JPH0242014A - Horn-like fiber dyeing composition - Google Patents

Abstract

PURPOSE:To obtain a horn-like fiber dyeing composition containing a diaminobenzene derivative or salt thereof as a developing substance, capable of dyeing horn-like fiber into intense color tone in high chroma and exhibiting excellent fastness. CONSTITUTION:In the aimed dyeing composition consisting of a developing substance and coupling substance, as the developing substance a diaminobenzene derivative expressed by the formula [R1 and R2 are H, 1-5C alkyl or hydroxyalkyl, -(CH2)nNR3R4, -(CH2)nCOOR5 (R3-R5 are H, 1-5C alkyl or hydroxyalkyl; n is 1-5); X is COOR6, CONHR7, SO3R8, etc., (R6-R8 is H, 1-5C alkyl or hydroxyalkyl) or salt thereof] is contained and a conventional wetting agent, emulsifier, solubilizer, etc., is added to above-mentioned main ingredients and the blend is prepared according to an ordinary method to provide the aimed product. The developing substance and coupling substance are used at a blend molar ratio of 1:0.5-1:2 and prepared in an agent type such as cream, emulsion, gel or solution.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention uses the following general formula (1) Rt R as a color developer.
.

\ / [In the formula, R1 and R2 are the same or different and are a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group, -(CH2) NR3R4
, -(CH2) C0OR, (where R3, R4 and R
5 is the same or different and represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group; L1. ii indicates the number from 1 to 5), and X is C0
OR,,C0NHR7,So,R,,5O3NHR,,
Cyaminobenzene represented by The present invention relates to a horny fiber dyeing composition containing the derivative.

[Conventional technology]

Conventionally, so-called oxidation dyes, which develop color by oxidative coupling of a color developer and a coupling substance, have been used to dye keratinous fibers such as hair because of their strong color tone and good fastness. . Color developing substances commonly used for these include p-phenylenecyamine derivatives, p-
Aminophenol derivative, cyaminobilicin derivative, 4
-Aminopyrazolone derivatives and peterocyclic pyrazolones are known, and m-phenylenecyamine derivatives, phenol derivatives, m-aminophenol derivatives and pyrazolone derivatives are known as cassilling substances.

[Problem to be solved by the invention]

However, conventional oxidation dyes are still unsatisfactory in saturation, dyeing power and fastness.

[Failure to solve the problem]

The inventors of the present invention have conducted various studies to solve the above problems, and have found that by using a specific cyaminobenzene derivative as a color developer, it is possible to dye horny fibers in strong colors with high saturation. The present invention was completed based on the discovery that the coloring process of Tonanashi and its dyeing has excellent fastness.

Finally, the present invention provides a dyeing composition comprising a color developing substance and a coupling substance, which contains a cyaminobenzene derivative represented by the above-mentioned formula (1) or an inorganic or organic salt thereof as the color developing substance. The present invention provides a horny fiber dyeing composition characterized by:

