JPH07118130A - Hair dye composition - Google Patents

Abstract

PURPOSE:To obtain a hair dye agent for human hair, shortened in time required for dyeing, capable of providing natural handle to hair and, simultaneously, exhibiting durability hardly removing even in washing hair and capable of safely using because of characteristic hardly causing dermatopathy. CONSTITUTION:This hair dye agent is obtained by mixing a methacrylic resin, an organic solvent, a gelling agent and an acidic dye with water and its pH is controlled to 1.5-5.0.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention, when dyeing human hair, has less skin damage, is safer, gives a natural texture, and exhibits durability that does not easily drop even after washing hair, and The present invention relates to a hair dye composition that can be dyed in a short time.

[0002]

2. Description of the Related Art Conventionally, a method widely used as a method for dyeing hair is as follows.
This is a method in which an oxidizing dye is used, and hydrogen peroxide is allowed to act in an alkaline condition to oxidatively polymerize the oxidizing dye inside the hair to develop a color. Although this method is excellent in dyeability, it usually has a very high pH value of 10 to 11, and therefore hair damage is likely to occur, and strong skin irritation is often exhibited. Furthermore, when amines are used as the alkaline agent, they tend to remain on the hair during use, and as a result, the gloss of the hair is lost, the tensile strength of the hair is reduced, and the hair is often dry. Therefore, as a safer method, hair dyes using tar-based acid dyes have been developed with less irritation.
However, the currently marketed acidic hair dyes have a drawback that they have low dyeing power for hair, durability of dyed hair and the like. In order to solve these problems, a hair dye containing xanthan gum, hydroxyethyl cellulose and an acidic dye (JP-A-61-25321), at least one selected from squalene, squalane, and a partially hydrogenated squalene and tar. A composition for hair dyeing, which comprises an acidic dye (Japanese Patent Laid-Open No. 63-241576) has been proposed.

However, these hair dyes have insufficient dyeability and are not yet satisfactory in dyeing fastness at the time of washing hair.

[0004]

Means for Solving the Problems The present inventors have conducted diligent studies in order to improve the dyeing fastness of hair dyeing compositions using the acid dye, and as a result, have found that the methacrylic resin has an extremely excellent effect. I found what to show. That is, with an acid dye,
By using a methacrylic polymer in combination, a composition for hair dyeing which has less skin irritation and a better feel of hair than a conventional hair dyeing composition using an acid dye, and further has excellent dyeing fastness during washing. I was able to get

A mixed solvent of ethyl alcohol and water is most suitable as a solvent for dissolving the methacrylic resin used in the present invention, but alcohols such as methyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol and propylene glycol, and the like. Ketones such as acetone and methyl ethyl ketone can be made stable solutions at room temperature by adjusting the ratio with water. On the other hand, in consideration of the dyeability of the tar-based acid dye on hair, there is a problem of familiarity with the surface of the hair, and a solvent having a certain degree of organicity and polarity improves the dyeing power. The hair dyeing degree changes depending on the mixing ratio with water, but if only the highest hair dyeing degree is taken, in the case of alcoholic solvents, the hair dyeing degree is ethyl alcohol <octyl alcohol <n-butanol <benzyl alcohol in that order. To rise.

Besides benzyl alcohol, aromatic alcohols generally exhibit excellent dyeing power. This dyeing power problem is not directly related to the solubility, and shows the maximum dyeing power in a certain solvent composition region in each solvent. This region is a state in which the solvent is a heterogeneous system in which it is dispersed in water, and it is shown that the affinity for hair increases when the methacrylic polymer and the tar acidic dye are dissolved in a delicate balance. ing. It is considered that this is because the dissociation state of the acid dye is different and the amount of adsorption to the hair is changed.

In addition to the above, the hair dye composition of the present invention may contain a thickener used in ordinary cosmetics. For example, celluloses such as carboxymethyl cellulose and hydroxyethyl cellulose and polysaccharides such as xanthan gum and carrageenan are used. Such a thickener has the effect of stabilizing the system and the effect of increasing the fastness of the dye adsorbed on the hair during washing. In particular, when sodium salt, potassium salt, or calcium salt of xanthan gum is used, the effect is remarkable.

