JPH04247018A - Keratin fiber dye composition - Google Patents

Abstract

PURPOSE:To provide a novel aminophenol derivative or a salt thereof having good dyeability, discoloration resistance, washing resistance and abrasion resistance and useful as a coupling substance for obtaining a color tone having a high chroma. CONSTITUTION:An aminophenol derivative of formula 1 (R<1> is lower alkyl; (n) is 2-4), e.g. 2-amino-4-hydroxy-5-methylphenoxyethanol. A nitrophenyl derivative of formula 2 (R<2> is H, alkylsulfonyl, arylsulfonyl) or a salt thereof as an intermediate, e.g. 5'-nitro-4'-(beta-hydroxyethoxy)-2'-methylphenylmethane sulfonate. The compound of formula I is obtained as follows; reacting a compound of formula III with ethylene oxide or an omegahaloalcohol to form a compound of formula II (R<2> is the groups excluding H), hydrolyzing the formed compound of formula II to form the compound of formula II (R<2> is H), and subsequently reducing the formed compound of formula II.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel aminophenol derivatives or salts thereof, intermediates useful for their production, and horny fiber dye compositions containing the aminophenol derivatives or salts thereof as coupling substances.

0002

BACKGROUND OF THE INVENTION Conventionally, so-called oxidation dyes, in which a color developer and a coupling substance are used in combination, have been widely used for dyeing keratinous fibers such as hair. This oxidative dye utilizes the fact that the so-called oxidized dye, which is produced by oxidative coupling between a color developing substance and a coupling substance, strongly dyes hair and the like. Conventionally, color developing substances generally include p-phenylenediamine derivatives, p-aminophenol derivatives, diaminopyridine derivatives, 4-aminopyrazolone derivatives, heterocyclic hydrazones, etc., and coupling substances 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, o-aminophenol, resorcinol, resorcinol 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-dimethylamino-4-hydroxyquinolone-2
, 1-amino-3-acetylacetamino-4-nitrobenzole, 1-amino-3-cyanoacetylamino-
4-Nitrobenzole, m-aminophenol, 4-chlororesorcin, 2-methylresorcin, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 3,5-diaminotrifluoromethylbenzene, 2,4
-Diaminofluorobenzene, 3,5-diaminophlorobenzene, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-triaminopyrimidine, 2-amino-4
, 6-dihydroxypyrimidine, 4-amino-2,6-
Dihydroxypyrimidine, 4,6-diamino-2-hydroxypyrimidine, p-nitro-o-phenylenediamine, 2-amino-5-nitrophenol, p-nitro-
m-phenylenediamine, o-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, etc. are used.

0003

[Problems to be Solved by the Invention] However, conventional oxidation dyes have not been fully satisfactory in saturation, dyeing strength, and fastness. Since these properties are greatly influenced by the characteristics of the coupling substance, finding a substance with excellent properties as a coupling substance is extremely important in obtaining an excellent oxidation dye. Therefore, a coupling substance with excellent color saturation, dyeing strength and fastness has been desired.

0004

[Means for Solving the Problems] Under these circumstances, the present inventors synthesized many compounds and studied their properties as coupling substances, and found that the following general formula (
The present invention was completed based on the discovery that the aminophenol derivative represented by 1) and its salt have the above-mentioned excellent properties.

That is, the present invention provides the following general formula (1)

The present invention provides a stratum corneum fiber dyeing composition characterized by containing an aminophenol derivative represented by the following formula or a salt thereof, and the aminophenol derivative as a coupling substance and a color developer.

The lower alkyl group represented by R1 in the formula of the aminophenol derivative (1) of the present invention includes a methyl group, an ethyl group, a propyl group, and a butyl group.

The aminophenol derivative (1) is produced, for example, according to the following reaction formula.

