JPH07539B2 - Keratin fiber dye composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a keratin fiber dyeing composition which is excellent in conditioning effect and therefore has a good feel on the hair during rinsing and finishing and is excellent in dyeing power.

[0002]

2. Description of the Related Art Oxidative hair dyes that have been widely used in the past basically consist of an oxidative dye and an oxidant. Since hydrogen peroxide acts in the presence of an alkali during treatment, depending on how to handle it. Risk of hair damage and primary irritation to the scalp. As a hair dye that overcomes the adverse effects of such an oxidative hair dye on the hair and scalp, a semi-permanent hair dye that uses a direct dye and has little effect on the scalp has been developed.

However, since such a semi-permanent hair dye generally uses a relatively large amount of solvent, it has the drawback that the feel of the hair such as finger passage, slippage and softness during rinsing and finishing becomes poor. . In particular, with semi-permanent hair dyes that are used by rinsing after applying the agent to the hair with bare hands like hair rinses that have been marketed in recent years, the feel of the hair from rinsing to drying is important because it is used in the same way as hair rinse. Therefore, there is a demand for a product having a higher conditioning effect.

On the other hand, as a method for imparting a conditioning effect to hair, JP-A-58-157713 discloses that a water-soluble cationic polymer and a water-soluble anionic activator are used to provide a hair styling effect with a certain degree of sustainability. A method for imparting a conditioning effect is disclosed in British Patent No. 21753515 by combining a direct dye, a cationic silicone activator and a silicone hydroxide derivative to impart a conditioning effect to hair. The conditioning effect at the time of finishing was not sufficiently satisfactory. Further, when an acid dye is used as a direct dye and used in combination with a cationic surfactant which is usually used as a conditioning agent in hair care products, there is a problem that the conditioning property is excellent but the dyeability is significantly reduced. .

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a keratin fiber dyeing agent containing a direct dye, which is excellent in dyeability and has a good conditioning effect. It is in.

[0006]

Under such circumstances, the present inventors have found that when a direct dye and a specific nonionic surfactant are used in combination, the feel of hair or the like is good both during rinsing and finishing. The inventors have found that a keratinous fiber dye composition can be obtained, and completed the present invention.

That is, the present invention has the following components (A) and (B) (A) direct dye (B) a branched acyl, branched alkyl or branched alkenyl group having 8 to 36 carbon atoms and HLB of 2 to 12: The present invention provides a keratinous fiber dyeing composition having a pH of 2.0 to 4.5 containing the nonionic surfactant which is

Examples of the direct dye (A) used in the present invention include nitro dyes such as 3-amino-4-hydroxynitrobenzene, 2-amino-5-hydroxynitrobenzene and 2-amino-3-hydroxynitrobenzene. , 2-amino-5-N, N-bis-β-hydroxyethylaminonitrobenzene, 2-amino-4-chloro-5-N-β-hydroxyethylaminonitrobenzene, 2-amino-4-methyl-5-N -Β-hydroxyethylaminonitrobenzene, 3,4-bis- (N-β
-Hydroxyethylamino) nitrobenzene, 2-amino-4-methyl-5-N-β, γ-dihydroxypropylaminonitrobenzene, 2-amino-4-methyl-5
-Β-Aminoethylaminonitrobenzene, 2-amino-4-hydroxynitrobenzene, and particularly advantageously; 3,4-diaminonitrobenzene, 2,5-diaminonitrobenzene, 2-amino-5-N-β-hydroxyethyl. Aminonitrobenzene, 2-N-β-hydroxyethylamino-5-N, N-bis-β-hydroxyethylaminonitrobenzene, 2-N-methylamino-5-N, N-bis (β-hydroxyethyl) aminonitrobenzene , 2-N-methylamino-5-N-methyl-N-β-hydroxyethylaminonitrobenzene, 2
-N-β-hydroxyethylamino-5-hydroxynitrobenzene, 3-methoxy-4-N-β-hydroxyethylaminonitrobenzene, 4-nitro-3-methylaminophenoxyethanol, 2-N-β-hydroxyethylamino-5 -Aminonitrobenzene, 2-N-β
-Hydroxyethylaminonitrobenzene, 3-amino-4-N-β-hydroxyethylaminonitrobenzene, 3-β-hydroxyethyloxy-4-N-β-hydroxyethylaminonitrobenzene, 2-amino-5-
N-methylaminonitrobenzene, 2-amino-3-methylnitrobenzene, 2-N-β-hydroxyethylamino-5-β, γ-dihydroxyproproxynitrobenzene, 3-hydroxy-4-N-β-hydroxyethylaminonitrobenzene , 3-hydroxy-4-aminonitrobenzene, 2,5-N, N'-β-hydroxyethylaminonitrobenzene, 2-N-methylamino-4
-O-β, γ-dihydroxyproproxynitrobenzene, 2-N-β-aminoethylamino-5-N, N-bis- (β-hydroxyethyl) aminonitrobenzene,
2-N-β-aminoethylamino-4-methoxynitrobenzene, 2-N-β-aminoethylamino-5-β-
Hydroxyethyloxynitrobenzene, 1-amino-4
-Methylaminoanthraquinone, 1,4-diaminoanthraquinone;