In the horny fiber dyeing composition of the present invention, preferred cyaminobenzene derivatives used as color developing substances include 2,5-cyaminobenzenesulfonic acid and z-
(2'-hydroxyethyl)amino-5-aminebenzenesulfonic acid, 2-(3'-hydroxypropyl)amino-5-aminebenzenesulfonic acid, 2-methylamino-5-aminebenzenesulfonic acid, 2-ethylamino −
5-Aminobenzenesulfonic acid, 2-(n-7')amino-5-aminebenzenesulfonic acid, 2-(n-
butyl)amino-5-aminobenzenesulfonic acid, 2.
Ethyl 5-cyaminobenzenesulfonate, 2-(2'-
ethyl hydroxyethyl)amino-5-aminobenzenesulfonate, ethyl 2-(3'-hydroxyzorobyl)amino-5-aminebenzenesulfonate, ethyl 2-methylamino-5-aminebenzenesulfonate, 2-ethylamino -5-aminobenzenesulfonic acid ethyl, 2-
Ethyl (n-7'lopyl)amino-5-aminebenzenesulfonate, 2-(n-butyl)amino-5-aminebenzenesulfonate ethyl, 2,5-cyaminobenzenesulfonamide, 2-(2' -hydroxyethyl)amino-5-aminobenzenesulfonic acid amide, 2-(3
'-Hydroxypropyl)amino-5-aminebenzenesulfonamide, 2-methylamino-5-aminebenzenesulfonamide, 2-ethylamino-5-aminebenzenesulfonamide, 2-(n-propyl)amino- 5-aminebenzenesulfonic acid amide, 2-(n-
7” thyl)amino-5-aminebenzenesulfonic acid amide, 2,5-cyaminobenzoic acid ff, 2-(2'-hydroxyethyl)amino-5-aminobenzoic acid, 2-(3'
-hydroxyzorobyl) amino-5-aminebenzoic acid,
2-Methylamino-5-aminobenzoic acid, 2-nitylhumino-5-aminobenzoic acid, 2-(n-propyl)amino-5-aminobenzoic acid, 2-(n-butyl)amino-
5-Aminebenzoic acid, ethyl 2.5-cyaminobenzoate, 2-(2'-hydroxyethyl)7mi/-5-aminobenzoic acid ether, 2-(3'-hydroxyzolobyl)amino-5-amino Ethyl benzoate, 2-methylamino-
Ethyl 5-ami7benzoate, 2-ethylamino-5-aminobenzoic acid ether, 2-(n-7'robil)amino-
Ethyl 5-aminobenzoate, ethyl 2-(n-butyl)amino-5-aminobenzoate, 2-carbamoyl-1,
4-cyaminobenzene, 2-carbamoyl-1-(2'
-hydroxyethyl)amino-4-aminebenzene, 2
-Carbamoyl-1-(3'-hydroxyzolobyl)amino-4-aminobenzene, 2-carbamoyl-1-methylamino-4-aminebenzene, 2-carbamoyl-
1-ethylamino-4-aminebenzene, 2-carbamoyl-1-(n-propyl)amino-4-aminebenzene, 2-cartumamoyl-1-(n-butyl)amino-
4-amine benzene is mentioned.

The cyaminobenzene derivative (D), which is a color developer, can be produced, for example, by reducing the compound of formula (1) according to the following reaction formula.

(+) [In the formula, R1s R2 and The reduction method is simple and efficient.

In catalytic hydrogenation, Q radium, platinum, copper, nickel, etc. are used as a catalyst. Preferred solvents include methanol, ethanol, ethyl acetate, and trimethylformamide. The reaction temperature ranges from room temperature to the boiling point of the solvent used,
Hydrogen pressure can be carried out in the range of 1 to 250 kg/cm''.

After completion of the reduction, the catalyst is separated, and the liquid f can be purified very easily by distillation or recrystallization after concentration.

In the reduction method using zinc, a water-miscible solvent such as methanol, ethanol, acetone, N,N-methylformamide, dimethyl sulfoxide, etc. is added as necessary in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide to remove excess. This can be carried out by heating under reflux in the presence of zinc. After the solid t-filtration is completed, the r-liquid is extracted with a suitable organic solvent, concentrated, and then easily purified by distillation or recrystallization.

Incidentally, the compound (pill) serving as a raw material is produced, for example, by reacting the corresponding chloroform (II) K amine according to the following reaction formula.

(II) In the C formula, RI% J and X have the same meanings as above] In the present invention, the cyaminobenzene derivative (1) can also be used in the form of an inorganic or organic salt, Inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid: carbon number 1
Carboxylic acids with ~20 straight-chain or branched alkyl groups, hydroxycardoic acids, ? Examples include salts of organic acids such as hydroxycarboxylic acids, and salts of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, zolopionic acid, lactic acid, citric acid and the like are particularly preferred.

