JPH0840852A - Oxidation hair dyeing agent composition - Google Patents

Abstract

PURPOSE:To obtain an oxidation hair dyeing agent composition free from dropping from hair in hair dyeing treatment, having good extensibility, coating property, uniformly dyeing property, good tension and stiffness, dyeability and washing resistance and having preventing effect on hair damage in hair dyeing. CONSTITUTION:This oxidation hair dyeing agent composition contains a saccharide derivative expressed by the general formula, a protein hydrolysate and an oxidation dye. In the hair dyeing agent composition, a saccharide-branched aliphatic ether and/or a branched aliphatic glycoside (e.g. multitolisostearyl ether and/or isostearyl glycoside) is preferably used as the saccharide derivative. The composition is composed of a multi-agent type and when required, these components are mixed so as to contain the saccharide derivative, the protein hydrolysate, an oxidation dye and an oxidizing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to improvements in hair dye compositions, especially oxidative hair dye compositions.

[0002]

2. Description of the Related Art Oxidative hair dyes are the most widely used permanent hair dyes. The oxidation dye in the hair dye penetrates into the hair, undergoes oxidative polymerization, and develops color to cause hair to grow. The feature is that the hair dyeing effect lasts because it is chemically dyed.
As the formulation of the oxidative hair dye, the first agent containing the oxidative dye,
Most of the two-component type is used by mixing with a second agent containing an oxidant at the time of use, but there is also a one-component type used as a powder formulation by mixing with water at the time of use, or a multi-component type of three or more agents.

In any case, the oxidative hair dye chemically dyes hair by an oxidative polymerization reaction. This oxidative polymerization is a fairly vigorous reaction, and uneven application of the oxidative hair dye to the hair may cause uneven dyeing. In order to eliminate this uneven coloring, when the hair dye composition is applied to the hair, various solvents, dispersion media, etc. are added to the oxidative hair dye composition so that it has high fluidity. It was provided in liquid form.

[0004]

However, in such a liquid having high fluidity, the hair dye drips from the hair during or after the hair dyeing treatment, and adheres to the skin or clothes or flows down the face. There was such a problem as On the other hand, if an attempt is made to increase the viscosity of the hair dye by using a thickener or the like so that the hair dye does not sag, the conventional thickener is poor in the spreadability, coatability, and levelness of the oxidative hair dye on the hair. Further, there is a problem that the dyeing property is deteriorated because the thickener inhibits the permeability of the oxidation dye into the hair.

Further, in hair dyeing with an oxidative hair dye, proteins and amino acids in the hair flow out, and the hair is easily damaged,
There are also problems that the hair after dyeing tends to be cut or split ends, and that the hair becomes less stiff and dull and dry.

The present invention has been made in view of the above problems of the prior art, and its object is extensibility, coatability, etc. even though the hair dye does not drip during the hair dyeing treatment. It is easy to use, has good evenness without uneven dyeing, and has good dyeing properties with oxidative dyes, and is less likely to cause hair damage during hair dyeing and has the effect of maintaining firmness and elasticity of hair. Another object of the present invention is to provide an oxidative hair dye composition.

[0007]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that the above-mentioned problems can be solved by adding a certain sugar derivative and a protein hydrolyzate to an oxidative hair dye. Found that is solved. That is,
The oxidative hair dye composition according to claim 1 of the present invention is characterized by containing a sugar derivative represented by the general formula 4, a protein hydrolyzate, and an oxidative dye.

[Chemical 4] (In the formula, A is a residue obtained by removing n hydroxyl groups from sugar, R is
Represents a fatty chain having a total carbon number of 18 to 32 and having a branched chain, and n represents 1 or more. )

The oxidative hair dye composition according to claim 2 is characterized in that, in the oxidative hair dye composition according to claim 1, the sugar derivative is a branched aliphatic glycoside represented by the general formula 5. To do.

Embedded image (However, in the formula, A is a residue obtained by removing a hemiacetal hydroxyl group from a sugar, and R is the same as the above Chemical formula 4.)

The oxidative hair dye composition according to claim 3 is characterized in that, in the oxidative hair dye composition according to claim 1, the sugar derivative is a sugar-branched aliphatic ether represented by the general formula (6). And

[Chemical 6] (However, in the formula, A is a residue obtained by removing n non-hemiacetal hydroxyl groups from a sugar, and R and n are the same as those in the above chemical formula 4.)

The oxidative hair dye composition according to claim 4 is characterized in that, in the oxidative hair dye composition according to claim 1 or 2, the sugar derivative is isostearyl maltoside.
The oxidative hair dye composition according to claim 5 is the oxidative hair dye composition according to claim 1 or 3, wherein the sugar derivative is maltitol isostearyl ether.

The oxidative hair dye composition according to claim 6 is the oxidative hair dye composition according to any one of claims 1 to 5, wherein the protein hydrolyzate is a collagen hydrolyzate, a keratin hydrolyzate,
Milk protein hydrolyzate, elastin hydrolyzate,
It is characterized by containing one or more kinds selected from the group of soybean protein hydrolysates or quaternary compounds thereof.

The oxidative hair dye composition according to claim 7 is characterized in that, in the oxidative hair dye composition according to claims 1 to 6, an oxidant is contained. The oxidative hair dye composition according to claim 8 is a multi-agent form of the oxidative hair dye composition according to claims 1 to 7, and when mixed, a sugar derivative, a protein hydrolyzate, and an oxidative dye, It is characterized by containing an oxidizing agent.

