polyaspartic acid. (Hair Dye Composition) The content of the acidic amino acid resin is not particularly limited, but is usually 0.01 to 50% by weight, preferably 0.05 to 30% by weight in the composition. If the content of the acidic amino acid resin is less than 0.01% by weight, sufficient suppleness cannot be given to hair, and 50% by weight
If it exceeds, the viscosity of the hair dye composition becomes too high, making it difficult to handle.

The p of the aqueous solution of the hair dye composition of the present invention
H is usually pH = 2 to 7, preferably pH = 2 to 6, and if the pH is too low, there is a risk of damaging the hair, and if the pH is too high, the dyeability may decrease. The adjustment of the pH is, for example, lactic acid, tartaric acid, acetic acid,
The reaction can be performed with an organic acid such as citric acid or oxalic acid, or an inorganic acid such as phosphoric acid or hydrochloric acid.

The hair dye composition of the present invention comprises (A) and (B)
In addition to the above-mentioned pH adjuster, a penetration enhancer, a preservative, a chelating agent, a fragrance, an oxidizing agent and the like may be appropriately blended according to the purpose. Further, the hair dye composition of the present invention is basically an aqueous solution in which the above components are dissolved, but as a solvent other than water, if necessary, an alcohol such as ethanol or another solvent soluble in water. May be used as a mixture with water.

The hair dye composition of the present invention is usually used in the form of a cream, emulsion, gel, solution, mousse or foam. The method for taking this form is not particularly limited.For example, in order to form a cream, an emulsion, a gel or a solution, the hair dye composition of the present invention may contain an emulsifier, which is usually used in the cosmetics field.
What is necessary is just to add a solubilizing agent, a stabilizer, a feeling improving agent, a hair styling base material, a fragrance, etc., and to manufacture by a conventional method. Examples of the emulsifier used here include, for example, alkylbenzene sulfonate, fatty alcohol sulfate, alkyl sulfonate, acylated amino acids, etc.
Examples of the hair styling substrate include silicone derivatives, higher alcohols, nonionic surfactants, and cationic surfactants.

In order to form a mousse or foam, for example, a hair dye composition of the present invention to which a nonionic surfactant and a thickener are added together with a liquefied gas such as propane gas is used. Can be obtained by filling an aerosol can. Optimal dyeing conditions for the hair dye composition of the present invention can be appropriately selected depending on the form, method of use, and the like.

[0024]

【Example】

Production Example 1 (Production of polyaspartate) After mixing and dispersing 5 kg of powdery L-aspartic acid and 500 g of 85% phosphoric acid in a nitrogen gas atmosphere for 5 minutes using a super mixer [manufactured by Kawata Corporation]. This mixture was kneaded with a kneader [S2KRC kneader manufactured by Kurimoto Steel Works Co., Ltd. (φ (D) = 50 mm, L = 661.5 mm, L / D =
13.2], a heating medium temperature of 260 ° C., a screw rotation speed of 30 rpm, and a discharge rate of 1 kg / h (average residence time of 16
Min), polycondensation was performed to obtain a brown powder. The resulting product was washed with water to remove phosphoric acid as a catalyst. The product is polysuccinimide,
Its weight average molecular weight was 17,000. However, the weight average molecular weight is “TSKge” manufactured by Tosoh Corporation.
l ”“ GMHHR-M ”+“ TSKgel ”“ G200
0HHR "column and 10 mM LiB as eluent
This is a polystyrene equivalent value obtained by gel permeation chromatography (differential refractometer) using dimethylformamide to which r is added. This polysuccinimide is referred to as resin A.

The polysuccinimide was hydrolyzed to obtain sodium polyaspartate. In the hydrolysis, 3 g of the polysuccinimide obtained above and 10 g of water were charged into a 100 cc beaker equipped with a stirrer, and an aqueous solution in which 1.4 g of sodium hydroxide was dissolved in 20 g of water was added under ice-cooling. Performed by stirring. After the reaction, the reaction solution was crystallized by pouring into 300 ml of methanol to obtain 3.3 g of yellow-white sodium polyaspartate. Hereinafter, this polyaspartate is referred to as resin B.

Production Example 2 (Production of sulfonic acid group-introduced polyaspartate) Resin A (94 g) and N, N-
Dimethylformamide (400 g) was charged and resin A was dissolved. Subsequently, taurine sodium salt (7.1)
After g) was added to the reaction solution, the mixture was attached to a rotary evaporator set to a bath temperature of 150 ° C. and heated for 3 hours. After completion of the reaction, the reaction solution was dropped into methanol (5 L) to crystallize the polymer. After filtering the mixture, the solid was washed twice with methanol (2 L) and dried under reduced pressure at 100 ° C. for 24 hours to obtain 84 g of a brown solid.