The dyeability of the tar-based acid dye used in the present invention on hair greatly changes depending on the type of acid used for pH adjustment. Acetic acid, which has a small dissociation constant, has a low acidity at low concentrations, so the hair dyeing power is poor and increases with increasing concentration.
As the concentration increases, the dyeing power decreases. Citric acid, phosphoric acid, etc. are not affected by the concentration and show relatively high dyeability.

Further, since the pH of the system changes depending on the amount of acid used, the dissociation degree of the acid dye may change and the adsorptivity to hair may change. Therefore, in order to enhance the dyeability of hair, how well the pH is controlled is important, and at the same time how to maintain the apparent non-uniformity is also an important point.

The present invention will be described in detail below. The acidic dye used in the present invention is a tar-based pigment,
Red No. 102, Yellow No. 4, Yellow No. 5, Red No. 201, Red No. 227, Orange No. 205, Brown No. 201, Red No. 502
No., red 503, red 504, red 506, orange 4
02, Yellow 402, Yellow 406, Yellow 407,
Azo dyes such as black No. 401, red No. 3, red 104
No., Red No. 105, Red No. 106, Orange No. 207, Yellow 2
Xanthene dyes such as No. 02 and Red No. 401, green 3
No. Blue No. 1, Blue No. 202, Blue No. 203, Blue No. 20
Triphenylmethane dyes such as No. 5 and Green No. 402, indigoid dyes such as Blue No. 2, quinoline dyes such as Yellow No. 203, anthraquinone dyes such as Green No. 201 and purple No. 401, nitro dyes such as Yellow No. 403, green Four
Examples include nitroso dyes such as No. 01.

The amount of the acid dye compounded is 0.01 to 10%, preferably 0.03% to 5%, based on the total amount of the composition.

The methacrylic resin in the present invention refers to a polymer containing methacryloic acid or its ester or a methacryloyl group in a repeating unit, and examples thereof include a methacrylic acid / butyl methacrylate copolymer solution and methacrylic acid / methyl methacrylate. Copolymer liquid, N-methacryloylethyl N, N-dimethylammonium / α-N
-Methylcarboxybetaine-stearyl methacrylate copolymer liquid, N-methacryloylethyl N, N-dimethylammonium-α-N-methylcarboxybetaine-
Butyl methacrylate copolymer, N-methacryloylethyl N, N-dimethylammonium / α-N-methylcarboxybetaine / N-methacryloylethyl N, N, N
-Trimethylammonium chloride / 2-hydroxyethyl methacrylate copolymer, N-methacryloylethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine polymer liquid, N-methacryloylethyl-N, N-dimethylammonium-α- N-methylcarboxybetaine.N-methacryloylethyl-N,
Examples thereof include N, N-trimethylammonium chloride / methacrylic acid methoxypolyethylene glycol copolymer solution, hydroxypropyl acrylate / (acrylic acid) / butylaminoethyl methacrylate / octylamide acrylic acid copolymer, and the like. The content of the methacrylic resin in the composition is 0.1 to 10%, preferably 0.2 to 5.0.
%.

In the present invention, the organic solvent used is C ₁ -C.
_One or more of ₁₀ aliphatic alcohols or glycols, C _{7 to} C ₁₀ aromatic alcohols, lower aliphatic ketones, lower alkylene carbonates or N-lower alkylpyrrolidones are used. Specific examples thereof include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, octyl alcohol,
Alcohols such as ethylene glycol, propylene glycol, butylene glycol, benzyl alcohol, phenethyl alcohol, γ-phenylpropyl alcohol, cinnamic alcohol, anis alcohol, p-methylbenzyl alcohol, α-α-dimethylphenethyl alcohol, α-phenylethanol and phenoxyethanol. , Acetone, ketones such as methyl ethyl ketone,
Examples thereof include alkylene carbonates such as ethylene carbonate and propylene carbonate, and N-alkali pyrrolidones such as N-methylpyrrolidone.