The structure of the present invention will be described in detail below. First, in the present invention, the sugar derivative is a compound in which the hydroxyl group of the sugar is alkylated with a branched aliphatic hydrocarbon group, and in particular, the hemiacetal hydroxyl group of the sugar and the branched aliphatic hydrocarbon group form a glycosidic bond. Branched aliphatic glycosides and other hydroxyl groups (called non-hemiacetal hydroxyl groups)
An ether-bonded product of a branched aliphatic hydrocarbon group and a branched aliphatic hydrocarbon group is called a sugar branched aliphatic ether. The hemiacetal hydroxyl group refers to one hydroxyl group of hemiacetal generated when a sugar forms a cyclic structure.

The branched aliphatic glycoside used in the present invention is represented by the above general formula 5, wherein A is a residue obtained by removing a hemiacetal hydroxyl group from a sugar, and such a sugar is glucose. , Monosaccharides such as galactose, xylose, fructose, altrose, talose, mannose, arabinose, idose, lyxose, ribose, and allose, and mixtures thereof, maltose, isomaltose, lactose, xylobiose, kentiobiose,
Cordiobiose, cellobiose, sophorose, nigerose, sucrose, melibiose, laminaribiose,
Examples thereof include disaccharides such as rutinose and mixtures thereof, trisaccharides such as maltotriose and mixtures thereof, or higher polysaccharides, polymers of monosaccharides, and mixtures of these saccharides.

The sugar-branched aliphatic ether used in the present invention is represented by the above-mentioned general formula 6, wherein A is a residue obtained by removing n non-hemiacetal hydroxyl groups from sugar,
Examples of such sugars include sugar alcohols such as maltitol, sorbitol, erythritol, mannitol, galactitol, glucitol, inositol, maltotriitol, maltotetriitol, and mixtures thereof. In addition, n represents the average number of branched fatty chains bonded to one sugar molecule.

In any of the general formulas, R is an aliphatic chain having a branched chain and has a total carbon number of 18 to 32. Specific examples of the branched chain include, for example, methyl group, ethyl group, propyl group,
Isopropyl group, butyl group, pentyl group, hexyl group,
Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group,
Examples thereof include a heptadecyl group, a hexadecyl group, a heptadecyl group and further higher fatty chains. The position and number of such branched chains are not particularly limited. Specific examples of R include 2-decyltetradecyl group, 2-tetradecyloctadecyl group, isostearyl group, isomyristyl group, 2,7-dimethylhexadecyl group, tetrahydrageranyl group, 2,7-dimethyloctadecyl group. Etc., but it is not particularly limited as long as it has a branched chain and has a total carbon number of 18 to 32. When R is a linear fatty chain or the total number of carbon atoms of R is less than 18, the thickening effect is not sufficiently exhibited, and when the total number of carbon atoms is greater than 32, the hydrophobicity becomes high and water Solubility is poor and it becomes difficult to use in water.

The sugar derivatives according to the present invention are all known substances, and the branched aliphatic glycoside represented by the general formula 5 is, for example, the acid catalyst for sugar modification described in JP-A-63-84637. In addition to the synthesizing method using the same, it is possible to synthesize by using the reaction generally used for glycosylation (König-Knol reaction, Helferreich method, or other ether exchange method).

On the other hand, the sugar-branched aliphatic ether represented by the general formula 6 is, for example, the method of Robert et al. (Tetrahedro).
n, 35 , 2169-2172 (1979)). That is, the sugar is dissolved in a non-aqueous solvent such as dimethylformamide or dimethylsulfoxide, and the compound represented by the following general formula 7 is added to the solution to give a solution in the presence of a catalyst.
It is obtained by reacting at 0 to 130 ° C.

Embedded image (wherein, X is a halogen salt of a hydroxyl group or a halogen group or a trialkylammonium group such as trimethylammonium bromide, and R is the same as in the above Chemical Formula 6).

Two or more sugar derivatives can be used in the oxidative hair dye composition of the present invention. For example, a mixture of sugar-branched aliphatic ether or a branched fatty chain of a branched aliphatic glycoside or a kind of sugar, and in the sugar-branched aliphatic ether, a mixture of sugar derivatives different in the number of bonded branched fatty chains or the bonding position may be used. Of course, a mixture of a sugar-branched aliphatic ether and a branched aliphatic glycoside may be used.

Examples of the protein hydrolyzate used in combination with the sugar derivative in the present invention include collagen hydrolyzate, keratin hydrolyzate, milk protein hydrolyzate, elastin hydrolyzate and soybean protein hydrolyzate. Examples include protein hydrolysates and quaternized products thereof. In the present invention, of these, one kind or two or more kinds can be arbitrarily used.

Examples of the oxidative dye used in the oxidative hair dye composition of the present invention include phenylenediamines, aminophenols, toluylenediamines, aminonitrophenols, diphenylamines, diaminophenylamines and N-. Examples thereof include phenylphenylenediamines, diaminopyridines, resorcin, pyrogallol, catechol, aminocresols and salts thereof. The blending amount of the oxidative dye is not particularly limited as long as it is within the range generally used for oxidative hair dyes. In the present invention,
In general, a color tone adjusting agent that changes a color tone in combination with an oxidative dye as a main agent is also included in the oxidative dye of the present invention.

Since the oxidative hair dye composition according to the present invention contains the above-mentioned sugar derivative, it has an appropriate viscosity so that it does not drip or flow, and moreover, it can be quickly and evenly applied to the hair for dyeing. Also has the effect of being uniform.
Further, the sugar derivative according to the present invention does not hinder the dye from penetrating into hair and dyeing, and good dyeing property can be obtained. Further, the sugar derivative of the present invention is characterized in that it is stable without being decomposed even in an acid or an alkali, has no sensitizing property or irritating property even when incorporated into a hair dye composition, and is excellent in safety.

