JPH03246216A - 2,4-dichloro-3-aminophenol-o-acylated material or salt thereof and keratin fiber dyeing agent composition containing same material or salt thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R is 2-4C acyl) or salt thereof. EXAMPLE:2,4-Dichloro-3-aminophenol acetate. USE:A component for keratin keratinous fiber dyeing agent composition having excellent chroma, dyeing force and fastness. PREPARATION:2,4-Dichloro-3-aminophenol acetate expressed by formula II is reacted with a lower fatty acid expressed by formula III and reactive derivative thereof to provide the compound expressed by formula III. The reactive derivative of compound expressed by III includes acid anhydride or acid chloride. The reaction is preferably carried out by adding e.g. lower fatty acid anhydride 1-2 times by mol based on the compound expressed by formula II, lower fatty acid having solvent amount or lower fatty acid alkali metal salt 0-2 times by mol based on the compound expressed by formula II to the compound expressed by formula II and refluxing the mixture.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a novel 2,4-dichloro-3-aminophenol-〇-acylated product or a salt thereof, and a method for improving color saturation, dyeing power and fastness containing the same. The present invention relates to a horny fiber dye composition with excellent properties.

[Conventional technology]

For dyeing keratinous fibers such as hair, so-called oxidation dyes, which use a combination of a color developer and a coupling substance, have been widely used. This oxidative dye utilizes the fact that the so-called oxidized dye, which is produced by oxidative coupling between a color developer and a coupling substance, strongly stains hair and the like.

Conventionally, the color developing substances generally include p-phenylenediamine derivatives, p-aminophenol derivatives, diaminopyridine derivatives, 4-aminopyrazolone derivatives, heterocyclic hydrazones, etc., and the coupling substances include α
-naphthol, 〇-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, resorcinol, resorcinol monomethyl ether, m-phunidinediamine, ■-phenyl-3-methyl-5-pyrazolone, 1-7enyl-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-penzole, m-aminophenol, 4-chlororesorcin,
2-methylresorcin, 2,4-diaminophenoxyethanol, 2,6-cyamitsupyridine, 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-cyhydroxypyrimidine, 4-amino-2,6-cyhydroxypyrimidine, 4゜6-diami2-hydroxypyrimidine, p-nitro-○-phenylenediamine, 2-
Amino-5-=)lophenol, p-nitrom-7
Enylene diamine, 0-nitro-p-7 22-diamine, 2-amino-4-nitrophenol, etc. are used.

[Problem 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 substance, finding a substance with excellent properties as a coupling substance is extremely important in obtaining an excellent oxidation dye.

[Means to solve the problem]

Under these circumstances, the present inventors synthesized many compounds and examined their properties as coupling substances, and found that 2,4-dichloro-3-amino compound represented by general formula (I) below The present invention was completed based on the discovery that phenol-0-acylated products or salts thereof have excellent properties as coupling substances.

That is, the first invention of the present invention is based on the following general formula (r
) nt+ 2 (wherein R represents a lower acyl group having 2 to 4 carbon atoms) or a salt thereof.

In the above general formula (I), examples of the lower acyl group represented by R include an acetyl group, a propionyl group, a butyryl group, and the like.

Compound (I) of the present invention can be produced, for example, according to the following reaction formula.

Below margin (I[) (I)[
In the formula, R has the same meaning as above] That is, 2,4-dichloro-3-aminophenol (
The compound (I) of the present invention can be obtained by reacting If) with a lower fatty acid [ROH (III)) and its reactive derivative.
is manufactured.

Reactive derivatives of lower fatty acids (In) include acid anhydrides,
Examples include acid chlorides.

The reaction may be carried out by adding, for example, a lower fatty acid anhydride in an amount of 1 to 2 times the mole of the compound (n), a lower fatty acid in a solvent amount, and a lower fatty acid alkali metal salt in an amount of 0 to 2 times the mole of the compound (n), followed by heating and refluxing.

The compound (I) of the present invention is isolated and purified by column chromatography using an organic solvent such as benzene or hexane, and then recrystallized using an organic solvent such as ethanol.