[0008]

[Image Omitted] That is, compound (3) has ethylene oxide or ω
- reacting a haloalcohol to obtain a compound (2a), hydrolyzing the compound (2a) to obtain a compound (2b),
This is then reduced to obtain the compound (1) of the present invention. In the above reaction formula, examples of the alkylsulfonyl group or arylsulfonyl group represented by R2 include a methylsulfonyl group, an ethylsulfonyl group, and a p-toluenesulfonyl group. Raw material compound (3) can be produced, for example, by the method described in JP-A-62-240960. The reaction between compound (3) and alkylene oxide is carried out in the presence of a base such as sodium hydrogen carbonate at room temperature to
Preferably, the reaction is carried out at 100°C for 1 to 30 hours. Also,
The hydrolysis reaction of compound (2a) is carried out using sodium hydroxide,
This is carried out according to a conventional method in the presence of a base such as potassium hydroxide. Further, the reduction of compound (2b) is preferably carried out by catalytic reduction using a catalyst such as palladium-carbon.

The aminophenol derivative (1) thus obtained may be used in the form of a salt in order to improve the ease of handling in formulation. Such salts include, for example, hydrochloric acid,
Salts with inorganic or organic acids such as sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid, and citric acid are preferred.

[0010] When the compound (1) of the present invention is used as a coupling substance together with a common color developing substance, it is possible to obtain a horny fiber dye composition exhibiting a wide range of color tones from yellow to orange to red to purple. . As the color developer in the present invention, those commonly used for oxidation dyes can be used, such as p-phenylenediamine, toluene-2,5-diamine, N-phenyl-p-
phenylenediamine, p-aminophenol, methoxy-p-phenylenediamine, 2,5-diaminopyridine, p-methylaminophenol, tetraaminopyrimidine, 2,4-diaminophenol, orthoaminophenol, orthochloro-p-phenylenediamine, 4,4
'-diaminodiphenylamine and the like. Among them, p-phenylenediamine, toluene-2,5-diamine, N-phenyl-p-phenylenediamine, methoxy-p-phenylenediamine, orthochloro-p-phenylenediamine, etc. are particularly preferred.

The blending ratio of the color developer and the aminophenol derivative or its salt (1) in the dye composition of the present invention is as follows:
Although one may be in excess compared to the other, it is preferable that the molar ratio is about 1:0.5 to 1:2. In addition, both the color developing substance and the coupling substance may be used alone or in combination.
Combinations of more than one species can also be used.

[0012] The dyeing compositions according to the invention can be incorporated with other coupling substances and, if necessary, direct dyes can also be incorporated in order to additionally change the shade. Examples of such direct dyes include 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, and
Nitro-p-phenylenediamine hydrochloride, nitro-p-phenylenediamine, p-aminophenylsulfamic acid, p-nitro-o-phenylenediamine, picramic acid, sodium picramate, picric acid, chrome brown RH, hematein, nitro-sulfate p-phenylenediamine, p-nitro-o-phenylenediamine sulfate, p-nitro-m-phenylenediamine sulfate, 1-amino-4
-Methylaminoanthraquinone, 1,4-diaminoanthraquinone; Acidic dyes Red No. 2, Red No. 3, Red No. 102, Red No. 104, Red No. 105, Red 1
No. 06, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1,
Blue No. 2, Red No. 201, Red No. 227, Red No. 23
No. 0, red No. 231, red No. 232, orange 205
Orange No. 207, Yellow No. 202, Yellow No. 203, Green No. 201, Green No. 204, Green No. 205, Blue No. 202, Blue No. 203, Blue No. 205, Brown No. 201, Red No. 401, Red No. 502 , red 5
No. 03, Red No. 504, Red No. 506, Orange 402
No., Yellow No. 402, Yellow No. 403, Yellow No. 406
Yellow No. 407, Green No. 401, Green No. 402, Purple No. 401, Black No. 401; oil-soluble dyes Red No. 215, Red No. 218, Red No. 225, Orange 2
No. 01, Orange No. 206, Yellow No. 201, Yellow No. 204
No., Green No. 202, Purple No. 201, Red No. 501
No., Red No. 505, Orange No. 403, Yellow No. 404,
Yellow No. 405, Blue No. 403; Basic dyes Red No. 213, Red No. 214; and Arianor
Basic dye Sienna Brown, Maho
gany, Madder Red, Steel Blue
Among them, nitrophenyl diamine, nitro-aminophenol, and anthraquinone dyes are particularly preferred.

The dye composition of the present invention causes oxidative coupling even with oxygen in the air and dyes hair, etc., but it is more preferable to cause oxidative coupling by adding a chemical oxidizing agent. . 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.