The hair dye composition may contain lower alcohols such as ethanol and isopropanol. When a surfactant is used as a thickener in such a system, the thickening effect is remarkably reduced. Therefore, it is necessary to add a large amount of a surfactant, and problems such as irritation and inhibition of dyeing property tend to occur. If the sugar derivative according to the present invention is used, a thickening effect can be obtained with a small amount even in such a system. In the oxidative hair dye composition of the present invention, the blending amount of the sugar derivative is not particularly limited as long as the effects of the present invention can be obtained, and the blending amount can be appropriately adjusted and used. It is 0.5 to 60% by weight, preferably 1 to 15% by weight.

Further, in the oxidative hair dye composition of the present invention, by using a protein hydrolyzate together with the above-mentioned sugar derivative, hair damage during hair dyeing treatment is extremely reduced, resulting in hair splits, cut hairs and the like. The effect of being less likely to be obtained is obtained, and moreover, there is a synergistic effect that the dyeing property and cleaning resistance by the oxide dye are significantly improved. The amount of the protein hydrolyzate to be incorporated into the oxidative hair dye composition of the present invention is preferably 0.01 to 3.0% by weight of the total composition. If it is less than 0.01% by weight, the desired effect cannot be obtained, and if it is used in excess of 3.0% by weight, the effect cannot be expected to increase.

The oxidative hair dye composition according to the present invention can take any one-form or multi-form of two or more parts. For example, 2
In the dosage form, a two-part composition in which a first agent containing a sugar derivative, a protein hydrolyzate and an oxidative dye and a second agent containing an oxidant are mixed at the time of use, a sugar derivative and an oxidative dye are used. A two-component composition in which the first agent contained and the second agent containing a protein hydrolyzate and an oxidizing agent are mixed and used at the time of use is preferable.
The mixing ratio of the first agent and the second agent is usually 1st agent: 2nd agent = 1: 1 in weight ratio, but the dripping and the usability,
There is no particular limitation as long as there is no inconvenience in level dyeability.
Examples of the oxidizing agent used in the present invention include hydrogen peroxide, persulfates, perborates, bromates, periodates,
Examples thereof include urea peroxide.

The oxidative hair dye composition of the present invention may contain other components usually used in hair dyes, as long as the effects of the present invention are not impaired. For example, as a component usually added to the first agent, glycerin, propylene glycol, dipropylene glycol, polyethylene glycol, chondroitin sulfate, hyaluronate, diglycerin, 1,3-butylene glycol, pyrrolidone carboxylate, sorbitol. Moisturizers such as maltitol, lactose, oligosaccharides, lanolin, squalane, liquid paraffin, petroleum jelly, higher fatty acids, triglycerides, oil components such as ester oils, methylphenylpolysiloxane,
Examples thereof include silicones such as dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymer, rubbery dimethylpolysiloxane, and amino-modified polysiloxane.

Further, antioxidants and stabilizers such as thioglycolate, L-ascorbate, bisulfite, hydrosulfite salt, bisulfate, ammonia water,
It is also possible to add an alkali agent such as alkanolamine, ammonium carbonate, sodium hydrogen carbonate, potassium hydroxide or the like.

It is also possible to use another amphipathic substance or a surfactant as the emulsifier. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid partial esters, polyoxyethylene hydrogenated castor oil derivatives, and other polyoxyethylene-based surfactants, octylpolyether. Alkyl polyglycosides such as glycosides, polyglycerin fatty acid esters, polyglycerin-based surfactants such as polyglycerin alkyl ethers, maltitol hydroxyalkyl ethers, sugar alcohol ethers such as sorbitol alkyl ethers, fatty acid diethanolamides, and the like, Anions such as higher fatty acid salts, alkylbenzene sulfonates, phosphoric acid esters, alkyl sulfates, alkyl sulfate ester salts, and polyoxyethylene alkyl sulfate ester salts Surfactants, amino acids, alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salts, alkyl cationic surfactants dimethylamine oxide, and the like, other surfactants can be appropriately used in combination.

Further, for example, ethanol, butanol,
Lower alcohols such as propanol and isopropanol, 2-ethylhexyl alcohol, 2-hexyldecyl alcohol, 2-decyltetradecyl alcohol, isostearyl alcohol, cetostearyl alcohol,
Higher alcohols such as lauryl alcohol, stearyl alcohol and cetyl alcohol, benzyl alcohol and the like can be added.

Examples of the sequestering agents and preservatives include hydroxyethanediphosphonates, phenacetin, EDTA and its salts, parabens, stannates, and the like. Polymeric compounds include poly (dimethylallylammonium ammonium). (Halide) type cationic polymer, polyethylene glycol, epichlorohydrin, propyleneamine and cocoylamine obtained from a condensation product type of tallowylamine obtained from tallow fatty acid, a cationic polymer, polyethylene glycol, epichlorohydrin, propyleneamine and coconut oil fatty acid The condensation polymer type cationic polymer, vinylpyrrolidone, dimethylaminomethacrylate copolymer type cationic polymer, quaternary nitrogen-containing cellulose ether type cationic polymer and the like can be mentioned.

Further, lauric acid diethanolamide, carboxymethyl cellulose, carboxy vinyl polymer, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, xanthan gum, carrageenan, alginate, pectin, phaceran, gum arabic, gut gum, karaya gum, tragacanth gum, agar powder, bentonite. Further, a thickener such as a crosslinkable polyacrylic acid salt can also be used in combination as long as the effect of the present invention is not impaired. Others, pH adjusters, fragrances, drugs,
A colorant, water, etc. can be appropriately added.