In addition, the compound (n) serving as a raw material is, for example, described in British Patent No.
It can be produced by the method described in the specification of No. 531335.

The compound (I) 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 invention of the present invention is the compound (I) of the present invention
An object of the present invention is to provide a horny fiber dye composition having excellent color saturation, dyeing power, and fastness by using 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-phenylene diamine, toluene-2,5-diamine, , N-phenyl-p-phenylenediamine, 2-chloro-p-7 22-diamine, etc.
-phenylenediamine derivative; p-aminophenol,
p-aminophenol derivatives such as 5-aminosalicylic acid and 2,4-diaminophenol; pyridine derivatives such as 2,5-diaminopyridine and 2,3-diaminopyridine;
Examples include pyrimidine derivatives such as tetraaminopyrimidine. Among these color developing substances, the following general formula (IV
) H2 (wherein R1 represents a hydrogen atom, a chlorine atom, or a methyl group) By using a p-phenylenediamine derivative represented by the following formula, a blue color tone with extremely high chroma and high fastness can be obtained.

The blending ratio of the color developer and compound (I) or its salt may be such that one is in excess compared to the other, but the molar ratio is 0.5.
The ratio is preferably about 1:2.

In addition, both the color developing substance and the coupling substance can be used alone or in combination.
You may use combinations of more than one species. Examples of coupling substances that can be used in combination with compound (I) 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 direct dyes include, for example, 2-amino-4 described in the dye raw material standards published by the Japan Hair Color Industry Association.
-ditrophenol, 2-amino-5-ditrophenol, nitro-p-phenylenediamine hydrochloride, nitro-p
-Phenylenediamine, p-aminophenylsulfamic acid, p-nitro-〇-phenylenediamine, picramic acid, sodium picramate, picric acid, Chrome Brown RH1 hematin, nitro-p-7 22-diamine sulfate, p-nitro sulfate -〇-phenylenediamine,
p-nitro-m-phenylenediamine sulfate, 1-amino-4-methylaminoanthraquinone, ■,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 Ar1ano
5ienna Brown, Ma.
Hogany, Madder Red, Steel
Examples include BlueSStraw Yellow, and nitrophenylenediamine, nitro-aminophenol, and anthraquinone dyes are particularly preferred.

These direct stains contain 0. O1~20
．． It is preferable to add 0% by weight.

The keratin fiber 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 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,
Preferably, it is provided in a dosage form such as a gel or 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 alkylbenzenesulfonates, fatty alcohols, sulfates, alkylsulfonates, fatty acid alkanolamides, and addition products of ethylene oxide and fatty alcohols. Examples of thickeners include methylcellulose, starch, higher fatty alcohols, paraffin oil, fatty acids, etc.; examples of stabilizers include reducing agents such as sulfites, hydroquinone derivatives, chelating agents, etc. Examples of improvers and hair styling bases include silicones, higher alcohols, oils 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 0.05 to 10% by weight (hereinafter simply expressed as %), particularly preferably 0.1 to 5%. Wetting agent (emulsifier)
It is preferable that the amount of the thickener is usually 0.5 to 30%, and the thickener is 0.1 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 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. Apply to horny fibers for 10 to 50 minutes, preferably 2
This is done by washing the keratinous fibers for an action time of about 5 to 35 minutes and then drying them. The application of the staining solution here takes place at 15-40°C.

〔Effect of the invention〕

In a stratum corneum fiber dyeing composition comprising a color developing substance and a coupling substance as in the case of ridges, the 2,4-dichloro-3-aminophenol-O- of the present invention is used as the coupling substance.
By using acylated products or their salts, a wide range of dyeings with excellent chroma, dyeing power, and fastness are possible.In particular, by combining p-fuynylenediamine derivatives as color developing substances, extremely high chroma and fastness can be achieved. It is possible to obtain a high blue color tone. Moreover, the obtained color tone has good light fastness,
It has wash resistance and abrasion resistance.