Acid dyes Red No. 2, Red No. 3, Red No. 102, Red No. 104, Red No. 105, Red No. 106.
No. 4, Yellow 4, Yellow 5, Green 3, Blue 1, Blue 2
No., Red No. 201, Red No. 227, Red No. 230, Red No. 231, Red No. 232, Orange No. 205, Orange No. 207
No., Yellow No. 202, Yellow No. 203, Green No. 201, Green No. 204, Green No. 205, Blue No. 202, Blue No. 203
No. 205, Blue No. 205, Brown No. 201, Red No. 401, Red No. 502, Red No. 503, Red No. 504, Red No. 506.
No., Orange No. 402, Yellow No. 402, Yellow No. 403, Yellow No. 406, Yellow No. 407, Green No. 401, Green No. 402
No. 401, purple No. 401, black No. 401; oil-soluble dyes Red No. 215, Red No. 218, Red No. 225, Orange 201
No., Orange No. 206, Yellow No. 201, Yellow No. 204, Green No. 202, Purple No. 201, Red 501, Red 505
No. 403, orange 403, yellow 404, yellow 405, blue 403; disperse dyes red 215, red 218.
No., Red 223, Red 225, Orange 201, Orange 206, Yellow 201, Yellow 204, Green 202
No. 201, purple No. 201, red No. 501, red No. 505, yellow No. 404, yellow No. 405, blue No. 403; basic dyes Red No. 213, Red No. 214; and William.
Basic dye of Siena Brown, M
ahogany, Madder Red, Steel
Blue, Draw Yellow, Disperse Black 9, which is a disperse dye, Disperse
Blue 1, Disperse Blue 3, D
isperse Violet 1, Disperse
Violet 4 etc. are mentioned.

When the dye composition of the present invention is used in the form of a rinse type that can be used with bare hands, acid dyes are preferable among these direct dyes, and particularly yellow No. 4 and green 204
No. 2, Red No. 2, Red No. 102, Green No. 3, Blue No. 1, Blue No. 205, Yellow No. 403, Red No. 106, Red No. 201
No. 205, orange No. 205, black No. 401, green No. 201 or purple No. 401, among which black No. 401,
Purple No. 401, Orange No. 205, Yellow No. 403 or Red 1
No. 06 is preferable.

These direct dyes may be used alone or in admixture of two or more, and may be used in the dyeing composition of the present invention in an amount of 0.02 to 5% by weight (hereinafter simply referred to as%), particularly 0%. ．
It is preferable that the content is 02 to 0.1%. If the blending amount of the direct dye is less than 0.01%, a sufficient dyeing effect cannot be obtained, and if it exceeds 5%, the hand skin is significantly soiled, which is a problem in practical use. When the dye composition of the present invention is used in the form of a rinse type that can be used with bare hands, about 0.02 to 0.1% is preferable from the viewpoint of achieving both hair dyeing power and suppression of stains on the skin of the hands.