The components to be added to the second agent include, for example, phenacetin, EDTA and salts thereof, parabens,
Sequestrants such as stannates and preservatives, higher grades such as 2-ethylhexyl alcohol, 2-hexyldecyl alcohol, 2-decyltetradecyl alcohol, isostearyl alcohol, cetostearyl alcohol, lauryl alcohol, stearyl alcohol, cetyl alcohol Alcohols, polyoxyethylene alkyl ethers, alkyl sulfate salts, surfactants such as acylmethyl taurines, organic acids such as citric acid, malic acid, acetic acid, lactic acid, oxalic acid, tartaric acid, formic acid, levulinic acid, Examples thereof include acids such as inorganic acids such as phosphoric acid and hydrochloric acid, pH adjusting agents, fragrances, drugs, coloring agents, water and the like.

[0033]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In addition, all the compounding amounts show weight%. Prior to the examples, the test method used in each example will be described.

[Hair Dyeing Test] The hair of 10 panelists was dyed with each test hair dye composition, and the hair fell down during hair dyeing, the spreadability / applicability to hair and the leveling property. Was relatively evaluated. The evaluation criteria are as follows. <Evaluation of dripping> ◎: No dripping, no dripping ○: Almost no dripping, dripping △: Dripping, dripping ×: Dripping, dripping is severe

<Evaluation of extensibility and coatability> ◎: Very good elongation and easy application ○: Fairly good elongation and easy application Δ: Not very good elongation and difficult application ×: Poor extension , Uneven coating

<Evaluation of Level Dyeability> ◎: Evenly dyed well ○: Almost uniformly dyed Δ: Some dyeing unevenness was formed ×: Dyeing unevenness was formed <Evaluation of firmness and elasticity> ◎: Very firm and firm feeling is felt. ○: Firm and firmness is felt. △: Firmness and firmness is poor. X: Firmness and firmness is not felt.

[Dyeability test] 2 g of a human hair bundle with white hair
Wash the area with commercially available shampoo, lightly wipe with a towel and place on an aluminum tray. Take 5g of hair dye composition in an aluminum tray and 2
Rub the back and front of the human hair bundle at 5 to 30 ° C with a toothbrush and leave for 15 minutes. Then, it was thoroughly washed with slightly warm water, wiped with a towel, then dried with a dryer, and the difference in color from that of human hair containing untreated white hair was visually judged.

<Evaluation of Dyeability> ◎: Very good ○: Good Δ: Somewhat bad ×: Bad

[Washing resistance test] After judgment in the dyeing test, the dyed human hair bundle is divided into two equal parts, one of which is impregnated with a commercial shampoo solution, hand-washed 10 times, and then dried. . Repeat this 10 times, with the human hair bundle before shampoo,
The color of human hair bundles after shampoo was visually compared to examine the wash resistance (shampoo resistance).

<Evaluation of Washing Resistance> ◎: Very good (no fading at all) ○: Good (slightly fading) △: Slightly bad (fading) X: Bad (fading marked)

[Hair Damage Test] A set of 12 human hair bundles each having a length of 6 cm and having a length of 6 cm was collected from human hair mixed with white hair, and the test hair dye composition was sufficiently applied to the human hair bundle for 5 minutes at 30 ° C. Dyed hair
After washing with water, it was dried. The stress I when the human hair bundle was extended by 20% was measured before dyeing (I ₁ ) and after dyeing (I ₀ ) respectively, and from the obtained hair intensity ratio (I ₁ / I ₀ ), The hair damage prevention effect was evaluated as follows. A hair strength ratio closer to 1 indicates less hair damage.

<Evaluation of hair damage prevention effect> ⊚: Hair strength ratio is 0.9 or more ○: Hair strength ratio is 0.8 or more and less than 0.9 Δ: Hair strength ratio is 0.6 or more and less than 0.7 × : Hair strength ratio is less than 0.6

Formulation Examples 1 and 2, Comparative Examples 1 and 2 First, the conventionally used thickener, Emarex O.
A hair dyeing test was conducted using P-5 as a comparative example. [Preparation of Hair Dye Composition] 1) Preparation of First Agent Using the samples shown in Table 1, a first agent was prepared according to a conventional method according to the following formulation.

<Formulation> First agent Isopropanol 5.0 wt% Sample (see Table 1) 5.0 to 26.0 Ammonium thioglycolate 0.1 L-Ascorbic acid 0.5 EDTA 0.5 Ammonia water 6.0 Paraphenylenediamine 1.0 Resorcin 1.0 Fragrance Suitable amount Ion-exchanged water Residual

[0045]

[Table 1] ──────────────────────────────────── Test materials (blending amount) ──── ──────────────────────────────── Formulation 1 Maltitol monoisostearyl ether (5.0 wt%) + keratin water Decomposition product (1.0 wt%) Formulation example 2 Isostearyl maltoside (5.0 wt%) + Keratin hydrolyzate (1.0 wt%) Comparative example 1 Emerex OP-5 * (25.0 wt%) Comparative example 2 Emarex OP-5 * (25.0 wt%) + keratin hydrolyzate (1.0 wt%) ──────────────────────────── ───────── * POE (5) octyl phenyl ether, manufactured by Nippon Emulsion Co., Ltd.

2) Preparation of Second Agent Next, a second liquid a which is a transparent liquid is prepared by a conventional method according to the formulation shown in Table 2 below.
And a cream liquid second agent b were prepared.