〔Example〕

Next, the present invention will be described in detail with reference to Reference Examples and Examples, but the present invention is not limited thereto.

Example 1 Production of 2.4-dichloro-3-aminophenol acetate: To 20 parts of acetic acid, 5.6 g (26 mmol) of 2.4-dichloro-3-aminophenol hydrochloride was added to 2 parts of sodium acetate.
4g (29mmof> and acetic anhydride 35-(36mmof)
of) was added and heated under reflux until almost no 2,4-dichloro-3-aminophenol was present. After cooling to room temperature, the salt was removed by filtration, and the solvent was distilled off under reduced pressure. Chromatography (silica gel 230-4
00 mesh, benzene-hexane), and 2
．． 1.6 g of crude 4-dichloro-3-aminophenyl acetate was obtained.

When this crude product is recrystallized from ethanol, the melting point is 80.
．． Colorless crystals of the title compound were obtained at 9-81.4°C.

'H-NMR (CDC1,): δ 2J4 (s, 3H
), 4.55(s(br).

2H), 6.50 (d, J=9Hz, 1)1), 7
．． 19(d, J=9Hz.

IH).

IR (Nujol): 3484.3380.17
60°1612 cm MS (20eV): 224 (I, 0%), 223 (I
1.2%).

222 (6.3%), 221 (66.1%).

220 (9.5%), 219M (I00%).

77 Example 2 Base composition: Nioleic acid, oleic acid, jetanol, amiolyl alcohol, ethanol, propylene glycol, ammonium chloride, 25% aqueous ammonia, base consisting of the above composition, 0.01 mol of color developer and 0.01 mol of coupling substance.
Mol was mixed in. Next, the pH of the composition was adjusted to 9.5 with ammonia to produce a horny fiber dye composition of the present invention.

To 100 g of this invention dyeing composition, an equal weight of 6% hydrogen peroxide aqueous solution was added to prepare a dyeing solution.

Apply this dye solution to gray 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, 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 change after holding for 100 hours at 40°C and 70% RH with the product stored at -5°C. All judgments were made visually.

Color developer P+: p-phenylenediamine P2: toluene-2,5-diamine Ps: p-aminophenol P4: 5-aminosalicylic acid coupling substance C,: 2,4-dichloro-3-aminophenyl acetate C2: m -Phenylenediamine C,:2,4-dichloro-3 Enol Judgment Criteria ◎: Very good ○: Good △: Slightly poor ×: Bad Acetylaminophore margin Example 3 Consisting of the composition described in Example 2 Table 2 in 100g of base
0.01 mol of the color developing substance and 0.01 mol of the coupling substance shown in
01 mole was mixed in and the same operation as in Example 2 was carried out to observe the dyeing properties of the hair obtained.

Judgment was made visually according to the criteria of Example 2.

The results are shown in Table 2.

Table 2 (P,, P2. C,, C, indicates the same as in Example 2) February 21, 1991 2゜Name of invention 2.4-dichloro-3-aminophenol-〇-acyl Chemical substance or salt thereof and horny fiber dye composition containing the same 3, Relationship to the amended case Applicant name (091) Kao Corporation 4, Agent address: 1-3 Nihonbashi Ningyocho, Chuo-ku, Tokyo No. 6 (〒103)
6. Column 7 of "Detailed Description of the Invention" of the specification to be amended, content of the amendment (I) In the specification, page 12, line 14, r0.05-10% by weight'' is ro, oot~ 10% by weight”.

(2) Page 12, line 15 It says "0.1-5%" rO, 01-5%”.

(3) Page 13, line 4 It says "10-50 minutes" I corrected it to ``5 to 50 minutes.''

Claims (1)

[Claims] 1. 2 represented by the following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (In the formula, R represents a lower acyl group having 2 to 4 carbon atoms) , 4-dichloro-3-aminophenol-O-acylated product or a salt thereof. 2. A keratin fiber dye composition containing the 2,4-dichloro-3-aminophenol-O-acylated product or its salt according to claim 1 as a coupling substance.