JPH0525851B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel 2,4-dichloro-3-aminophenol-O-acylated product or a salt thereof, and a horny fiber dye containing the same that has excellent color saturation, dyeing power, and fastness. The present invention relates to a drug composition. [Prior Art] So-called oxidation dyes, which use a combination of a color developer and a coupling substance, 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 of 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-tolylene diamine, 4-aminophenol, resorcin, resorcin monomethyl ether, m-phenylene Diamine, 1-phenyl-3
-Methyl-5-pyrazolone, 1-phenyl-3-
Amino-5-pyrazolone, 1-phenyl-3,5
-diketo-pyrazolidine, 1-methyl-7-dimethyl-amino-4-hydroxyquinolone-2,1
-Amino-3-acetyl-acetamino-4-nitrobenzole, 1-amino-3-cyanoacetyl-amino-4-nitro-benzole, m-aminophenol, 4-chlororesorcin, 2-methylresorcin, 2,4- Diaminophenoxyethanol, 2,6-diaminopyridine, 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, p-nitro- o-phenylenediamine, 2-
Amino-5-nitrophenol, p-nitro-m
-phenylenediamine, o-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, etc. are used. [Problems to be Solved by the Invention] However, conventional oxidation dyes have not been fully satisfactory in saturation, dyeing power, and fastness. Since these properties are greatly influenced by the characteristics of the coupling material, finding a material with excellent properties as a coupling material is extremely important in obtaining an excellent oxidation dye. [Means for Solving the Problems] Under these circumstances, the present inventors synthesized many compounds and studied their characteristics as coupling substances, and found that 2, represented by the general formula () below, The present invention was completed based on the discovery that 4-dichloro-3-aminophenol-O-acylated product or a salt thereof has excellent properties as a coupling substance. That is, the first invention of the present invention is the following general formula () (In the formula, R represents a lower acyl group having 2 to 4 carbon atoms.) 2,4-dichloro-3-aminophenol-O-acylated product or a salt thereof is provided. In the above general formula (), examples of the lower acyl group represented by R include an acetyl group, a propionyl group, a butyryl group, and the like. The compound () of the present invention can be produced, for example, according to the following reaction formula. [In the formula, R has the same meaning as above] That is, the compound of the present invention () is produced by reacting 2,4-dichloro-3-aminophenol () with a lower fatty acid [ROH ()] and its reactive derivative. is manufactured. Examples of reactive derivatives of lower fatty acids include acid anhydrides and acid chlorides. The reaction may be carried out by adding, for example, 1 to 2 times the mole of lower fatty acid anhydride, a dissolved amount of lower fatty acid, and 0 to 2 times the mole of a lower fatty acid alkali metal salt to the compound (2), followed by heating and refluxing. The isolation and purification of the compound of the present invention () is carried out using benzene,
Purification is performed by column chromatography using an organic solvent such as hexane, followed by recrystallization using an organic solvent such as ethanol. The starting compound () can be produced, for example, by the method described in the specification of British Patent No. 1,531,335. The compound () of the present invention thus obtained can be converted into a salt of an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, etc. or an organic acid such as propionic acid, lactic acid, citric acid, etc. by a conventional method. Furthermore, the second aspect of the present invention is to provide a horny fiber dyeing composition having excellent color saturation, dyeing power, and fastness by using the compound of the present invention () or a salt thereof as a coupling substance. The color developer used in the dye composition of the present invention is not particularly limited as long as it is normally used in oxidative hair dyes, but examples include p-phenylenediamine, toluene-2,5- diamine, N
p-phenylenediamine derivatives such as p-phenyl-p-phenylenediamine and 2-chloro-p-phenylenediamine; p-aminophenol derivatives such as p-aminophenol, 5-aminosalicylic acid, and 2,4-diaminophenol ; pyridine derivatives such as 2,5-diaminopyridine and 2,3-diaminopyridine; pyrimidine derivatives such as tetraminopyrimidine; and the like. Among these color developing substances, the following general formula () (In the formula, R ₁ represents a hydrogen atom, a chlorine atom, or a methyl group.) By using the p-phenylenediamine derivative represented by the following formula, a blue color tone with extremely high chroma and high fastness can be obtained. The mixing ratio of the color developing substance and the compound () or its salt may be such that one is in excess compared to the other, but the molar ratio is preferably about 1:0.5 to 1:2. Further, the color developing substance and the coupling substance may be used alone or in combination of two or more types. Examples of coupling substances that can be used in combination with compound () include those mentioned above, such as α-naphthol. Further, if necessary, a direct dye can be added to the horny fiber dyeing composition of the present invention to additionally change the hue. Such linear dyes include, for example, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, nitro-p-phenylenediamine hydrochloride, which are described in the dye raw material standards published by the Japan Hair Color Industry Association. Nitro-p-phenylenediamine, p-aminophenylsulfamic acid, p-nitro-o-phenylenediamine,
Picramic acid, sodium picramate, picric acid, Chrome Brown RH, hematein, nitro-p-phenylenediamine sulfate, p-nitro-o-phenylenediamine sulfate, p-nitro-m sulfate
-phenylenediamine, 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,
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
No., Yellow No. 203, Green No. 201, Green No. 204, Green No. 205
No., Blue No. 202, Blue No. 203, Blue No. 205, and Color
No. 201, Red No. 401, Red No. 502, 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. 401, black No. 401; oil-soluble dyes Red No. 215, Red No. 218, Red No. 225, Orange No. 201, Orange