[Table 2] ──────────────────────────────────── 2nd agent component a (transparent liquid) b (cream liquid) ──────────────────────────────────── Hydrogen peroxide 30% 15.0 15 0.0 Phosphate buffer solution Adjusted to pH 3 Adjusted to pH 3 Methylparaben 0.1 0.1 Sodium stannate 0.1 0.1 Liquid paraffin-5.0 Stearyl alcohol-3.0 Sodium lauryl sulfate-0.5 POE (20 ) Cetyl ether − 0.5 Ion-exchanged water Residual residue ─────────────────────────────────────

[Hair Dyeing Test] An oxidative hair dye composition obtained by mixing each of the first agents of Formulation Examples 1 and 2 and Comparative Examples 1 and 2 and each of the second agents at a weight ratio of 1: 1. Was used to carry out a hair dyeing test. Table 3 shows the properties before and after mixing and the results of the hair dyeing test.

[Table 3] ──────────────────────────────────── 1st agent 2nd agent Properties Dripping extension Uniformity Before mixing After mixing ・ Applicability ──────────────────────────────────── Formulation example 1 a Gel-like gel-like ◎ ◎ ◎ ◎ Blending example 2 a Gel-like gel-like ◎ ◎ ◎ ◎ Comparative example 1 a Liquid liquid × ○ × Comparative example 2 a Liquid liquid × ○ × ───────────── ─────────────────────── Blending example 1 b Gel-like gel-like ◎ ◎ ◎ ◎ Blending example 2 b Gel-like gel-like ◎ ◎ ◎ ◎ Comparative example 1 b Liquid Liquid × ○ × Comparative Example 2b Liquid Liquid × ○ × ─────────────────────────────────────

As can be seen from Table 3, the first agent (formulation examples 1 and 2) in which the sugar derivative and the protein hydrolyzate (keratin hydrolyzate) were used in combination was in the form of gel and was mixed with any of the second agents. Also had a gel form, the first agent using a conventional thickener (Emarex OP-5) (Comparative Example 1) or the first agent using this in combination with a protein hydrolyzate (Comparative Example) The liquid 2) was liquid and remained liquid after mixing with the second agent, which was difficult to mix and was likely to be non-uniform. In the hair dye test,
The oxidative hair dye compositions using the first agent of Formulation Examples 1 and 2 did not drip or run off, and had good spreadability and coatability on hair and excellent levelness. On the other hand, since the mixtures of Comparative Examples 1 and 2 using the conventional thickeners are liquid, they have a problem such as dripping or runoff and poor level dyeing property.

Comparative Examples 3 to 5 Using the samples shown in Table 4, a first agent (Comparative Examples 3 to 5) containing only a sugar derivative or a protein hydrolyzate was prepared in the same formulation as in the above Formulation Examples 1 and 2. An oxidative hair dye composition was prepared by mixing the respective second agents in a weight ratio of 1: 1.

[Table 4] ──────────────────────────────────── 1st agent Reagent (blending amount) ─ ─────────────────────────────────── Comparative Example 3 Maltitol monoisostearyl ether (5.0 wt%) Comparative Example 4 Isostearyl Maltoside (5.0 wt%) Comparative Example 5 Keratin Hydrolyzate (1.0 wt%) ───────────────────────── ─────────────

Properties of hair dye compositions using the first agent of Comparative Examples 3 to 5 and hair dye compositions using the above-mentioned Formulation Examples 1 and 2,
Tables 5 and 6 show a comparison of the results of the hair dyeing test, the dyeing property test, the wash resistance test, and the hair damage test.

[Table 5] ──────────────────────────────────── 1st agent 2nd agent Properties Dripping extension Properties Level dyeing Dyeing properties Harness Washing resistance (after mixing) ・ Applicability ・ Stiffness ───────────────────────────── ─────── Formulation 1 a gel ◎ ◎ ◎ ◎ ◎ ◎ ○ Formulation 2 a gel ◎ ◎ ◎ ◎ ◎ ◎ ○ Comparative Example 3 a gel ◎ ◎ ◎ ○ △ △ Comparative Example 4 a gel ◎ ◎ ◎ ○ △ △ Comparative Example 5 a Liquid × △ × × × × ─────────────────────────────────── ── Combination example 1 b-shaped ◎ ◎ ◎ ◎ ◎ ◎ ○ Composition example 2 b-shaped ◎ ◎ ◎ ◎ ◎ ○ Comparative example 3 b-shaped ◎ ◎ ◎ ○ △ △ Comparative example 4 b-shaped ◎ ◎ ◎ ◎ ○ △ △ Comparative Example 5b Liquid × × × × × × ──────────────────── ────────────────

[Table 6]

As can be seen from Tables 5 and 6, when a sugar derivative and a protein hydrolyzate (keratin hydrolyzate) are used in combination (formulation examples 1 and 2), gel hair dye compositions are obtained. No dripping, good spreadability / applicability to hair and level dyeability. It was also excellent in firmness / resilience, dyeability and wash resistance. In addition, hair damage was also very low. On the other hand, when only the sugar derivative is blended (Comparative Examples 3 to 4), although the properties and hair dyeing test results are not much different from those of Blending Examples 1 and 2, the dyeing property, washing resistance, and hair damage preventing effect are obtained. Was inferior in.

When only the protein hydrolyzate was blended (Comparative Example 5), although the hair damage was small, the obtained hair dye composition was in a liquid form and drooped and spreaded in the hair dye test. -Evaluation of coating property, level dyeing property, dyeing property, and washing resistance was significantly inferior. From the above, it is understood that the effects of the present invention are obtained when a sugar derivative and a protein hydrolyzate are used in combination.

Formulation Examples 3 to 5 and Comparative Examples 6 to 8 Using the samples of Table 7, a first agent was prepared in the same formulation as in the formulation examples 1 and 2, and the weight ratio of each of the second agents was 1: 1. To obtain an oxidative hair dye composition.