The compounding amount of the organic solvent in the composition is 0.5-5.
It is 0%, preferably 1.5 to 25%.

Examples of the gelling agent used in the present invention include methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, ethyl cellulose,
Cellulose such as hydroxypropyl cellulose, hydroxypropyl methyl cellulose, xanthan gum,
Carrageenan, alginate, propyl alginate, acacia, hyaluronic acid, chitosan, guar gum, polysaccharides such as pullulan, and polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl resin, etc. may be mentioned. The content of the gelling agent in the composition is 0.1 to 8.0%, preferably 1.0 to 5.0%.

A wide range of general organic acids or inorganic acids can be used to adjust the pH, and examples thereof include citric acid, glycolic acid, succinic acid, tartaric acid, lactic acid, fumaric acid, propionic acid, and trichlor. Organic acids such as acetic acid, malic acid, lipric acid, butyric acid, valeric acid, oxalic acid, maleic acid, fumaric acid and mandelic acid, and inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid and nitric acid. The amount of acid blended is p
It is a necessary amount for adjusting H to 1.5 to 2.0.

In the product of the present invention, water is another component, that is, a tar-based acid dye, a methacrylic polymer, a solvent,
It is the balance of the thickener and the acid used for pH adjustment, but it is important to adjust so that the heterogeneity of the system is stably maintained.

The hair dyeing composition of the present invention contains the above-mentioned essential components as well as the natural and natural ingredients used in ordinary cosmetics as long as the stability and pH of the object and system of the present invention are not impaired. It is also possible to mix known additives such as synthetic flavors, preservatives, chelating agents and antioxidants.

[0019]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Prior to the description of the examples, the evaluation method will be described. a. Evaluation method 1. Dyeability: 1.0 g of a 10 cm yak white hair bundle is washed twice with 2.0 g of a 5% sodium lauryl sulfate aqueous solution. Then, the moisture in the hair bundle is removed so that the water content attached to the hair bundle is 1.0 g. 2.5 g of the sample is evenly applied to the lower half of the tuft. After leaving for 5 minutes, rinse well with warm water for 30 seconds,
Allow to air dry. Color difference meter (Minolta CR-
100) was used to measure La ^* b ^*, and the measured a ^* b ^*
* The color difference between the untreated hair of a ^* b ^* was calculated to evaluate the dyeing properties in this value. The larger this value, the better the dyeability.

2. Dyeing fastness 1. As shown in the dyeability section of Yak,
After dyeing for one minute and air-drying, it is thoroughly shampooed with 2.0 g of 5% sodium lauryl sulfate aqueous solution. After rinsing well with warm water, air-dry this bundle of hair and use a color difference meter to measure La.
^* b ^* was measured, and the color fastness after the hair wash test was determined by the following formula.

3. Rinse finish feeling 10 g of healthy human hair of 15 cm is made into a hair bundle and washed twice with 2.0 g of 5% sodium lauryl sulfate. After squeezing the water lightly, 2.5 g of the sample is evenly applied, left for 5 minutes, rinsed with warm water for 30 seconds and air dried. The texture from the application of the sample to the drying was sensory evaluated as follows. ◎: Good ○: Normal to somewhat good △: Normal to slightly bad ×: Bad

4. Comprehensive Evaluation The above three items for the test sample: dyeability, dyeing fastness, and rinsing feeling were comprehensively compared and evaluated. ◎: Good ○: Normal to somewhat good △: Normal to slightly bad ×: Bad

B. Manufacturing method Each component was blended with the composition shown in Table 1. For example, in Example 1, acid and orange color No. 205 were dissolved in water, guar gum was dispersed therein, and the mixture was heated to about 60 ° C. to increase the viscosity. After cooling to room temperature, ethanol, benzyl alcohol, MAMA
Was added and stirred uniformly to obtain a gel hair dyeing composition.
Similarly, compositions for hair dyeing were prepared for Examples 2 to 4 and Comparative Examples 1 to 3. The above evaluations were performed on these compositions (Table 1).