Next, in order to carry out the hydrolysis, 93% sodium hydroxide (40.5 g) and water (4
80 g) and sodium hydroxide was dissolved therein. After cooling the beaker with ice water, the brown solid was added little by little, and then stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was dropped into methanol (5 L) to crystallize the polymer. After filtering the mixture, the solid was removed from methanol (2 L).
And dried under reduced pressure at 50 ° C. for 24 hours to obtain 81 g of a yellow solid. Hereinafter, this product is referred to as resin C. Proton NMR of this resin (dimethyl sulfoxide-
The introduction rate of the taurine salt calculated according to d ₆ ) was 4.7%.
Met.

Production Example 3 (Production of Amino Group-Introduced Polyaspartate) Resin A (94 g) and N, N-
Dimethylformamide (400 g) was charged and at room temperature,
Resin A was dissolved. Subsequently, N, N-diethyl-1,3
-After adding propanediamine (12.6 g) to the reaction solution, the reaction solution was attached to a rotary evaporator and reacted at room temperature for 3 hours. After completion of the reaction, the reaction solution was treated with methanol (5
L) and the polymer was crystallized. After filtering the mixture,
The solid was washed twice with methanol (2 L) and
Drying under reduced pressure for 4 hours gave 103.2 g of a pale yellow solid.

Next, in order to carry out the hydrolysis, 93% sodium hydroxide (38 g) and water (480 g) were placed in a 1 L beaker.
g) was charged to dissolve sodium hydroxide. After cooling the beaker with ice water, the brown solid was added little by little, and then stirred at room temperature for 1 hour. After the reaction,
The reaction solution was dropped into methanol (5 L) to crystallize the polymer. After filtration of the mixture, the solid was washed with methanol (2 L)
It was washed twice and dried under reduced pressure at 50 ° C. for 24 hours to obtain 135 g of a pale yellow solid. Hereinafter, this product is referred to as resin D. Proton NMR of this resin (dimethyl sulfoxide-
The introduction rate of N, N-diethyl-1,3-propanediamine calculated according to d ₆ ) was 9.7%.

Example 1 0.5 g of Red No. 106 and resin B obtained in Production Example 1
1.0 g of benzyl alcohol 7.0 g, ethanol 1
Dissolve in a mixed solution consisting of 0.0 g and 81.5 g of water, and further adjust the pH of this solution to pH = 4 with lactate buffer,
A hair dye composition was prepared. The hair dye composition was applied to human hair, left at 30 ° C. for 1 hour, washed with a normal shampoo, and then subjected to a sensory evaluation of dyeability and suppleness of the hair. Then, the hair is further shampooed for 5
After washing twice, the dyeability was sensory evaluated. Table 1 shows the results.

Example 2 The same evaluation as in Example 1 was performed, except that the resin B in Example 1 was changed to the resin C. Table 1 shows the results.

Example 3 The same evaluation as in Example 1 was performed except that the resin B in Example 1 was changed to the resin D. Table 1 shows the results.

Example 4 The same evaluation as in Example 1 was carried out except that benzyl alcohol in Example 3 was changed to 2-benzyloxyethanol. Table 1 shows the results.

Comparative Example 1 The same evaluation as in Example 1 was performed except that the resin B in Example 1 was changed to carboxymethyl cellulose. Table 1 shows the results
Shown in

Comparative Example 2 The same evaluation as in Example 1 was performed except that the resin B of Example 1 was changed to carboxymethyl cellulose and the benzyl alcohol was changed to 2-benzyloxyethanol. Table 1 shows the results.

Comparative Example 3 The same evaluation as in Example 1 was performed except that the resin B in Example 1 was changed to hydroxyethyl cellulose. Table 1 shows the results
Shown in

[0037]

According to the present invention, it is possible to obtain a hair dye composition which has good dyeing properties and color, and is highly safe for hair and scalp.

[0038]

[Table 1] ◎: very good, ：: good, Δ: normal, ×: bad.

Claims (5)

[Claims] 1. A hair dye composition comprising (A) an acid dye and (B) an acidic amino acid resin. 2. The hair dye composition according to claim 1, wherein the acidic amino acid resin is polyaspartic acid and / or a polyaspartic acid derivative. 3. The hair dye composition according to claim 1, wherein the content of the acidic amino acid resin in the whole composition is 0.05 to 30% by weight. 4. The acidic amino acid resin having a weight average molecular weight of 5
The hair dye composition according to any one of claims 1 to 3, which is a water-soluble resin of from 00 to 500,000. 5. The acidic amino acid is polyaspartic acid and / or a polyaspartic acid derivative obtained by polycondensing an aspartic acid-containing monomer in the presence of a catalyst in the absence of a solvent, and then hydrolyzing it. The hair dye composition according to claim 2, wherein