[0014] The dye composition of the present invention is usually a cream,
Preferably, it is provided in a dosage form such as an emulsion or gel solution. In order to form such a dosage form, the color developing substance and the coupling substance must be combined with a wetting agent (emulsifier), a solubilizer, a thickener, a stabilizer, a feel improver, and a hair styling group, which are commonly used in the cosmetics field. It may be manufactured according to a conventional method by adding agents, fragrances, etc. 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, and the like. In addition, as a thickener,
Examples include methylcellulose, starch, higher fatty alcohols, paraffin oil, fatty acids, etc. Stabilizers include reducing agents such as sulfites, hydroquinone derivatives, chelating agents, etc., and are used as feel improvers and hair styling bases. Examples include silicones, higher alcohols, oil agents such as various nonionic surfactants, and various cationic polymers. The total amount of the color developing substance and the coupling substance in these dosage forms is preferably 0.001 to 10% by weight (hereinafter simply expressed as %), particularly preferably 0.01 to 5%. Wetting agents (emulsifiers) are usually 0.5 to 30%, and thickeners are 0.5% to 30%.
Preferably, the amount is 1 to 25%.

In order to dye horny fibers using the dye composition of the present invention, for example, an oxidizing agent is added to the dye composition of the present invention to perform oxidative coupling to prepare a dye solution, and this dyeing solution is This is carried out by applying the solution to the stratum corneum fibers, washing the stratum corneum fibers for an action time of 5 to 50 minutes, preferably around 25 to 35 minutes, and then drying. The application of the staining solution here takes place at 15-40°C.

[0016]

Effects of the Invention As described above, when the aminophenol derivative of the present invention or its salt (1) is used as the coupling substance in a horny fiber dye composition comprising a color developing substance and a coupling substance, good dyeing properties can be obtained. It is possible to obtain a highly saturated color tone having good light resistance, resistance to fading, washing resistance, and abrasion resistance.

[0017]

EXAMPLES Next, the present invention will be explained in more detail with reference to synthesis examples and examples, but the present invention is not limited thereto.

Synthesis Example 1 5'-nitro-4'-(β-hydroxyethoxy)-2
Synthesis of '-methylphenyl methanesulfonate (2a-1) (R1: methyl group, R2: methanesulfonyl group,
n: 2) In a 200 ml autoclave, 10.0 g (40.5 mmo
l), ethanol 100ml, ethylene oxide 5g (1
14 mmol, 2.8 eq. ) and 500 mg of sodium hydrogen carbonate were added, and the mixture was heated and stirred all day and night. After cooling,
Evaporation of the solvent under reduced pressure gave a brown oil. This was purified using silica gel column chromatography (Merck Si60, 70-23).
The raw material was recovered from the first fraction. From the second fraction, 4 pale yellow crystals of the title compound (2a-1) were obtained.
．． 60g (15.8mmol) was obtained. Yield 39%. Physical data of (2a-1) Melting point 106.0-107.5 °C 1H-NMR (200MHz, CDCl3) δppm
;2.30(3H,s), 3.60(2H,t,J
=4.1Hz), 3.71(3H,s), 4.02
(2H, t, J = 4.1Hz), 6.92 (1H, s
), 7.65 (1H, s) IR (KBr) νc
m-1; 3350, 1346, 1330, 119
2, 1172 elemental analysis (as C10H13NO7S) Calculated value C; 41.24%, H; 4.50%, N
; 4.81%, S; 11.01% Actual value C; 41.07%, H; 4.38%, N;
4.72%, S; 10.77%