[0025]

[Table 1]

C. Description of Evaluation Results In Examples 1 and 2, since methacrylic resin MAMA, an organic solvent, a gelling agent, and an acid dye are contained and the pH is adjusted, excellent dyeing properties and dyeing fastness are obtained. It can be a hair dye composition having a feeling.

Further, in Examples 3 and 4, MACB was blended as a methacrylic resin and the organic solvent, the gelling agent and the acid dye were contained as in Examples 1 and 2, and the pH was adjusted. It is possible to obtain a composition for hair dyeing which is excellent in dyeing fastness and dyeing fastness.

On the other hand, in Comparative Example 1, methacrylic resin,
Since no gelling agent is added, the dyeing property, dyeing fastness, and rinsing feeling are poor. Comparative Example 2 is inferior in dyeing property, dyeing fastness, and rinsing feeling to Comparative Example 2 because no methacrylic resin is blended therein.

[0029]

EFFECTS OF THE INVENTION According to the present invention, when dyeing human hair, there is less skin damage, a safer and more natural texture is provided, and durability that does not easily drop even after washing hair is exhibited.
Further, a hair dyeing composition that can be dyed in a short time can be obtained.

Claims (10)

[Claims] 1. A methacrylic resin (a), an organic solvent (b), a gelling agent (c), and an acid dye (d) are mixed with water and the pH thereof is adjusted to 1.5 to 5.0. A composition for hair dyeing. 2. The methacrylic resin is a methacrylic acid / butyl methacrylate copolymer liquid, a methacrylic acid / methyl methacrylate copolymer, or N-methacryloylethyl N, N.
-Dimethylammonium / α-N-methylcarboxybetaine / stearyl methacrylate copolymer liquid, N-methacryloylethyl N, N-dimethylammonium / α-
N-methylcarboxybetaine / butyl methacrylate copolymer, N-methacryloylethyl N, N-dimethylammonium / α-N-methylcarboxybetaine / N-
One of methacryloylethyl N, N, N-trimethylammonium chloride / 2-hydroxyethyl methacrylate copolymer, hydroxypropyl acrylate / (acrylic acid) / butylaminoethyl methacrylate / octylamide acrylate copolymer Or the composition of Claim 1 which is 2 or more types. 3. The composition according to claim 1, wherein the methacrylic resin is contained in an amount of 0.1 to 10%, preferably 0.2 to 5.0%. 4. The organic solvent is _one or more of C _{1 to} C ₁₀ aliphatic alcohol or glycol, C _{7 to} C ₁₀ aromatic alcohol, lower aliphatic ketone, lower alkylene carbonate or N-lower alkylpyrrolidone. 2. The composition of claim 1, which is: 5. The organic solvent is methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, octyl alcohol, ethylene glycol, propylene glycol, butylene glycol, benzyl alcohol, phenethyl alcohol, γ-phenylpropyl alcohol, cinnamic alcohol, anise. Alcohol, p-
5. Methylbenzyl alcohol, .alpha .-. Alpha.-dimethylphenethyl alcohol, .alpha.-phenylethanol, phenoxyethanol, acetone, methylethylketone, ethylene carbonate, propylene carbonate or N-methylpyrrolidone, or a mixture of two or more thereof. Composition. 6. The composition contains 0.5 to 50% of an organic solvent.
The composition according to claim 1, which is (preferably 1.5 to 25%) blended. 7. The gelling agent is methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose,
Ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, xanthan gum,
One or two of carrageenan, alginate, propyl alginate, acacia, hyaluronic acid, chitosan, guar gum, pullulan, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl resin
The composition of claim 1 which is more than one species. 8. A gelling agent in the composition is 0.1 to 8.0.
%, Preferably 1.0 to 5.0%, The composition for hair dyeing according to claim 1. 9. The composition according to claim 1, wherein the acidic dye is one or more of tar-based pigments. 10. An acid dye in the composition of 0.01 to 10
% (Preferably 0.03 to 5%) of the composition according to claim 1.