The component (B) nonionic surfactant used in the present invention is an acyl having 8 to 36 carbon atoms and a branched chain,
It has an alkyl or alkenyl group and has an HLB value of 2-12. When the HLB is less than 2, the oily feeling is strong, and when it exceeds 12, the conditioning effect is low and it is not preferable. A particularly preferred range is 3 to 10. In addition,
HLB is hydrophilic-lipophilic balance (Hydroph
ilic-Lypophilic Balance), and in the present invention, a value calculated using the following equation by Oda / Teramura et al. is used.

[0013]

[Equation 1]

Examples of the component (B) include branched fatty acid ester, branched fatty acid polyol ester, branched fatty acid polyol ester alkylene oxide adduct, branched fatty acid alkylene oxide adduct, branched fatty acid amide,
Alkylene oxide adducts of branched alcohols, mono-, di- or triglyceryl ethers of branched alcohols, alkylene oxide adducts of glyceryl ethers of branched alcohols, polyol glyceryl branched alkyl ethers, trimethylol branched alkanes, but especially the following general formula ( Glycerylated polyols represented by 1), A _x (G) (1) [wherein G is x is a hydroxyl group selected from a polyol selected from pentaerythritol, sorbitol, maltitol, glucose, fructose and alkyl glycosides] Is a residue, A is

[0015]

[Chemical 1]

And / or

[0017]

[Chemical 2]

(Wherein R ¹ represents a branched alkyl group or alkenyl group having 10 to 36 carbon atoms), x is a number of 1 or more and does not exceed the total number of the hydroxyl groups of the polyol] and formula _{(2) R-OCH 2 CH} (OH) CH 2 OH (2) [wherein, R is a methyl branched saturated hydrocarbon group having 12 to 24 carbon atoms, R represents the following general formula

[0019]

[Chemical 3]

(In the formula, m is an integer of 2 to 14, and n is 3 to
The group represented by the integer of 11 and the sum of m and n is 9 to 21) is preferable. [Alpha] -mono (methyl-branched alkyl) glyceryl ether and the like are preferable.

As the branched acyl group, branched alkyl group or branched alkenyl group of these nonionic surfactants,
As mentioned above, those branched at the α position, those branched at the β position,
Examples include multi-branched ones. Examples of the branched fatty acid used as the material for the branched acyl group include methyl branched type synthesized by a by-product reaction of dimer acid synthesis, oxo reaction, Koch reaction, etc., oxidation of gerbet alcohol, oxidation of aldol, etc. Examples include branched long-chain alkyl type; branched higher alcohols used as materials for branched alkyl groups and branched alkenyl groups include those synthesized by oxo reaction. The glycerylated polyols (1) are produced, for example, by reacting a polyol with a corresponding branched alkyl glycidyl ether according to the following formula in the presence of a basic catalyst.

[0022]

[Chemical 4]

[In the formula, A, x, G and R ¹ have the above-mentioned meanings]

The reaction molar ratio between the polyol and the branched alkyl glycidyl ether (3) in this reaction can be appropriately selected depending on the degree of etherification of the desired glycerylated polyol. For example, in order to obtain a desired glycerylated polyol having a high content of 1 mol adduct, it is usually necessary to use the polyol in excess at a ratio of 1.2: 1.0 to 10.0: 1.0. In consideration of the amount of 1 mol adduct produced and the recovery of polyol, 1.5:
A ratio of 1.0 to 5.0: 1.0 is preferable. Further, in order to obtain a desired product having a high content of 2 mol adduct of glycerylated polyol, it is usually 0.3: 1.0 to 1.1: 1.
If the branched alkyl glycidyl ether is used in excess at a ratio of 0, considering the production amount of the 2 mol adduct,
A ratio of 0.4: 1.0 to 0.8: 1.0 is preferable.

The reaction is usually carried out without a solvent, but it is preferable to use an organic solvent for the purpose of assisting the mixing of the polyol and the branched alkyl glycidyl ether. Examples of the organic solvent include dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, etc.
It is preferable to use 0 times the amount.

