JPH04330009A - Dyeing agent composition for cuticla fiber - Google Patents

Abstract

PURPOSE:To provide a dyeing agent composition containing a precursor substance for oxidation dye and an alkoxy-modified silicone derivative, useful for dyeing hair without damaging the hair, etc., and giving dyed hair resistant to discoloration, lowering of the feeling quality and damage of the hair in shampooing. CONSTITUTION:The objective composition contains (A) an oxidation dye precursor composed of a precursor such as p-phenylenediamines, 2,5-aminopyridine derivative and p-aminophenols and a coupler such as alpha-naphthol, o-cresol and 2,6-dimethylphenols and (B) a modified silicone derivative having one or more alkoxy groups in the molecule and having a melting point of >=30 deg.C, e.g. the compound of formula I (R<1> is 1-28C alkyl; R<2> is methyl or phenyl; (k) is 0-6; (l) is 1-3,000; (m) and (n) are integers; (m+n) is 1-500), especially a compound of formula II (l) is 1-100; (m) is 1-50). The amounts of the components A and B are preferably 0.5-10wt.% and 0.2-5wt.%, respectively.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a keratinous fiber dyeing composition, and more specifically to a keratinous fiber dyeing composition that causes no damage to the hair during dyeing, and which causes less discoloration, less deterioration of the feel of the hair, and less damage when hair is washed. The present invention relates to a drug composition.

0002

[Prior Art and Problems to be Solved by the Invention] Oxidative dye compositions are widely used for dyeing keratinous fibers such as hair because they provide various color tones and have excellent dyeing power. . This oxidation dye composition generates a pigment by permeating colorless low-molecular oxidation precursors (precursors, couplers) into the horny fibers and causing oxidation in the horny fibers with air or an oxidizing agent. Although it is used for dyeing, it has the disadvantage that the keratinous fibers are severely damaged during dyeing and the fastness of the dyeing is not sufficient. Therefore, after dyeing, the hair loses its suppleness, becomes difficult to comb, and when washed, etc., the hair loses moisture and luster, fades, and becomes unnatural in color. was there.

[0003] In order to solve these problems, a product containing a dialkyl type quaternary ammonium salt (Japanese Unexamined Patent Application Publication No. 1989-1999) was developed.
2-96749), those containing specific cationic polymers, fatty acids and benzyl alcohol (Japanese Patent Application Laid-open No.
-49340), containing a cationic polymer and an anionic activator (Japanese Patent Application Laid-Open No. 157713/1982)
, basic amino acids (JP-A-56-77220), keratin hydrolysates (JP-A-57-192309), aldohexoses (JP-A-59-93017), mucopolysaccharides (JP-A-1-56611) ), deoxyribonucleic acid (JP-A-1-68311), cationic denatured protein (
JP-A-1-275519) or glucan (JP-A-1-275519)
No. 279819) has been disclosed, but none of them had sufficient effects. Therefore, there has been a strong desire for a horny fiber dye composition that does not damage the horny fibers during dyeing and has sufficient dyeing fastness.

0004

[Means for Solving the Problems] In view of the above-mentioned circumstances, the inventors of the present invention have conducted intensive studies on horny fiber dye compositions, and have found that if the oxidation dye contains a specific alkoxy-modified silicone derivative, the horny fibers will be dyed. The present inventors have discovered that damage to the hair, fading of color, deterioration of texture, and damage to hair due to repeated washing etc. can be effectively prevented, and the present invention has been completed.

That is, the present invention provides an oxidation dye precursor having one or more alkoxy groups in the molecule and having a melting point of 30°C.
The present invention provides a horny fiber dye composition containing the above-mentioned modified silicone derivative.

The oxidative dye precursor used in the horny fiber dye composition of the present invention has a benzene nucleus or a heteroaromatic nucleus having an amino group and/or a hydroxyl group in a para or ortho relationship, and is easily oxidized by an oxidizing agent. It consists of a compound to be oxidized (hereinafter referred to as "precursors") and a substance (hereinafter referred to as "couplers") that easily undergoes a coupling reaction with the oxidized form of the precursors to produce a dye.

