JP2699133B2 - Keratinized 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 keratinous fiber dye composition and, more particularly, to a keratinous fiber dye composition having excellent dyeing properties and a good conditioning effect.

[0002]

2. Description of the Related Art Oxidative hair dyes, which have been widely used in the past, are basically composed of an oxidative dye and an oxidizing agent. Risk of primary irritation to hair damage and scalp. As a hair dye overcoming the adverse effects of the oxidative hair dye on hair and scalp, a semi-permanent hair dye using direct dye and having little effect on hair and scalp has been developed.

[0003] However, such semi-permanent hair dyes generally have a drawback that the use of a relatively large amount of solvent deteriorates the feel of the hair, such as finger wiping, slipping, and softness during rinsing and finishing. . Especially in the case of semi-permanent hair dyes, which are used for rinsing after applying the agent to the hair with bare hands, such as the recently marketed hair rinse, the feel of the hair from rinsing to drying is important in order to use it in the same way as a hair rinse. It is important point and what has a higher conditioning effect is demanded.

On the other hand, as a method for imparting a conditioning effect to hair, Japanese Patent Publication No. 61-55887 discloses a method in which a silicone derivative such as polyether-modified silicone is incorporated into a hair dye composition.
No. 713 discloses a method for imparting a hair styling effect with a certain degree of durability by using a water-soluble cationic polymer and a water-soluble anionic activator. Methods for imparting a conditioning effect to hair by combining an agent and a hydroxylated silicone derivative have been disclosed, but none of these methods have sufficiently satisfied conditioning effects at the time of rinsing and finishing. In addition, among hair dyes using acid dyes among direct dyes, when a quaternary salt-type cationic surfactant, which is widely used in hair care products as a hair conditioning agent, is compounded, it forms an ionic bond with the acid dye and becomes water-soluble. To form an insoluble complex,
There was a problem that the dyeability was reduced.

[0005]

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

[0006]

Under such circumstances, the present inventors have found that when a direct dye, a specific polyoxyalkylene-modified organopolysiloxane and an organic solvent are combined and adjusted to a specific pH and used, rinsing and finishing can be performed. In each case, it was found that a keratinous fiber dye composition having a good feel to hair and the like was obtained, and the present invention was completed.

That is, the present invention provides the following component (A):
(B) and (C): (A) a direct dye, (B) a polyoxyalkylene-modified organopolysiloxane containing 3 to 30% by weight of a polyoxyalkylene group in a molecule and dispersible in water, (C) an organic A keratinous fiber dye composition comprising a solvent and a pH of 2.0 to 4.5.

The direct dye (A) used in the present invention includes, for example, 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
-[Beta] -aminoethylaminonitrobenzene, 2-amino-4-hydroxynitrobenzene and, with particular preference; 3,4-diaminonitrobenzene, 2,5-diaminonitrobenzene, 2-amino-5-N- [beta] -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-dihydroxypropoxy nitrobenzene, 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 2, Red 3, Red 102, Red 104, Red 105, Red 106
No. 4, Yellow No. 5, Yellow No. 5, Green No. 3, Blue No. 1, Blue No. 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., Blue No. 205, Brown No. 201, Red No. 401, Red No. 502, Red No. 503, Red No. 504, Red No. 506
No. 402, Yellow 402, Yellow 403, Yellow 406, Yellow 407, Green 401, Green 402
No. Purple No. 401, Black No. 401; Oil-soluble dyes Red No. 215, Red No. 218, Red No. 225, Orange 201
No. 206, Orange No. 201, Yellow No. 201, Yellow No. 204, Green No. 202, Purple No. 201, Red No. 501, Red No. 505
No. 403, Yellow No. 404, Yellow No. 405, Blue No. 403; Disperse dyes Red No. 215, Red No. 218
No., Red No. 223, Red No. 225, Orange No. 201, Orange No. 206, Yellow No. 201, Yellow No. 204, Green No. 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
s company's basic dye, Sienna Brown, M
ahogany, Madder Red, Steel
Blue, Straw Yellow, Disperse Black 9, disperse dye, Disperse
Blue 1, Disperse Blue 3, D
isperse Violet 1, Disperse
Violet 4 and the like.

When the dye composition of the present invention is to be used in the form of a rinse type which can be used with bare hands, acidic dyes are preferred among these direct dyes, 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 201
No. Orange No. 205, Black No. 401, Green No. 201 or Purple No. 401 are preferable, and among them, Black No. 401,
Purple 401, Orange 205, Yellow 403 or Red 1
No. 06 is preferred.