As the catalyst, an acid or basic catalyst generally known as an epoxy group reaction catalyst can be used. When an acid catalyst is used, a side reaction is
It is not preferable because a decomposition reaction of the ether bond or a dehydration reaction of the hydroxyl group of the generated glycerylated polyols occurs.
It is preferable to use a basic catalyst. The basic catalyst used is not particularly limited, but sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium hydride and the like can be mentioned from the viewpoint of reactivity and economy. These basic catalysts are contained in the polyol in an amount of 0.01 to 20.0%, particularly 0.1 to 10.0%.
It is preferable to use in the range of.

The reaction is carried out at 50 to 200 ° C., preferably 80
It is carried out at ˜150 ° C. If the reaction temperature is less than 50 ° C, the reaction rate is slow, and if it exceeds 200 ° C, the product is colored, which is not preferable.

After completion of the reaction, an organic acid such as acetic acid or citric acid or an inorganic acid such as sulfuric acid, hydrochloric acid or phosphoric acid is added to neutralize the catalyst, and then the organic solvent used in the reaction is removed. In order to avoid thermal decomposition of the reaction product, the organic solvent is preferably removed under reduced pressure, usually at a temperature of 120 ° C or lower.

The glycerylated polyols (1) are usually prepared by adding 1 molecule of a branched alkyl glycidyl ether (3) to 1 molecule of a polyol, 2 moles of an adduct of 2 molecules, and 1 mole of a polyol. It is obtained as a mixture of polymorphic adducts to which 3 or more molecules of branched alkyl glycidyl ether (3) are added. The glycerylated polyols (1) thus obtained are usually used as a mixture of these 1-mole adduct, 2-mole adduct, or multi-mole adduct, but the reasons for performance and blending into products are If there is a problem with the above, it can be purified using a known purification method such as a silica gel column or solvent extraction. The glycerylated polyols (1) may contain unreacted glycosides in addition to the desired 1 mol adduct, 2 mol adduct, or polymolar adduct. Such an unreacted glycoside can be used as it is contained if there is no problem in practical use. If there is a problem, an organic solvent such as ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, chloroform or the like is used. The layer can be removed by a method using an extraction solvent system or a known purification method such as Smith thin film distillation.

On the other hand, the α-mono (methyl-branched alkyl) glyceryl ether represented by the general formula (2) is disclosed in
It can be produced by the method described in JP-A No. 7-120513.

The keratin fiber dye composition of the present invention has a pH of 2
It is set to ~ 4.5. Therefore, among the above-mentioned nonionic surfactants, those which do not contain a functional group such as an ester bond which is easily decomposed under acidic conditions are preferable. Preferred examples of this include alkylene oxide adducts of branched alcohols such as methyl-branched isostearyl alcohol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, and 2-dodecylhexadecanol; methyl-branched isostearyl alcohol. Branched alkyl glyceryl ethers such as monoglyceryl ether and monoglyceryl ether of 2-octyldodecanol; polyols such as pentaerythritol, sorbitol, maltitol, glucose, fructose and glycerin, and methyl branched isostearyl glycidyl ether, 2-dodecyl hexadecanol. Polyglyceryl branched alkyl ether which is a reaction product with branched glycidyl ether such as; branched alcohol such as methyl branched isostearyl alcohol Trimethylol branched alkanes such as obtained by reacting an aldehyde with formaldehyde is oxidized product thereof.

The blending amount of the component (B) is 0.01 to 10%,
Particularly, 0.1 to 5% is preferable. If this amount is less than 0.01%, the sufficient effect of the present invention cannot be obtained, and if it exceeds 10%, stickiness may occur, which is not preferable.