[0007] Here, as the precursors, for example, p
-phenylenediamine, p-tolylenediamine, N-
Methyl-p-phenylenediamine, N,N-dimethyl-
p-phenylenediamine, N,N-diethyl-2-methyl-p-phenylenediamine, N-ethyl-N-(hydroxyethyl)-p-phenylenediamine, chlor-p
-phenylenediamine, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, methoxy-p-
Phenylenediamine, 2,6-dichloro-p-phenylenediamine, 2-chloro-6-bromo-p-phenylenediamine, 2-chloro-6-methyl-p-phenylenediamine, 6-methoxy-3-methyl-p- Phenylenediamine, 2,5-diaminoanisole, N-(2-hydroxypropyl)-p-phenylenediamine, N-2-
One or more NH2- groups, NHR- groups or N(R)2- groups such as methoxyethyl-p-phenylenediamine (
R represents an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms); 2,5-diaminopyridine derivative; para-aminophenol, 2-methyl-
4-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol, 2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4 -aminophenol, 2,3-dimethyl-4-aminophenol, 2,5
Examples include p-aminophenols such as -dimethyl-4-aminophenol, 2,4-diaminophenol, and 5-aminosalicylic acid, o-aminophenols, and o-phenylenediamines.

[0008] Also, examples of couplers include α-
naphthol, o-cresol, m-cresol, 2,6
-dimethylphenol, 2,5-dimethylphenol,
3,4-dimethylphenol, 3,5-dimethylphenol, benzcatechin, pyrogallol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene,
5-amino-2-methylphenol, hydroquinone, 2
, 4-diaminoanisole, m-tolylenediamine,
4-Aminophenol, resorcin, resorcin monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 1-phenyl-3-amino-5-pyrazolone, 1-phenyl-3,5-diketo- Pyrazolidine, 1-methyl-7-dimethyl-amino-
4-hydroxy-2-quinolone, m-aminophenol, 4-chlororesorcin, 2-methylresorcin, 2,
4-diaminophenoxyethanol, 3,5-diamino-trifluoromethylbenzene, 2,4-diamino-fluorobenzene, 3,5-diamino-fluorobenzene, 2,
4-diamino-6-hydroxypyrimidine, 2,4,6
-triaminopyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 4,6-diamino-2-hydroxypyrimidine, 2,6-diaminopyrimidine, and the like.

These precursors and couplers may be used alone or in combination of two or more. The amount of these oxidation dye precursors to be blended is not particularly limited, but is preferably 0.1 to 20% by weight, particularly 0.5 to 10% by weight, based on the total composition.

The modified silicone derivative used in the present invention is a siloxane polymer having a melting point of 30° C. or higher (solid at room temperature (25° C.)) and having one or more alkoxy groups in one molecule. . The molecular form may be either linear or reticular. In addition to alkoxy groups, organosiloxanes forming modified silicone derivatives include alkyl groups such as methyl, ethyl, and propyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl and naphthyl groups; cyclohexyl A functional group such as a cycloalkyl group may also be included. Those containing a methyl group are generally used.

A typical example of the alkoxy group contained in the above-mentioned modified silicone derivative is shown by the following general formula (1). -(CH2)kO-R1 (1) (In the above formula, R1 represents an alkyl group having 1 to 28 carbon atoms (preferably 12 to 22 carbon atoms), and k represents an integer of 0 to 6.)

Representative alkoxy-modified silicone derivatives include those represented by the following general formula (2).

[0013]

[Chemical formula 1]

(In the above formula, R2 represents a methyl group or a phenyl group, l represents an integer of 1 to 3000, m and n represent integers such that m+n=1 to 500, and R1 and k represent the above formula (synonymous with (1), but these may be the same or different)

Particularly preferred among the alkoxy-modified silicone derivatives represented above are those represented by the following general formula (3).