The coupling substances used in the dyeing composition of the present invention are not particularly limited as long as they are commonly used in oxidative hair dyes, but include sidelight, α-naphthol, O-cresol, m-cresol, and p-cresol. -amino-0-cresol, 2
．． 6-tmethylphenol, 2.5-tmethylphenol, 3.4-tmethylphenol, 3.5-tmethylphenol, benzcatechin, pyrogallol, 1.5- or 1.7-dihydroxynaphthalene, 5-amino -2-
Methylphenol, hydroquinone, 2,4-zoaminoanineol, m-tolylenecyamine, 4-aminephenol, resorcin, resorcin monomethyl ether, m
-phenylenecyamine, 1-phenyl-3-methyl-pyrazolone, 1-phenyl-3-aminovilasolone, 1
-Phenyl-3,5-zoketovirazolizone, 1-methyl-7-dimethyl-amino-4-hydroxyquinolone-
2,1 amino-3-acetyl-acetamino-4-nitrobenzole or 1-amino-3-cyanoacetelamino-4-nitro-benzo-/l/, m-7mi/phenol, 4-chlororesorcinol, 2-methylresorcin,
2.4-&aminoenoxyethanol, 2,6-cyaminopyricine, 3.5-cyamino-triflomethylbenzene, 2.4-cyamino-70lobenzene, 3.5-
Cyamino-fluorobenzene, 2,4-cyamino-6-hydroxypyrimizone, 2,4.6 ~
rear amino acid, 2-amino-4,
6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 4,6-zoamino-2-hydroxypyrimizone, p-nitro-〇-phenylenecyamine, 2-amino-5-ditrophenol, p-nitro-m
Examples include -phenylenecyamine, 0-nitro-p-phenylenecyamine, 2-amino-4-nitrophenol, and the like.

The mixing ratio of the color developing substance and the coupling substance in the dyeing composition of the present invention is approximately 1:α5 to 1:2 in molar ratio, although it is acceptable even if one component is in excess compared to the other. It is preferable. Further, the color developing substance and the coupling substance can be used alone or in combination of two or more.

Further, the dyeing composition of the present invention may contain known color developing substances and ordinary direct dyes, if necessary, in order to obtain a desired color tone.

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

The dyeing composition of the present invention is usually a cream, an emulsion,
It is preferably provided in a dosage form such as a dal or a solution. In order to form such a dosage form, in addition to the color developing substance and the cassillating substance, wetting or emulsifying agents, solubilizers, thickeners, stabilizers, feel improvers, hair styling bases, and perfumes commonly used in the cosmetics field are added. etc., and may be manufactured according to a conventional method.

Wetting or emulsifying agents used here include, for example, alkylbenzene sulfonates, fatty alcohol sulfates, alkyl sulfonates, fatty acid alkanolamides, addition products of ethylene oxide and fatty alcohols, and the like. In addition, as thickeners, methylcellulose, dengun, higher fatty alcohol, NoQ rough oil,
Examples of stabilizers include reducing agents such as sulfites, hydroquinone derivatives, chelating agents, etc., and examples of feel improvers and hair styling bases include silicones, higher alcohols, and various nonionic interfaces. Examples include oil agents such as activators, various cation-rimers, and the like.

The total amount of the color developing substance and the cassillating substance in these dosage forms is preferably 0.1 to 10% by weight (hereinafter simply expressed as %), particularly preferably 1 to 5%. Wetting or emulsifying agent is usually 0
．． It is preferable that the amount of sizing agent is 01 to 25%.

In addition, in these dosage forms, the pH of the entire composition is 8 to 1.
It is preferable to adjust it to about 0.

In order to dye horny fibers using the dyeing composition of the present invention, for example, an oxidizing agent is added to the dyeing composition of the present invention to perform oxidative cassilling to prepare a dyeing solution, and this dyeing solution is applied to the horny fibers. This is carried out by washing the stratum corneum fibers for an action time of about 10 to 50 minutes, preferably about 25 to 35 minutes, and then drying them. Here, the application temperature of the staining solution is 15~
Performed at 40°C.