These direct dyes can be used alone or as a mixture of two or more, and are preferably 0.02 to 5% by weight (hereinafter simply referred to as%) in the dye composition of the present invention. Particularly preferably, the content is 0.02 to 1.0%.
When the amount of the direct dye is less than 0.01%, a sufficient dyeing effect cannot be obtained, and when it exceeds 5%, the stain on the hand skin is remarkable, and there is a problem in practical use. When the dye composition of the present invention is in the form of a rinse type that can be used with bare hands, from the viewpoint of achieving both hair dyeing power and suppression of stains on the hand skin, 0.02 to 0.02.
About 0.1% is preferable.

The polyoxyalkylene-modified organopolysiloxane (B) containing 3 to 30% of a polyoxyalkylene group in the molecule used in the present invention and dispersible in water.
The polyoxyalkylene group may be bonded to any position of the polysiloxane chain, and examples thereof include those having structures represented by the following formulas (B-1) to (B-4).

[0012]

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[0013]

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[In the above formula, R¹Has 1 to 3 carbon atoms
Represents an alkyl group or a phenyl group; ^TwoIs a hydrogen atom or
Represents an alkyl group having 1 to 12 carbon atoms, and m is 20 to 200.
N is an integer of 1 to 10, x is an integer of 0 to 15, y
Is an integer of 0 to 10, z is an integer of 0 to 15, p is 1 to 5
An integer, t represents an integer of 0 to 10, and x + y + z is 1
The integer is equal to or larger than 20 and equal to or smaller than 20. ]

In the polyoxyalkylene-modified organopolysiloxane (B) used in the present invention, the polyoxyalkylene group contained in the molecule is 3 to 30%, preferably 5 to 25%. When the content is less than 3%, the polyoxyalkylene-modified organopolysiloxane is difficult to disperse in water, so that it is difficult to obtain an excellent conditioning effect, and the user often feels squeaking during rinsing. On the other hand, if the content exceeds 30%, the modified organopolysiloxane is easily dissolved in water, so that the modified organopolysiloxane is easily washed off at the time of rinsing, and it becomes difficult to obtain the desired conditioning effect as described above. The polyoxyalkylene-modified organopolysiloxane used in the present invention is dispersible in water at 25 ° C., and has no or very little squeaky feeling when rinsing, and has an excellent conditioning effect such as moderate sliding and softness after drying. Is shown. Here, the polyoxyalkylene-modified organopolysiloxane dispersible in water is a polyoxyalkylene-modified organopolysiloxane that is not visually transparently dissolved at 25 ° C. when a 1% aqueous solution is prepared, and a part thereof is dissolved. This includes those that float without sinking and those that settle.

These polyoxyalkylene-modified organopolysiloxanes can be used alone or in admixture of two or more, and are preferably 0.01 to 10%, particularly preferably 0 to 10%, in the dye composition of the present invention. 0.1 to 4%. When the blending amount of the modified organopolysiloxane is 0.01
If it is less than 10%, a sufficient conditioning effect cannot be obtained, and if it exceeds 10%, stickiness occurs, which is not preferable.

The dye composition of the present invention may be applied to keratinous fibers such as hair using gloves or the like, left for a certain period of time, and then washed off to form a usual dye used. It is preferable to apply directly to the hair or the like with bare hands without using gloves or the like, leave it for a short time of 30 to 300 seconds, and then rinse it to form a hair rinse type dye to be used. In the case of the latter type of hair rinse, although it varies depending on the hair quality and the method of use, it is usually about 5 to 5.
A hair dyeing effect such as inconspicuous gray hair can be obtained after ten uses.

The organic solvent (C) used in the present invention includes a compound represented by the following formula (C-1) and a compound represented by the following formula (C-
N-alkylpyrrolidone represented by 2) or 1 carbon atom
To 4 alkylene carbonates.

[0019]

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[0020]

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Specific examples of these organic solvents include, for example, ethanol, isopropanol, n-propanol,
n-butanol, isobutanol, ethylene glycol, propylene glycol, isoprene 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 Examples thereof include carbitol, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, glycerin, N-methylpyrrolidone, N-octylpyrrolidone, and N-laurylpyrrolidone. The amount of the organic solvent (C) is preferably 0.5 to 50%, particularly preferably 1 to 35%, in the dye composition of the present invention.
If the amount is less than 0.5%, when the dye composition of the present invention is used with bare hands, a sufficient hair dyeing effect cannot be obtained in a short standing time, and even if it is more than 50%, the effect of the effect is not improved. No improvement is observed.

The pH (measured as a 10% aqueous solution) of the dye composition of the present invention is preferably from 2.0 to 4.5, more preferably from 2.5 to 4.5, and particularly preferably from 2.5 to 4.0. It is. When the pH exceeds 4.5, when the dye composition of the present invention is used with bare hands, the leaving time after applying the composition to the hair is not shortened, which is not preferable. If so, irritation of the hand skin by the acid component becomes a problem.