[0016]

[Case 2]

(In the above formula, l represents an integer of 1 to 100, m represents an integer of 1 to 50, and R1 has the same meaning as in the above formula (1).) The melting point of the alkoxy-modified silicone derivative is 30 ℃ or higher and 60℃ or lower, preferably 40℃ or higher and 50℃ or lower. As a specific example, in general formula (3), as stearoxy-modified silicone, l = 5 to 30, m = 2 to 15, preferably l = 7 to 1.
3, m = 2 to 8, cetyloxy modified silicone, l = 5 to 30, m = 2 to 15, preferably l = 7 to
13, m = 2 to 8, as myristyroxy modified silicone, l = 5 to 30, m = 2 to 15, preferably l
= 6 to 10, and m = 3 to 9. The above-mentioned alkoxy-modified silicone derivatives have good compatibility with fats and oils such as higher alcohols, and their use improves the storage stability of emulsions. Furthermore, since it is in a solid state, it does not feel sticky when applied to hair and has excellent water occlusion properties.

The alkoxy-modified silicone derivative used in the present invention is preferably contained in the composition usually in the range of 0.1 to 10% by weight, particularly 0.2 to 5% by weight.
A range of is preferred.

The horny fiber dyeing composition of the present invention may be further blended with a direct dye to additionally change the hue. Such direct dyes include, for example, 2-amino-
4-nitrophenol, 2-amino-5-nitrophenol, nitro-p-phenylenediamine hydrochloride, nitro-
p-phenylenediamine, p-aminophenylsulfamic acid, p-nitro-o-phenylenedimine, picramic acid, sodium picramate, picric acid, chrome brown RH, hematein, nitro-p-phenylenediamine sulfate, p-nitro-sulfate o-phenylenediamine,
p-nitro-m-phenylenediamine sulfate, 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. 10
No. 6, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1, Blue No. 2, Red No. 201, Red No. 227, Red No. 230, Red No. 231, Red No. 232, Orange No. 205, Orange No. 207 ,
Yellow No. 202, Yellow No. 203, Green No. 201, Green 20
No. 4, Green No. 205, Blue No. 202, Blue No. 203, Blue No. 205, Brown No. 201, Red No. 401, Red No. 50
No. 2, Red No. 503, Red No. 504, Red No. 506, Orange No. 402, Yellow No. 402, Yellow No. 403, Yellow No. 406, Yellow No. 407, Green No. 401, Green No. 402, Purple No. 4
No. 01, black No. 401; red No. 215, which is an oil-soluble dye;
Red No. 218, Red No. 225, Orange No. 201, Orange No. 206, Yellow No. 201, Yellow No. 204, Green No. 202, Purple 2
No. 01, Red No. 501, Red No. 505, Orange No. 403, Yellow No. 404, Yellow No. 405, Blue No. 403; basic dyes Red No. 213, Red No. 214; and Willia
ms basic dye Sienna Brown, Ma.
hogany, Madder Red, Steel B
Examples include blue, Straw Yellow, etc.
Particularly preferred are nitrophenyl diamine, nitro-aminophenol and anthraquinone dyes. When direct dyes are incorporated into the horny fiber dye composition of the present invention, the total amount of these direct dyes in the composition is 0.001 to 20% by weight,
In particular, it is preferably 0.01 to 10% by weight.

The keratin fiber dyeing composition of the present invention causes oxidative coupling even with oxygen in the air and dyes hair, etc., but it is possible to cause oxidative coupling by adding a chemical oxidizing agent. More preferred. Particularly preferred oxidizing agents include hydrogen peroxide; products of addition of hydrogen peroxide to urea, melamine or sodium borate; mixtures of such hydrogen peroxide adducts with potassium peroxide-disulfuric acid, and the like.

The stratum corneum fiber dyeing composition of the present invention is usually preferably provided in the form of a cream, emulsion, or the like. To form such a dosage form, emulsifiers, solubilizers, thickeners, stabilizers, hair styling bases, fragrances, etc. commonly used in the cosmetics field are added to the oxidative dye precursor, modified silicone derivative, etc. However, it can be manufactured according to conventional methods. Examples of wetting agents (emulsifiers) used here include alkylbenzene sulfonates, fatty alcohol sulfates, alkyl sulfonates, fatty acid alkanolamides, addition products of ethylene oxide and fatty alcohols, linear alkyl ammonium salts, branched chain alkyl ammonium salts, etc. Can be mentioned. Further, examples of thickeners include methyl cellulose, hydroxyethyl cellulose, starch, higher fatty alcohols, paraffin oil, fatty acids, etc., and examples of stabilizers include reducing agents such as sulfites, hydroquinone derivatives, chelating agents, etc. Examples of hair styling bases include higher alcohols, oils such as various nonionic surfactants, and various cationic polymers.