Synthesis Example 2 Synthesis of hydrochloride of 2-amino-4-hydroxy-5-methylphenoxyethanol (1-1) (R1: methyl group, n: 2) The compound obtained in Synthesis Example 1 (R1: methyl group, n: 2) was added to 30 ml of methanol. 2a-1) 4.50 g (15.5 mmol) and 5 ml of 8N aqueous sodium hydroxide solution were added, and the mixture was heated under reflux for 30 minutes. After cooling, neutralize with concentrated hydrochloric acid and pour into 150 ml of water to obtain 4-hydroxy-5-methyl-2-nitrophenoxyethanol (2b-1) (R: methyl group, n: 2).
crystals were precipitated. The crystals were used in the next reaction without being filtered or dried. Add these crystals to a 200 ml autoclave, add 100 ml of ethanol and 500 mg of 10% palladium on carbon, and then add 50 kg/cm2 of hydrogen.
was press-fitted and stirred at 50°C for 3 hours. After cooling, the palladium on carbon was filtered and the solvent was distilled off under reduced pressure to obtain a brown oil. This was dissolved in 20 ml of ethanol, hydrogen chloride gas was blown into it, and then 100 ml of ether was added to precipitate crystals. By filtering and drying this, 1.33 g (6.06 mmol) of the hydrochloride of the title compound (1-1) was obtained.
I got it. Yield 39% from (2a-1). In addition, compound (2b-1) can be purified by recrystallization from ethanol. Physical data of (2b-1) Melting point 154.0-156.0 °C 1H-NMR (200MHz, DMSO-d6) δp
pm; 2.19 (3H, s), 3.67 (2H, t
d, J=6.0, 6.0Hz), 4.05(2H, t
, J=6.0Hz), 4.83(1H,t,J=6.0
Hz), 7.13 (1H, s), 7.24 (1H,
s), 9.73(1H,s)IR(KBr) νcm
-1; 3400, 3080, 1524 elemental analysis (C
9H11NO5) Calculated value C: 50.71%, H: 5.20%, N;
6.57% actual value C; 50.82%, H; 5.2
Physical data of hydrochloride of 4%, N; 6.30% (1-1) Melting point 203.0-206.0 °C 1H-NMR (200MHz, DMSO-d6) δp
pm; 2.10 (3H, s), 3.69 (2H, t
, J=4.1Hz), 3.98 (2H, t, J=4.
1Hz), 6.90 (2H, s), 9.43 (1H
,brs), 9.95(2H,br) IR(KBr
) νcm-1; 3364, 3040, 2768,
2592 elemental analysis (as C9H14NO3Cl) Calculated value C; 49.21%, H; 6.42%, N; 6
．． 38%, Cl; 16.14% Actual value C; 48.83%, H; 6.34%, N;
6.31%, Cl; 16.02%

Example 1 Base composition:

(%) oleic acid

10
Oleic acid diethanolamide

8 Oleyl alcohol

2 Polyoxyethylene octyl dodecyl ether
10 (Average E.O. 20 moles added) Ethanol

15 Propylene glycol
10 Ammonium chloride

3 25% ammonia

7 Water


35 total

1
00 In 100 g of the base having the above composition, 0.01 mol of the color developing substance and 0.01 mol of the coupling substance shown in Table 1 were added.
Mol was mixed in. Next, the pH of the composition was adjusted to 9.5 with ammonia to produce a dye composition of the present invention.

A dyeing solution was prepared by adding an equal weight of 6% aqueous hydrogen peroxide solution to 100 g of the dye composition of the present invention. Apply this dye solution to gray human hair and dye it at 30℃ for 30 minutes.
Leave it for a minute. The hair was then washed with regular shampoo and dried. Table 1 shows the results of observing the color tone, dyeability, saturation, and resistance to fading of the obtained dyed hair. The change and fading resistance was determined based on the following criteria after being stored at 40° C. and 75% RH for 60 hours, dried at room temperature, and visually compared with dyed hair tresses stored at -5° C.

(Evaluation criteria for dyeability, saturation, and resistance to fading) ◎: Very good ○: Good △: Slightly poor ×: Bad Color developer P1; Paraphenylene diamine P2; Toluene-2,5-diamine P3; para-aminophenol P4; 5-aminosalicylic acid coupling substance C1; 2-amino-4-hydroxy-5-methyl-phenoxyethanol (product of the present invention) C2; para-aminoorthocresol (comparative product) C3
;2-Methyl-5-(β-hydroxyethyl)aminophenol (comparative product)

[0023]

[Table 1]

Claims (3)

[Claims] [Claim 1] The following general formula (1) [Chemical formula 1] An aminophenol derivative represented by or a salt thereof. [Claim 2] The following general formula (2) [Case 2] A nitrophenol derivative or a salt thereof. 3. A stratum corneum fiber dyeing composition comprising the aminophenol derivative or its salt according to claim 1 and a color developer as a coupling substance.