In the keratin fiber dye composition of the present invention,
In addition to the above components (A) and (B), the component (C) has a linear acyl, linear alkyl or linear alkenyl group having 8 to 36 carbon atoms, and has an HLB of 7 or less, preferably 5 or less. By adding an oil agent, the feel can be further improved. The term "straight chain" as used herein means that all of the acyl, alkyl, and alkenyl groups do not include a part of the branched chain. Examples of the component (C) include saturated or unsaturated straight-chain acyl, higher alcohol having straight-chain alkyl or straight-chain alkenyl group, higher fatty acid, higher fatty acid ester, polyol ester of higher fatty acid, and alkylene oxide addition of these compounds. Substances, hydrocarbons, cholesterols and the like. Among them, higher alcohols such as myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol and oleyl alcohol, and higher fatty acids such as palmitic acid, stearic acid, behenic acid and oleic acid are preferable. Particularly preferred are higher alcohols such as myristyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol. The blending amount of the component (C) is preferably 0.1 to 10%, particularly preferably 0.5 to 5%.

The dye composition of the present invention has a pH (measured as a 10% by weight aqueous solution) of 2.0 to 4.5, preferably 2.5 to 4.5, and particularly preferably 2.5 to 4.0. Is. When the pH is 4.5 or more, the dyeing power is lowered or the standing time after application is prolonged, which is not preferable, and the pH is 2.
When it is less than 0, irritation of the hand skin due to the acid component becomes a problem.

The dye composition of the present invention can be applied to keratinous fibers such as hair by using gloves, left for a certain period of time, and then rinsed off to be used in the form of a usual dye. It is preferable that the hair rinse type dyeing agent is used by directly applying it to hair or the like with bare hands without using gloves, leaving it for a short time of 30 to 120 seconds, and then rinsing it. When the latter type of hair rinse type is used, it depends on the quality of hair and the method of use, but it is usually about 5 to 5.
A hair dyeing effect such as white hair becoming inconspicuous can be obtained by using it 10 times.

In the case of such a dye composition for use with bare hands, in addition to the above components (A), (B) and (C),
It is preferable to add an organic solvent. Examples of the organic solvent used here include a compound represented by the following formula (D-1), an N-alkylpyrrolidone represented by the following formula (D-2), and an alkylene carbonate having 1 to 4 carbon atoms.

[0037]

[Chemical 5]

[0038]

[Chemical 6]

Specific examples of these organic solvents include ethanol, isopropanol, n-propanol,
n-butanol, isobutanol, ethylene glycol, propylene glycol, 1,3-butanediol,
Benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxyethanol, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, triethylene glycol mono. Ethyl ether, triethylene glycol monobutyl ether, glycerin,
N-methylpyrrolidone, N-octylpyrrolidone, N-
Examples thereof include laurylpyrrolidone. The amount of such an organic solvent blended is 0.5 to 50%, particularly 1% in the dye composition of the present invention.
~ 35% is preferred. If it is less than 0.5%, a sufficient hair dyeing effect cannot be obtained in a short standing time, and if it exceeds 50%, the effect is not improved.

The dye composition of the present invention of the type to be used with bare hands has a composition such that its 10% aqueous solution has a buffering capacity of 0.005 to 0.2 gram equivalent / l. It is particularly preferable because the standing time after coating is shortened. Here, the buffering capacity in the present invention is a value obtained by the following equation using the concentration of the base required to raise the pH of a 10% aqueous solution of the dye composition at 25 ° C by 1 from the initial value as a scale.

[0041]

[Equation 2]

If the buffer capacity is less than 0.005 gram equivalent / l, a sufficient effect cannot be obtained with a short standing time,
When it exceeds 0.2 gram equivalent / l, the hair dyeing effect is not markedly improved, and it is not preferable because the pH buffering agent which imparts the buffering ability and other compounding components become difficult to dissolve. A more preferable buffer capacity is 0.01 to 0.05 gram equivalent / l.

Such a buffering ability can be imparted by adding a pH buffer, a surfactant, a chelating agent, an antiseptic and the like to the dye composition. Among them, as the pH buffering agent, an organic acid or an inorganic acid and / or a salt thereof having a buffering action in the range of pH 2.0 to 4.5 can be used. Examples of the organic acid include citric acid, glycolic acid,
Examples include succinic acid, tartaric acid, lactic acid, fumaric acid, malic acid, levulinic acid, butyric acid, valeric acid, oxalic acid, maleic acid, fumaric acid, and mandelic acid. Examples of the inorganic acid include phosphoric acid, sulfuric acid, Nitric acid etc. can be mentioned. Examples of salts of these acids include sodium salts, potassium salts, ammonium salts, alkanolamine salts such as triethanolamine salts, and the like. The compounding amount of the compound that provides the buffering capacity is not particularly limited, and varies depending on the type of the compound that provides the buffering capacity. For example, when sodium citrate is mainly used as a compound that gives a buffering capacity, it is mixed at a concentration of about 2-2.5% or more.