Furthermore, the horny fiber dye composition of the present invention contains:
Other silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, cyclic silicone, polyether-modified silicone, amino-modified silicone, etc. can also be blended to improve the feel. In order to dye horny fibers using the horny fiber dye composition of the present invention, for example, an oxidizing agent is added to the horny fiber dye composition of the present invention to perform oxidative coupling to prepare a dyeing solution. Apply the dye solution to the horny fibers for 10-50 minutes, preferably 25 minutes.
This is done by washing the keratinous fibers after an action time of about 35 minutes and then drying them. Here, the application of staining solution is 1
It is carried out at 5-40°C. Further, it is preferable to adjust the pH of the composition as appropriate using ammonia or the like.

[0023]

Effects of the Invention The keratin fiber dye composition of the present invention not only has good dyeing properties but also has excellent fastness and does not cause discoloration of the hair even after repeated hair washing. It is an excellent product that leaves the hair feeling good and shows no damage even after repeated hair washing.

[0024]

EXAMPLES Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. Example 1 Cream-like products 1, 2, and 2 of the present invention having the compositions shown in Table 1 below.
No. 3 and a comparative product were prepared, and an equal amount of the following second agent (oxidizing agent composition) was added to each of these and mixed. After applying this to gray hair tresses and leaving it for 30 minutes at 30℃,
Rinsed, shampooed and rinsed, and dried. As a result, sufficient dyeability was obtained for each gray hair tress. These were further subjected to evaluation tests as shown in (1) and (2) below. The results are shown in Tables 2 and 3.

[0025]

[Table 1]

1) Stearoxy-modified silicone (formula (3)
), R=C18H37, m. p. =40~50℃, l
=8-12, m=3-7 2) Cetyloxy-modified silicone (in formula (3), R=C1
6H33, m. p. =40~50℃, l=8~12, m
=3~7)

Second agent Hydrogen peroxide

6.0 (wt%) Methylparaben

0.1 Phosphoric acid

Amount of water to adjust pH to 3.5

balance meter

100.0 Production method: Heat and dissolve p-phenylenediamine, resorcinol, and ascorbic acid in water, and separately dissolve in propylene glycol.
Heat-dissolved behenyltrimethylammonium chloride, 2-octyldodecyltrimethylammonium chloride, cetostearyl alcohol, 2-octyldodecanol, and modified silicone were mixed at about 70°C. After cooling to 40° C., strong aqueous ammonia was added to obtain the first agents of products 1, 2, and 3 of the present invention and comparative products. Evaluation test: (1) Immediately after dyeing (after dyeing, leaving, rinsing, shampooing,
After rinsing and drying) a Hair feel ○: Flexible and easy to comb. Δ: Slightly poor flexibility and combability. ×: Lack of flexibility and poor combability. b. Hair damage The surface of the hair before and after dyeing was observed with a scanning electron microscope (3000x magnification), and the degree of damage to the hair epidermis was evaluated according to the following criteria. ○: Same as before hair dyeing, no damage observed. △: Slight damage such as bumps, cracks, and peeling of the hair epidermis is observed. ×: Significant damage such as bumps, cracks, and peeling is observed in the hair epidermis.

(2) After washing, the dyed hair was washed and dried four times with a commercially available shampoo, and compared with the treated and dyed hair, the following evaluations were made. c Color tone ○: No change in color tone is observed. ×: The color tone has changed slightly. d Hair feel ○: No difference observed from untreated hair. △: Slightly inferior in flexibility and combability compared to untreated hair. ×: The flexibility and combability are considerably inferior to that of untreated hair. e Hair damage (scanning electron microscope: observed at 3000x magnification) ○: No difference from untreated hair observed. △: Compared to untreated hair, slight protuberances, cracks, peeling, etc. of the hair epidermis are observed. ×: Compared to untreated hair, the hair epidermis has significant protuberances, cracks, peeling, etc.

[0029]

[Table 2]

[0030]

[Table 3]

Claims (1)

[Claims] 1. A keratin fiber dye composition comprising an oxidation dye precursor and a modified silicone derivative having one or more alkoxy groups in the molecule and having a melting point of 30° C. or higher.