No. 206, Yellow No. 201, Yellow No. 204, Green No. 202, Purple
No. 201, Red No. 105, 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's basic dyes Sienna Brown, Mahogany, Madder.
Red, Steel Blue, Straw Yellow, etc., but especially nitrophenylenediamine, nitro-
Aminophenol and anthraquinone dyes are preferred. These direct stains can be present in the composition of the present invention from 0.01 to
It is preferable to add 20.0% by weight. The keratin fiber dye composition of the present invention also causes oxidative coupling 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;
Examples include products in which hydrogen peroxide is added 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 preferably provided in the form of a cream, emulsion, gel, solution, or the like. In order to form such a dosage form, a wetting agent (emulsifier), a solubilizer, a thickener, a stabilizer, a feel improver, and a hair styling base, which are usually used in the cosmetic field, are added to the color developing substance and coupling substance. , fragrance, etc., and may be manufactured according to a conventional method. Examples of wetting agents (emulsifiers) used here include alkylbenzene sulfonates, fatty alcohol sulfates, alkyl sulfonates, fatty acid alkanolamides, and addition products of ethylene oxide and fatty alcohols. Further, examples of thickeners include methyl 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. to improve the feel. Examples of the agent and hair styling base include silicone, higher alcohol, oil agents such as various nonionic surfactants, and various cationic polymers. The total amount of the color developing substance and 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 3.0%, thickeners are 0.1 to 3.0%.
It is preferable to mix 25%. In these dosage forms, the pH of the entire composition is preferably adjusted to about 8 to 10. 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 dyeing composition of the present invention to perform oxidative coupling to prepare a dyeing solution, and this dyeing solution is used to dye horny fibers. applied to fibers,
This is carried out by washing the horny fibers for an action time of 5 to 50 minutes, preferably around 25 to 35 minutes, and then drying. Here the application of the staining solution is carried out at 15-40 °C. [Effects of the Invention] As described above, in a horny fiber dye composition comprising a color developing substance and a coupling substance, the 2,4-dichloro-3-aminophenol-O-acylated product of the present invention or a salt thereof is used as the coupling substance. By using p-phenylenediamine derivatives, a wide range of dyeings with excellent color saturation, dyeing power, and fastness are possible.
A blue tone with extremely high saturation and high durability can be obtained. Moreover, the obtained color tone has good light fastness, wash resistance and abrasion resistance. [Example] Next, the present invention will be explained in detail with reference to Reference Examples and Examples, but the present invention is not limited thereto. Example 1 Preparation of 2,4-dichloro-3-amiphenol acetate: 2,4-dichloro-3-aminophenol hydrochloride 5.6 g (26 mmol) sodium acetate in 20 ml acetic acid
2.4g (29mmol) and 35ml (36mmol) of acetic anhydride
was added, and the mixture was heated under reflux until almost all 2,4-dichloro-3-aminophenol disappeared. After cooling this to room temperature, the salt was removed by filtration, and the solvent was distilled off under reduced pressure. The residue was separated by column chromatography (silica gel 230-400 mesh, benzene-hexane) to obtain 1.6 g of crude 2,4-dichloro-3-aminophenol acetate.
Recrystallization of this crude product from ethanol gave colorless crystals of the title compound with a melting point of 80.9-81.4°C. ^1H -NMR ( _CDCl3 ): δ 2.34 (s, 3H), 4.55
(s(br), 2H), 6.50(d, J=9Hz, 1H),
7.19 ( ^d .
%), 221 (66.1%), 220 (9.5%), 219M (100
%), 177 Example 2 Base composition: (%) Olefiic acid 10 Oleic acid diethanolamide 8 Oleyl alcohol 2 Polyoxyethylene octyl dodel ether (average EO 20 mole addition) 10 Ethanol 15 Propylene glycol 10 Ammonium chloride 3 25% ammonia 7 Water 35 0.01 mol of a color developing substance and 0.01 mol of a coupling substance shown in Table 1 were mixed into 100 g of a base having the above composition. Then adjust the pH of the composition with ammonia.
The horny fiber dye composition of the present invention was prepared by adjusting the dye composition to 9.5. A dyeing solution was prepared by adding an equal weight of 6% aqueous hydrogen peroxide solution to 100 g of this dyeing composition of the present invention.
Apply this dye solution to gray human hair and heat it at 30℃.
It was left for 30 minutes. The hair was then washed with regular shampoo and dried. Table 1 shows the results of observing the color tone, saturation, and resistance to fading of the obtained dyeing. Note that the dyeability was good in all cases. The fastness was determined by comparing the changes after storage at 40°C and 70% RH for 100 hours with those stored at -5°C.
All judgments were made visually. Color developer P ₁ : p-Tolphenylenediamine P ₂ : Toluene-2,5-diamine P ₃ : p-aminophenol P ₄ : 5-aminosalicylic acid Coupling substance C ₁ : 2,4-dichloro-3-amino Uhenyl acetate C ₂ : m-phenylenediamine C ₃ : 2,4-dichloro-3-acetylaminophenol Judgment criteria ◎: Very good ○: Good △: Slightly poor ×: Bad

[Table] Example 3 From the composition described in Example 2, 0.01 mol of color developing substance and coupling substance shown in Table 2 were added to 100 g of base.
0.01 mol was mixed in and the same operation as in Example 2 was carried out to observe the dyeing property of the hair obtained. Judgment was made visually according to the criteria of Example 2. The results are shown in Table 2.

[Table]

Claims (1)

[Claims] First-order general formula () (In the formula, R represents a lower acyl group having 2 to 4 carbon atoms.) A 2,4-dichloro-3-aminophenol-O-acylated product or a salt thereof. 2. A keratinous fiber dye composition containing the 2,4-dichloro-3-aminophenol-O-acylated product or its salt according to claim 1 as a coupling substance.