Further, the dye composition of the present invention has 10%
It is particularly preferable that the aqueous solution has a composition having a buffer capacity of 0.01 to 0.2 gram equivalent / l, because the standing time after application is reduced. Here, the buffer capacity in the present invention refers to the pH of a 10% aqueous solution of the dye composition at 25 ° C.
Is a value obtained by the following equation using the concentration of the base required to increase the value of the base by 1 from the initial value.

[0024]

(Equation 1)

If the buffer capacity is less than 0.01 gram equivalent / l, a sufficient effect cannot be obtained with a short standing time.
If it exceeds 2 gram equivalent / l, no noticeable improvement in the hair dyeing effect is observed, and it is not preferable because the pH buffering agent imparting the buffering ability and other components are difficult to dissolve. In addition, more preferable buffer capacity is 0.01-0.05 gram equivalent / l.

Such a buffering ability can be imparted by adding a pH buffer, a surfactant, a chelating agent, a preservative and the like to the stain 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 a range of pH 2.0 to 4.5 can be used. Examples of the organic acid include citric acid, glycolic acid,
Succinic acid, tartaric acid, lactic acid, fumaric acid, malic acid, levulinic acid, butyric acid, valeric acid, oxalic acid, maleic acid, fumaric acid, mandelic acid, and the like.Examples of inorganic acids include phosphoric acid, sulfuric acid, Nitric acid and the like can be mentioned. Examples of the salts of these acids include sodium salts, potassium salts, ammonium salts, and alkanolamine salts such as triethanolamine salts. The amount of the compound providing the buffer capacity is not particularly limited, and varies depending on the type of the compound providing the buffer capacity. For example, when sodium citrate is used as a compound mainly providing a buffering capacity, the compound is added at a concentration of about 2 to 2.5% or more.

The dye composition of the present invention contains various surfactants, cationic polymers, oily components, thickeners such as hydroxyethylcellulose and xanthan gum, and the above-mentioned components (as long as the effects of the present invention are not impaired). Silicone derivatives other than B), fragrances, preservatives, ultraviolet absorbers, antioxidants,
A bactericide, a pearlizing agent, a turbidity agent and the like may be added. Here, as the surfactant, olefin sulfonic acid, alkane sulfonic acid, fatty acid alkyl ether carboxylic acid, N-
Anionic surfactants such as acylamino acids; amphoteric surfactants such as amidobetaine, carbobetaine and hydroxysulfobetaine; cationic surfactants such as mono- or dialkyl quaternary ammonium salts; nonionic surfactants such as polyoxyalkylene alkyl ethers Any of the activators can be used. Examples of the cationic polymer include cationized cellulose, cationized starch, cationized guar gum, diallyl quaternary ammonium salt polymer, diallyl quaternary ammonium salt / acrylamide copolymer, hydroxyethylcellulose dimethyldiallyl quaternary ammonium copolymer and the like. Is mentioned. Examples of the oil component include fatty acid esters, linear or branched alkyl glyceryl ethers, and branched higher alcohols.

The dye composition of the present invention can be produced by mixing the above-mentioned components by a conventional method, and the method of use is as described above.

[0029]

The keratinous fiber dye composition of the present invention has an excellent hair dyeing effect and an excellent conditioning effect, so that the hair feel is very good at the time of rinsing and finishing.

[0030]

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

Examples 1 to 3 After about 10 g of a tress of dried white hair was shampooed, water was drained, and 3 g of each of the compositions shown in Table 1 was quickly and uniformly applied with bare hands. The hair was left to stand at 35 ° C. for 30 seconds, rinsed, dried, and rinsed and dried, and the following evaluation was performed by 10 expert panelists. Table 1 shows the obtained results.
Shown in Evaluation of conditioning effect a) Finger passing at the time of rinsing ◎: There is no creaking and finger passing is very good. ：: The creaking is weak, and finger passing is good. Δ: The squeak is slightly strong and the finger is hard to pass. ×: Strong creaking and poor finger passage. b) Softness during rinsing and drying ：: very soft and supple. Δ: Soft. ×: Apply softness. c) Comb passage during drying ○: Comb passage is good and smooth. Δ: Slightly caught when passing through the comb. X: Comb streets such as hair tips are badly stuck.

[0032]

[Table 1]

Example 4 A hairdresser shampooed about 10 g of a female monitor of the age of 40 who had about 10% of white hair on the forehead, and then a beautician applied about 15 g of the composition of Example 3 (Table 1). It was applied, left at 35 ° C. for 60 seconds, rinsed, and further dried with a dryer.
After the same operation was further repeated four times, the conspicuousness of gray hair was visually evaluated by 10 panelists. Table 2 shows the results.
It was shown to.

[0034]

[Table 2]

Example 5 The following composition was applied to about 5 g of a Western blonde hair bundle.
2.5 g was applied and left at 30 ° C. for 30 minutes. afterwards,
Rinse with running water and dry. The feel of the hair during rinsing and drying was good.