[Table 7] ──────────────────────────────────── Mixing example Mixing example Mixing example Comparative example Comparative example Comparative Example Sample 3 4 5 6 7 8 ──────────────────────────────────── Isostearyl maltoside 7.0 − − − − − Maltitol Isostearyl Ether − 7.0 − − − − 2-Tetradecyl Octadecyl Maltosit − − 7.0 − − − Stearyl Maltosit − − − 7.0 − − 2-Hexyl Tesyl Maltosit − − − − 7.0 − 2-Hexadecyl octadecyl maltoside − − − − − 7.0 Keratin hydrolyzate 0.5 0.5 0.5 0.5 0.5 0.5 ──────────────────────────── ───────── Properties Before mixing Gel-like gel-like gel-like liquid liquid separation After combination (+ 2nd agent a) Gel-like gel-like gel-like liquid-liquid separation After mixing (+ 2nd agent b) gel-like gel-like gel-like liquid liquid separation Hair dyeing test Dripping ◎ ◎ ◎ × ×-* Extensibility・ Applicability ◎ ◎ ◎ ○ ○ − * Level dyeing ◎ ◎ ◎ × × − * ────────────────────────────── ---: Indicates that the hair dyeing test was not performed.

As can be seen from Table 7, in Formulation Examples 3 to 5 in which the sugar derivative of the present invention is blended, gel-like oxidative hair dye compositions can be obtained, but when the fatty chain is linear (comparison In Example 6) or when the total number of carbon atoms in the branched fatty chain was less than 18 (Comparative Example 7), the hair dye composition was liquid and did not form a gel. In addition, when the total number of carbon atoms in the branched fatty chain was larger than 32 (Comparative Example 8), separation occurred and a uniform hair dye composition could not be obtained. Further, the hair dye compositions using Formulation Examples 3 to 5 were excellent in the hair dyeing test and the hair damage preventing effect, but the hair dye compositions using the first agent of Comparative Examples 6 to 7 were liquid. For this reason, there was dripping and the like, and the extensibility, coating property, and leveling property were inferior to those of the formulation examples 1 to 3 of the present invention.

Formulation Examples 6 to 12 Using the samples shown in Tables 8 and 9, each first agent was prepared in the same formulation as in Formulation Examples 1 and 2, and the weight ratio to each of the second agents was 1:
The mixture was mixed in No. 1, and a hair dyeing test and a hair damage test were performed on each mixture.

[Table 8] ──────────────────────────────────── Composition example Sample 6 7 8 9 10 11 12 ──────────────────────────────────── Isostearyl maltoside 8.0 8.0 8.0 8.0 8.0 4.0 − Maltitol Isostearyl ether − − − − − 4.0 8.0 Collagen hydrolyzate 1.0 − − − 0.5 1.0 − Keratin hydrolyzate − 1.0 − − 0.5 − 1.0 Soybean protein hydrolyzate − − 1.0 − − − − Milk flotein hydrolyzate − − − 1.0 − − 1.0 ──────────────────────────────────── Dripping ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Extendability / applicability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Level dyeing ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Dyeing property ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Toughness ◎ ◎ ◎ ◎ ◎ ◎ ◎ Washing resistance ○ ○ ○ ○ ○ ○ ○ Hair damage prevention effect ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ─ ──────────────────────────── ─────────

[Table 9] ─────────────────────────── Example of composition Sample 13 14 15 16 16 ─────────── ──────────────── Isostearyl maltoside 8.0 8.0 8.0 8.0 Maltitol isostearyl ether − − − − Collagen hydrolyzate − − − − Elastin hydrolyzate 0.005 0.01 3.0 5.0 Soybean Tanpak Hydrolyzate − − − − Milk Protein Hydrolyzate − − − − ─────────────────────────── dripping ◎ ◎ ◎ ◎ Spreadability / Applicability ◎ ◎ ◎ ◎ Level dyeing ◎ ◎ ◎ ◎ Dyeing ability ◎ ◎ ◎ ◎ ○ Elasticity and elasticity ○ ◎ ◎ ◎ Wash resistance ○ ○ ○ ○ Hair damage prevention effect ○ ◎ ◎ ◎ ──── ────────────────────────

From the above, by using the sugar derivative of the present invention in combination with a protein hydrolyzate, an oxidative hair dye, which is gel-like and is excellent in hair dyeing property, dyeing property, washing resistance and hair damage preventing effect, is obtained. It is understood that an agent composition is obtained.

[Table 10] ──────────────────────────────────── Comparative Examples Compound Examples Compound Examples Compound Examples Comparative Examples Sample 8 12 13 14 9 ──────────────────────────────────── Isostearyl maltoside 8.0 8.0 8.0 8.0 8.0 Methylphenylpolysiloxane 0.05 0.01 3.0 5.0 7.0 ──────────────────────────────────── dripping ◎ ◎ ◎ ◎ ◎ ◎ Extendability / applicability ◎ ◎ ◎ ◎ ◎ ◎ Level dyeing ◎ ◎ ◎ ◎ ◎ ◎ Dyeing property ○ ◎ ◎ ◎ ◎ ○ Smoothness △ ◎ ◎ ◎ △ △ Stability ◎ ◎ ◎ ◎ △ ──────── ─────────────────────────────

From the above, by using the sugar derivative of the present invention in combination with a protein hydrolyzate, a gel-like, hair-dyeing property,
It is understood that an oxidative hair dye composition having excellent dyeing properties, wash resistance, and hair damage prevention effect can be obtained.