In the dye composition of the present invention, various surfactants other than the component (B), cationic polymers, oily components, hydroxyethyl cellulose, xanthan gum, etc. may be added to the dye composition in an amount that does not impair the effects of the present invention. You may mix | blend a viscous agent, a silicone derivative, a fragrance | flavor, a preservative, an ultraviolet absorber, an antioxidant, a bactericide, a pearling agent, a clouding agent, etc.

As the surfactant, anionic surfactants such as olefin sulfonic acid, alkane sulfonic acid, fatty acid alkyl ether carboxylic acid and N-acyl amino acid; amphoteric surfactants such as amidobetaine, carbobetaine and hydroxysulfobetaine. Any of cationic surfactants such as mono- or dialkyl quaternary ammonium salts; and nonionic surfactants containing no branched alkyl groups such as polyoxyalkylene alkyl ethers can be used. As the cationic polymer, cationized cellulose, cationized starch, cationized guar gum, diallyl quaternary ammonium salt polymer, diallyl quaternary ammonium salt / acrylamide copolymer, hydroxyethyl cellulose dimethyl diallyl quaternary ammonium copolymer, etc. Is mentioned.

The dye composition of the present invention can be produced by a conventional method by mixing the above components, and the method for using the same is as described above.

[0047]

EFFECTS OF THE INVENTION The keratin fiber dyeing composition of the present invention is excellent in dyeing effect and conditioning effect, so that the feel of hair during rinsing and finishing is very good.

[0048]

The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Synthesis Example 1 Pentaerythritol 82 g, dimethyl sulfoxide 2
00 g and 1 g of sodium hydroxide were put into a 500 ml flask, heated and dissolved at 105 ° C., dry nitrogen gas was blown thereinto, and about 20 g of water and dimethyl sulfoxide were distilled out to remove water in the reaction system. After 39 g of isostearyl glycidyl ether was added dropwise to this over 1 hour, 1
The reaction was carried out at 05 ° C. for 4 hours with stirring. After the reaction,
Acetic acid (1.5 g) was added to the reaction mixture to neutralize the catalyst, dimethyl sulfoxide was completely distilled off at 80 ° C. under reduced pressure, and 99% ethanol was added to the residue to separate unreacted pentaerythritol by filtration. did. Ethanol was distilled off from the obtained filtrate under reduced pressure, and water was added to the residue 500 times.
ml and ethyl acetate (500 ml) were added and the mixture was extracted with ethyl acetate. The solvent was distilled off from the ethyl acetate-soluble fraction to obtain 63 g of a pale yellow adduct of pentaerythritol isostearyl glycidyl ether. When this crude product is separated and purified using silica gel column chromatography with an elution solvent of acetone: hexane = 2: 1,
The desired pentaerythritol-isostearyl glycidyl ether 1 mol adduct was eluted, and the elution fractions were collected and the solvent was distilled off to obtain the desired pentaerythritol isostearyl glycidyl ether 1 mol adduct 16 g ( Yield 30%) was obtained. Hydroxyl value 482 (calculated value 486) NMR (CDCl ₃ ): δ (ppm) 3.95 (1H, m, -OCH ₂ -C H OH-CH ₂ O-), 3.67 (6H, s, -C (C H ₂ O
H) ₃ ), 3.46 (8H, m, -OCH _2- ), 1.30-1.59 (29H, b, -CH ₂ -,-CH
-), 0.88 (6H, m, -CH ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 to 3400; ν _CH (stretching) (-CH-,-CH ₂ -,-CH ₃ ) 2850, 2920; ν _CH (Deflection) (-CH-,-CH ₂ -,-CH ₃ ) 1375, 1460; ν _CO (-CO-) 1110, 1035, 1010