[0036]

(Composition) (%) (1) Steel Blue 0.025 (2) 2-amino-5-β-N-hydroxyethyl aminonitrobenzene 0.050 (3) Behenyltrimethylammonium chloride 1.0 (4 ) Cetostearyl alcohol 4.0 (5) Propylene glycol 7.0 (6) Polyoxyethylene modified organopolysiloxane (polyoxyethylene group 20% by weight, molecular weight of about 5,5000), general formula (B-1) R ¹ = CH ₃ , R ² = hydrogen atom, m = 50-55, n = 2-3, x = 9-11, y = z = 0, p = 3) 2.0 (7) NaOH ( (Adjusted to pH 4.3) Suitable amount (8) Phosphoric acid (Adjusted to pH 4.3) Appropriate amount (9) Water balance

Example 6 The following composition was applied to about 5 g of a Western blonde hair bundle.
2.5 g was applied and left at 30 ° C. for 30 minutes. afterwards,
Rinse with running water and dry. The feel of the hair during rinsing and drying was good.

[0038]

(Composition) (%) (1) 1,3-butylene glycol 20.0 (2) 2-benzyloxyethanol 7.0 (3) Lactic acid 2.0 (4) Black No. 401 0.02 ( 5) Purple No. 401 0.02 (6) Orange No. 205 0.04 (7) Polyoxyethylene-modified organopolysiloxane (polyoxyethylene group 18% by weight, molecular weight about 6,700, general formula (B-2); R ¹ = CH ₃ , R ² = hydrogen atom, m = 65-75, n = 1, x = 8-10, y = z = 0, p = 3) 1.5 (8) Hydroxyethyl cellulose 1.5 (9) NaOH (adjusted to pH 3.5) Suitable amount (10) Water balance

Example 7 The following composition was applied to about 5 g of a Western blonde hair bundle.
2.5 g was applied and left at 30 ° C. for 30 minutes. afterwards,
Rinse with running water and dry. The feel of the hair during rinsing and drying was good.

[0040]

(Composition) (%) (1) Ethanol 20.0 (2) Benzyl alcohol 7.0 (3) Lactic acid 2.0 (4) Black No. 401 0.01 (5) Purple No. 401 0.01 (6) Red No. 227 0.03 (7) Polyoxyethylene-modified organopolysiloxane (polyoxyethylene group 7% by weight, molecular weight about 13,000, general formula (B-3); R ¹ = CH ₃ , R ² = hydrogen Atom, m = 150-170, x = 8-12, y = z = 0, p = 3) 2.5 (8) Xanthan gum 1.0 (9) NaOH (adjusted to pH 3.0) Suitable amount (10) Water balance

Example 8 The following composition was applied to about 5 g of a Western blonde hair bundle.
2.5 g was applied and left at 30 ° C. for 30 minutes. afterwards,
Rinse with running water and dry. The feel of the hair during rinsing and drying was good.

[0042]

(Composition) (%) (1) Ethanol 20.0 (2) Benzyl alcohol 3.0 (3) Citric acid 2.0 (4) Black No. 401 0.01 (5) Purple No. 401 01 (6) Orange No. 227 0.03 (7) Polyoxyethylene-modified organopolysiloxane (19% by weight of polyoxyethylene group, molecular weight of about 4,200, general formula (B-1); R ¹ = CH ₃ , R ² = Hydrogen atom, m = 35-45, n = 1-3, x = 8-10, y = z = 0, p = 3) 0.5 (8) hydroxyethyl cellulose 1.5 (9) NaOH (pH 4.0) (Adjusted to the appropriate amount) (10) water balance

 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-194161 (JP, A) JP-A-4-74113 (JP, A)

Claims (1)

(57) [Claims] 1. The following components (A), (B) and (C): (A) direct dye (B) a polyoxyalkylene group containing 3 to 30% by weight in the molecule and dispersible in water Oxyalkylene-modified organopolysiloxane (C) Formula (C-1) [Wherein, R ³ represents a hydrogen atom, a lower alkyl group or a group A hand or a saturated or unsaturated divalent hydrocarbon group having 1 to 3 carbon atoms), A and B each represent a hydrogen atom or a hydroxyl group, and a, b and c each represent an integer of 0 to 5. Where a = b
= C = 0 and A = H, and a = b = c = 0 and R ³ =
Excluding the case where H and A = OH], a compound represented by the formula (C-2) Wherein, in the formula, R ⁶ represents a linear or branched alkyl group having 1 to 18 carbon atoms, and an organic solvent selected from alkylene carbonates having 1 to 4 carbon atoms and a pH of 1 to 4; Is in the range of 2.0 to 4.5.