〔Example〕

The present invention will be further explained below with reference to Reference Examples and Examples, but the present invention is not limited thereto.

Reference Example 1 Synthesis of 2-(2'-hydroxyethyl)amino-5-aminobenzoic acid: (i) 2-chloro-5-nitrobenzoic acid 12. Of (
0.06 mol) of ethanol and 9.0 of ethanolamine (0.15 mol) were added and refluxed for 6 hours. The reaction mixture was dissolved in water and neutralized with hydrochloric acid, and the precipitated solid was separated from P, washed with diluted hydrochloric acid, dried, and further recrystallized from ethanol to give 2-(2'-hydroxyethyl)amino. -5-Nitrobenzoic acid [979(
A yield of 62% was obtained.

Melting point 16 & 5~16g, 7℃ Elemental analysis Calculated value (% H4,46, C47,80,
N1139 actual measurement value (to) H4, 52, C47, 99, N
12.12(ii) 2 −(2' obtained in (i)
-hydroxyethyl)amino-5-nitrobenzoic acid8.
After dissolving 97f in 200d of methanol and adding 1.5F of 5% 97f carbon, the theoretical amount of hydrogen was absorbed at room temperature and 1 atm. After separating the catalyst from F, hydrochloric acid was added to the F solution and concentrated to produce 2-(2'-hydroxyethyl)amino-5-aminobenzoic acid as a hydrochloride.
94f was isolated (76% yield).

Melting point: Decomposition elemental analysis at 200℃ Calculated value (total) H! 1L24. C40,16
, N1α41 (as hydrochloride) Actual value (to) H5,36, C4α22. N1α38 Reference Example 2 Synthesis of 2-(3'-hydroxyzorobyl)7mi/-5-aminobenzoic acid: (1) Addition of 3-amino-1 to ethanolamine
2-(3'-Hydroxyzorobyl)amino-
5-Nitrobenzoic acid was obtained with a yield of 72%.

Melting point 1413-151.0℃ Elemental analysis Calculated value % HNO3, C49, 99, N1
t66 actual value (to) Ha21. C5α08. N11.
99(11) In the same manner as in Reference Example 1(ii), 2-(3
'-Hydroxyzorobyl)amino-5-aminobenzoic acid hydrochloride was obtained with a yield of 62%.

Melting point: Decomposes at 220℃ Obtained with a yield of 76%.

Actual value (% Ha41.C42,12,N9.72 Reference example 3 Synthesis of 2-(n-butyl)amino-5-aminobenzoic acid: (1) Reference example except using n-butylamine instead of ethanolamine Similarly to 1(1), 2-(n
-butyl)amino-5-nitrobenzoic acid was obtained with a yield of 81%.

Melting point 181.0-182.5℃ Elemental analysis Calculated value (g) H5,92, C55,45, N1t76 actual value (to) Ha86, C3N40, N1t78 (1
1) In the same manner as in Reference Example 1 (ii), 2-(n-butyl)amino-5-aminobenzoic acid hydrochloride was prepared with a melting point of 16αO.
~161.2℃ Actual value (to) H6,32, C4N81, N9.2
2 Reference Example 4 Synthesis of ethyl 2-(n-butyl)amino-5-benzoate: (i) Ethyl 2-chloro-5-nitrobenzoate 10
n-butylamine 8F (α
11 mol) and ethanol 10W11 were added and refluxed for 6 hours. The reaction mixture was added to water, and the precipitated solid was washed with water, dried, and recrystallized from hexane to give 11.82 f of ethyl 2-(n-butyl)amino-5-nitrobenzoate.
(yield 95%).