Examples 1 to 3 After shampooing about 10 g of a dried white hair bundle, the water was drained, and 3 g of each of the compositions shown in Table 1 was quickly and uniformly applied thereto with bare hands. The hair was left to stand at 35 ° C. for 30 seconds, rinsed and dried, and the following evaluation was performed on the hair during rinsing and drying by 10 professional panelists. The results obtained are shown in Table 1.
Shown in. Evaluation of conditioning effect a) Finger rub during rinsing ⊚: No squeaking and very good finger rub. ◯: The squeak is weak and the fingers can be easily passed. B: Slightly squeaky and difficult for fingers to pass. X: Strong squeak and poor finger passage. b) Softness during rinsing and drying ◯: Very soft and supple. Δ: Soft X: Softness is applied. c) Comb passage when dried ○: Comb passage is good and smooth. Δ: It takes some time to pass the comb. X: Comb passage of hair tips and the like is poor, and the hair is caught.

[0051]

[Table 1]

Example 4 Ten female monitors in the 40's having a gray hair ratio of about 10% on the forehead were shampooed, and then a hairdresser applied about 15 g of the composition of Example 3 (Table 1). After coating, the mixture was left at 35 ° C. for 60 seconds, rinsed, and then dried with a dryer.
After repeating the same operation four more times, the conspicuousness of white hair was visually evaluated by 10 panelists. The results are shown in Table 2.
It was shown to.

[0053]

[Table 2]

Example 5 The following composition (pH 3.5) was added to about 5 g of a blond hair bundle of Europeans and Americans.
On the other hand, 2.5 g was applied and left at 30 ° C. for 30 minutes. Then, it was rinsed with running water and dried. The feel of the hair during rinsing and drying was good. (Composition) (%) (1) Yellow No. 4 0.025 (2) Orange No. 205 0.025 (3) Pentaerythritol glyceryl isostearyl ether ^{* 4} 3.0 (4) Citric acid 4.0 (5) Propylene Glycol 20.0 (6) Benzyl alcohol 5.0 (7) NaOH Adjusted amount to pH 3.5 (8) Xanthan gum 1.5 * 4: Reaction product of pentaethritol and monomethyl branched isostearyl glycidyl ether HLB9.
2 (obtained in Synthesis Example 1)

Example 6 The following composition (pH 4.0) was added to about 5 g of a European and American blonde hair bundle.
On the other hand, 2.5 g was applied and left at 30 ° C. for 30 minutes. Then, it was rinsed with running water and dried. The feel of the hair during rinsing and drying was good. (Composition) (%) (1) Red No. 106 0.025 (2) Orange No. 205 0.025 (3) Glyceryl glyceryl isostearyl ether 4.0 (4) Lactic acid 5.0 (5) Ethanol 20.0 ( 6) 2-benzyloxyethanol 5.0 (7) Stearyl alcohol (HLB2.8) 1.0 (8) Polyoxyethylene lauryl ether (EO15) 3.0 (9) NaOH Adjusted amount to pH 4.0 (10) Xanthan gum 1.5 * 4: Reaction product of glycerin and monomethyl branched isostearyl glycidyl ether HLB7.9

Claims (2)

[Claims] 1. The following components (A) and (B) (A) direct dye (B) having a branched acyl, branched alkyl or branched alkenyl group having 8 to 36 carbon atoms and having an HLB of 2 to 12; A keratinous fiber dye composition containing an ionic surfactant and having a pH of 2.0 to 4.5. 2. The following components (A), (B) and (C) (A) direct dye (B) having a branched acyl, branched alkyl or branched alkenyl group having 8 to 36 carbon atoms and having an HLB of 2 to 2; 12 nonionic surfactant (C) containing an oil agent having a linear acyl, linear alkyl or linear alkenyl group having 8 to 36 carbon atoms and having an HLB of 7 or less, and having a pH of 2.0 ~ 4.5 horny fiber dye composition.