Formulation Example 17 The first agent and the second agent c prepared by the following formulation were mixed in a weight ratio of 1:
When mixed in No. 1, it was a gel composition having a uniform and appropriate viscosity, and did not drip from the hair during hair dyeing treatment.
Good extensibility, coating property, level dyeing property, dyeing property, washing resistance,
Moreover, an oxidative hair dye composition having an excellent hair damage preventing effect was obtained. <First Agent> Isopropanol 5.0 Isostearyl Maltoside 5.0 Natrim Hydrosulfite 0.1 L-Ascorbic Acid 0.5 EDTA 0.1 Monoethanolamine 1.0 Ammonia Water 6.0 Paraphenylenediamine 1. 0 Resorcin 0.5 Meta aminophenol 0.1 Perfume Suitable amount Exchanged water Residual <Second agent c> Hydrogen peroxide water 15.0 Phosphate buffer solution Suitable amount Sodium stannate 0.1 Methylparaben 0.1 Keratin hydrolysis Thing 1.0

Formulation Example 18 Three-component hair dye <First agent> Isopropanol 5.0 Isostearyl maltoside 5.0 Thioglycol ammonium 1.0 L-Ascorbic acid 0.5 EDTA 0.5 Ammonia water 7.0 Parafinylenediamine 1.0 Fragrance Appropriate amount Ion exchange water Residual <Second agent d> Hydrogen peroxide water 30% 15.0 Phosphate buffer 0.1 Methylparaben 0.1 Sodium stannate 0.1 Ion exchange Water Residual keratin protein hydrolyzate 2.0 <Third agent> Ammonium sulfate 2.0 Sodium metasilicate 20.0 Ammonium persulfate 75.0 EDTA 1.0 Carboxymethylcellulose 2.0

(Manufacturing Method) The formulation of the above-mentioned first agent was sequentially dissolved in ion-exchanged water to obtain a first agent. Also, the second agent d was prepared in the same manner. Each component of the third agent was well pulverized and mixed to obtain a third agent. Dissolve the third agent in the second agent d,
The agents were mixed to obtain a three-component hair dye. Usually, they are mixed in the above order, but the order is not limited to this. When the first agent, the second agent d, and the third agent are mixed in a weight ratio of 1: 1: 1 in the above formulation, a gel composition having a uniform and appropriate viscosity is obtained.
An oxidative hair dye composition was obtained which did not drip from the hair during hair dyeing treatment, had good spreadability, applicability, and wash resistance, and was also excellent in preventing hair damage.

The first agent prepared according to the formulations of the following formulation examples 19 to 27 was mixed with the second agent a or the second agent b in Table 3 in a weight ratio of 1:
When mixed in 1, a gel-like oxidative hair dye composition having a uniform and appropriate viscosity was obtained. All of these do not drip from the hair during hair dyeing treatment, and have extensibility, applicability,
An oxidative hair dye composition having good levelness, dyeing property and washing resistance, and having an excellent effect of preventing hair damage was obtained. Also,
Each hair dye composition was a safe hair dye composition with no irritation to the scalp.

Formulation Example 19 1,3-butylene glycol 14.0 Sodium chondroitin sulfate 0.1 Isopropanol 5.0 Methylphenylpolysiloxane 1.0 (Silicone KF56: manufactured by Shin-Etsu Chemical Co., Ltd.) Quaternized collagen hydrolysis Product 0.5 Isostearyl maltoside 5.0 Ammonium thioglycolate 0.1 L-Ascorbic acid 0.5 EDTA 0.5 Monoethanolamine 0.5 Sodium hydrogen carbonate 1.0 Paraphenylenediamine 1.0 Metaaminophenol 1.0 Orthoaminophenol 0.1 Metaphenylenediamine 0.01 Paraaminoorthocresol 0.01 Perfume Appropriate amount Ion-exchanged water Residual

Formulation Example 20 Sorbit 15.0 Sodium hyaluronate 0.1 Benzyl alcohol 2.0 Isostearyl maltoside 8.0 Sodium pyrosulfite 0.1 L-Ascorbic acid 0.5 EDTA 0.5 Milk protein hydrolyzate 0.1 Monoethanolamine 0.5 Paraphenylenediamine 1.0 Resorcinol 1.0 Orthoaminophenol 0.2 Metaaminophenol 0.1 Paraaminoorthocresol 0.05 Perfume Suitable amount Ion exchange water Residual

Formulation 21 Diglycerin 13.0 Mabit 2.0 Isopropanol 5.0 Isostearyl Maltoside 5.0 Sodium lauryl sulfate 0.5 Cetanol 4.0 Emarex OP-5 3.0 (POE (5) octyl Phenyl ether, manufactured by Nippon Emulsion Co., Ltd.) Keratin hydrolyzate 0.3 Sodium hydrosulfite 0.1 L-Ascorbic acid 0.5 EDTA 0.5 Ammonia water 6.0 Paraphenylenediamine 1.0 Paraaminophenol 1. 0 Para-amino orthocresol 0.02 Fragrance Suitable amount Ion-exchanged water

Formulation Example 22 Propylene glycol 13.0 Liquid paraffin 2.0 Isopropanol 5.0 Isostearyl maltoside 5.0 Dimethylsiloxane methyl (polyoxyethylene) 0.3 Siloxane copolymer (EO = 24) (Silicone SC-9450: manufactured by Shin-Etsu Chemical Co., Ltd.) Stearyl trimethyl ammonium chloride 0.2 Collagen hydrolyzate 0.3 Sodium hydrosulfite 0.1 L-Ascorbic acid 0.5 EDTA 0.5 Ammonia water 6.0 Paraphenylene Diamine 1.0 Metaaminophenol 1.0 Paranitroorthophenylenediamine 0.02 Fragrance Suitable amount Ion-exchanged water Residual