Melting point 76.2-79.1℃ Elemental analysis Calculated value pJ Ha81, C58,63,
N10.52 Actual value% Ha29. C5&32. N1
0.711r) Ethyl 2-(n-butyl)amino-5-nitrobenzoate obtained in (t) 10. OQP
(α036 mol) was dissolved in 300 m of methanol, 5%
After adding Norazoum Cargon t8f'e, room temperature, 1
A theoretical amount of hydrogen was absorbed under atmospheric pressure. After removing the catalyst, it is concentrated and distilled to give F)2-(n-7”thyl)amino-5-
Ethyl aminobenzoate total a29F was isolated (yield 62%)
).

Boiling point 134-135°C/α2 mmHf Elemental analysis Calculated value ff, e H&, 53. C6&07. N11.86
Actual measurement value (G) H&21, C66,31, N11.8
9 Reference Example 5 Synthesis of 2-(2'-hydroxyethyl)amino-5-aminobenzoic acid ether: (1) Proceed as in Reference Example 4(1) except that ethanolamine is used instead of n-butylamine. -(2'-
Hydroquinethyl)amino-5-nitrobenzoic acid 86
% yield.

Melting point 11LIL1~122.5℃ Elemental analysis calculated value (to) H5.54, C51.96, N11.02
Actual value (to) I (5, 35, C51, 85, N10.
98(11) Reference Example 1 In the same manner as in (i), 2-(2
Ethyl '-hydroxyethyl)amino-5-aminobenzoate hydrochloride was obtained with a yield of 75%.

Melting point: Decomposition elemental analysis at 195℃ Calculated value (to) H&10, C44,45
, N9.43 (as hydrochloride) Actual value (% Ha13.C44,37, N9.28p
Example paste composition by adjusting H to 9.5 with ammonia Nioleic acid 10 (%)
Oleic acid zoethanolamide 8 Oleyl alcohol 2 Ethanol 15 Zolopyrene glycol 10 Ammonium chloride
325% ammonia
7 water
35 001 mol of color developing substance and coupling substance α0 shown in Table 1 in 100f of paste consisting of the above composition.
1 mol was mixed. Next, the composition was glued to produce a dyeing composition of the present invention.

A dyeing solution was prepared by adding an equal weight of 6% aqueous hydrogen peroxide solution to 100f of the dyeing composition of the present invention. This dye solution was applied to the hair of a mixed white hair and left at 30° C. for 30 minutes.

The hair was then washed with regular shampoo and dried.

Table 1 shows the results of observing the color tone of the obtained dyeing.

Color developer Pl:2 P2:2 5-cyaminebenzenesulfonic acid (2'-hydroxyethyl)amino-aminobenzoic acid (21-hydroxyethyl)amino-aminobenzoic acid ether P3:2 P4: 2- (n- Glythyl) amino-5-aminobenzoic acid Table 1 C1: C2: C3: C4: p-amino-〇-cresol α-su7tol 1, 5-dihydroxynaphthalene 1.7-dihydroxynaphthalene Below margin [Effects of the invention ] If keratinous fibers are dyed using the dyeing composition of the present invention, a wide range of dyeing from red to purple to blue is possible due to the combination of color developer and coupling substance, which is extremely useful for toning hair dyes. Yes, the color tone is highly saturated. Moreover, the obtained color tone has good light fastness, wash resistance and abrasion resistance.

that's all

Claims (1)

[Claims] 1. In a dyeing composition comprising a color developer and a coupling substance, the color developer has the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 and R_2 are the same or different,
Hydrogen atom, linear or branched alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms, -(CH_2)_nN
R_3R_4, -(CH_2)_nCOOR_5 (where R_3, R_4 and R_5 are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group, and n is a 1 to 5 carbon number ), where X is COOR_6, CONHR_7, S
O_3R_8, SO_3NHR_9, NHCOCH_3
(However, R_6, R_7, R_8 and R_9 are the same or different and represent a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group)
] A horny fiber dyeing composition characterized by containing a diaminobenzene derivative represented by the following or an inorganic or organic salt thereof.