Formulation Example 23 Polyethylene glycol 2.0 Lanolin 2.0 Ethanol 5.0 Isostearyl maltoside 10.0 Quaternized soy protein hydrolyzate 0.5 Xanthan gum 0.5 POE (60) hydrogenated castor oil 1. 0 (HCO-60: Nikko Chemicals Co., Ltd.) Elastin hydrolyzate 0.2 Sodium pyrosulfite 0.1 Sodium hydroxide 0.3 L-Ascorbic acid 0.5 EDTA 0.5 Methylparaben 1.0 Ammonia water 6 0.0 paratoluene diaminosulfate 1.0 resorcin 1.0 paraaminoorthocresol 0.5 perfume proper amount ion-exchanged water residual

Formulation Example 24 Isopropanol 6.0 Isostearyl maltoside 7.0 Compound represented by the above general formula 3, wherein A is a 2.0 polymer of three glucose monosaccharides, and R is an isostearyl group 4. Graded milk protein hydrolyzate 0.5 Ammonium thioglycolate 0.5 L-Ascorbic acid 0.5 EDTA 0.5 Monoethanolamine 0.5 Paratoluene diaminosulfate 1.0 Resorcin 1.0 Orthoaminophenol 0. 1 Metaphenylenediamine 0.01 Paraaminoorthocresol 0.05 Perfume Appropriate amount Ion-exchanged water Residual

Formulation Example 25 Isopropanol 8.0 Isostearyl Maltoside 3.0 Compound represented by the above general formula 3, wherein A is a 1.0 polymer of three glucose monosaccharides, and R is an isostearyl group A compound represented by the general formula 3 in which A is a 1.0 polymer of four glucose monosaccharides, R is an isostearyl group, quaternized keratin hydrolyzate 1.0 L-ascorbic acid 0.5 EDTA 0 .5 Methylparaben 1.0 Monoethanolamine 0.5 Sodium hydroxide 0.2 Paraphenylenediamine 1.0 Paraaminoorthocresol 1.0 Orthoaminophenol 0.1 Perfume Suitable amount Ion exchange water Residual

Formulation Example 26 Benzyl alcohol 2.0 Isostearyl maltoside 8.0 Quaternized elastin hydrolyzate 1.0 Sodium pyrosulfite 0.1 L-Ascorbic acid 0.5 EDTA 0.5 Monoethanolamine 0. 5 Paraphenylenediamine 1.0 Resorcinol 1.0 Orthoaminophenol 0.2 Metaaminophenol 0.1 Paraaminoorthocresol 0.05 Perfume Suitable amount Ion-exchanged water Residual

Formulation Example 27 Cetyl alcohol 2.0 Isostearyl maltoside 1.0 Soy protein hydrolyzate 1.0 Ammonium thioglycolate 2.0 Edetate 0.2 Paraphenylenediamine 2.0 Orthoaminophenol 2. 0 Resorcin 0.2 Ion-exchanged water Residual

[0071]

EFFECTS OF THE INVENTION The oxidative hair dye composition according to the present invention has an appropriate viscosity by blending a sugar derivative and a protein hydrolyzate, and does not drip from the hair during hair dyeing treatment. , Extensibility, coatability, level dyeability, firmness / resilience, dyeability,
It is characterized by good washing resistance and excellent hair damage prevention effect.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Keiichi Uehara 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Inside Shiseido Daiichi Research Center, Inc. (72) Inventor Masakazu Okumura 5-1-1 Umei, Takasago-shi, Hyogo No. 1 Inside the Nippon Seika Co., Ltd. (72) Inventor Takafumi Kusumoto 2-3-7 Shimbashi, Minato-ku, Tokyo Inside Nihon Seika Co., Ltd. Tokyo Branch

Claims (8)

[Claims] 1. An oxidative hair dye composition comprising a sugar derivative represented by the general formula 1, a protein hydrolyzate, and an oxidative dye. Embedded image (In the formula, A is a residue obtained by removing n hydroxyl groups from sugar, R is
Represents a fatty chain having a total carbon number of 18 to 32 and having a branched chain, and n represents 1 or more. ) 2. The oxidative hair dye composition according to claim 1, wherein the sugar derivative is a branched aliphatic glycoside represented by the general formula 2. Embedded image (However, in the formula, A is a residue obtained by removing a hemiacetal hydroxyl group from a sugar, and R is the same as the above chemical formula 1.) 3. The oxidative hair dye composition according to claim 1, wherein the sugar derivative is a sugar-branched aliphatic ether represented by the general formula 3. Embedded image (However, in the formula, A is a residue obtained by removing n non-hemiacetal hydroxyl groups from a sugar, and R and n are the same as those in the above chemical formula 1.) 4. The oxidative hair dye composition according to claim 1, wherein the sugar derivative is isostearyl maltoside. 5. The oxidative hair dye composition according to claim 1 or 3, wherein the sugar derivative is maltitol isostearyl ether. 6. The oxidative hair dye composition according to claim 1, wherein the protein hydrolyzate is collagen hydrolyzate, keratin hydrolyzate, milk protein hydrolyzate, elastin hydrolyzate, soybean protein hydrolyzate. An oxidative hair dye composition comprising one or two or more selected from the group consisting of a product and a quaternized product thereof. 7. The oxidative hair dye composition according to any one of claims 1 to 6, further comprising an oxidant. 8. The oxidative hair dye composition according to any one of claims 1 to 7, which is of a multi-agent type and which, when mixed, contains a sugar derivative, a protein hydrolyzate, an oxidative dye, and an oxidant. Hair composition.