JPS61204115A - Hair dye - Google Patents

Abstract

NEW MATERIAL:A naphthalene derivative expressed by the formula (R is H, methyl or ethyl; n is 1, 2 or 3). EXAMPLE:6-Hydroxyethylamino-2,3-dihydro-5,8- dihydroxynaphthalene-1,4-dione. USE:An excellent hair dye, capable of dyeing hair safely and well under mild conditions in a very low concentration with almost no influence of dyeing conditions, and having stable color formation and good storage stability. PREPARATION:The corresponding 2-alkoxyalkylamino-5,8-dihydroxynaphthoqu inone is reacted with a reducing agent, e.g. Na2S2O6, in the presence of an alkali, e.g. KOH, NaOH or Na2CO3, and water, alcohol or a mixture solution thereof or zinc in an aqueous solution of hydrochloric acid to give the aimed compound expressed by the formula. The amount of the above-mentioned com pound to be incorporated is >=0.05wt%, particularly >=0.1wt% based on the total weight of the hair dye.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel hair dye that can dye hair in a strong manner.

[Prior Art] Conventionally, p-phenylenediamine, p-)lylenediamine, etc., which are one of the benzene derivatives, have been used as developers.
So-called oxidation dyes, which use resorcinol, m-aminophenol, m-phenylenediamine, etc. as couplers and dye hair through oxidative polymerization and color development with hydrogen peroxide and ammonia, have become the mainstream of hair dyes.

Hair dyes made of indole and pyrimidine derivatives (West German Patent No. 3016905, etc.) are also oxidative dyes that are dyed in a similar manner.

In addition, several patents for hair dyes containing quinone pigments have been reported (West German Patent Publication No. 3244454, West German Patent Publication No. 3244452, French Patent No. 1567219, etc.).
These are used as direct dyes, and rather than dyeing the hair, they impart some shade to the hair.

Although some reports have been made on hair dyeing using extracts from plants such as pliers, chamomile, and walnut, the dyeing power of these dyes is also not fully satisfactory.

[Problems to be Solved by the Invention] Oxidation dyes dye hair well, but the color is produced through an oxidative polymerization reaction, which is extremely complex and produces miscellaneous oxidation products, so only a small amount Due to differences in dyeing conditions, the color development often differs markedly even when dyed with the same dye. Furthermore, since these dyes are unstable in the air or in a solvent (oxidation or oxidative polymerization, etc.), sufficient care must be taken to store them under a nitrogen atmosphere.

Furthermore, since some people may experience skin disorders and severe hair damage, we have developed a new type that has sufficient dyeing power, stable color development, good storage stability, and excellent safety. The need for hair dye was increasing.

Under these circumstances, the present inventors have focused on vat dyes as one of the potential new hair dye materials, and have been continuing research on hair dyes.
The inventors have now completed the present invention by discovering that hair can be dyed under mild conditions, resulting in excellent safety, good storage stability, and sufficient color development.

Means for Solving Problem L] That is, the present invention is a hair dye characterized by containing a naphthalene derivative represented by the following general formula (I).

[In formula (1), R represents hydrogen, a lower alkyl group such as methyl or ethyl, and n represents a number from 1 to 3. ] The above-mentioned naphthalene derivatives are new compounds synthesized for the first time by the present inventor, and each of these derivatives was prepared by converting the corresponding 2-alkoxyalkylamino-5,8=dihydroxynaphthoquinone into potassium hydroxide, sodium hydroxide, sodium carbonate, etc. It can be obtained by reduction in water, alcohol, a water-alcohol mixed solution using a reducing agent such as sodium dithionate in the presence of an alkali, or in an aqueous hydrochloric acid solution in the presence of zinc. Suitable reaction conditions are anaerobic reaction at room temperature to reflux temperature for 1 to 5 hours.

The amount of the naphthalene derivative mentioned above is 0.0 in the hair dye amount.
It is at least 5% by weight, preferably at least 0.1% by weight.

There is no particular upper limit, but if it exceeds 2% by weight, the dyeing power will gradually reach a plateau, and there is little point in adding more than 5% by weight.

[Effect]

Conventional vat dyes for textiles are of the type that uses a reducing agent in a bath to convert the dye into a leuco form, and while the fiber is immersed in the bath, the leuco form is oxidized in the air to develop color and is adsorbed onto the fiber. It is. For example, when dyeing indigo, which is a typical vat dye, fibers are immersed in a solution containing indigo, an alkali, and a reducing agent. Under the above conditions, indigo becomes a leuco substance, and it is thought that this substance develops color through air oxidation, and at the same time dyes the fibers. In addition, there are other vat dyes such as indasthrene dyes and anthraquinone dyes, which are also thought to be dyed by a similar mechanism.

However, these leuco bodies are very unstable and are immediately oxidized when exposed to air, so it is necessary to coexist a large amount of reducing agent in the bath, which creates harsh conditions for the fibers. Furthermore, since the reduction was carried out under strongly alkaline conditions, this caused even more damage to the fibers.

He1indon developed by Ca5sella
YellowR is a naphthoquinone dye with a fused Carbazole ring, and is a yellow vat dye for wool.
It is well known that it was not commercially available because it required a strong alkaline bath for reduction.

When the leuco form of indigo is converted into a sulfate ester, the stability is improved, but the sulfate ester is, on the contrary, too stable and cannot be colored unless a strong oxidizing agent such as potassium permanganate is used.

This is also not a good condition for the fibers. As described above, it has been impossible to apply conventional vat dyeing methods directly to hair dyeing.

The naphthalene derivative of the present invention has appropriate stability, that is, it can be isolated as a leuco form, and it is a leuco form that develops a strong color when oxidized under mild conditions, so it can be said to be an ideal hair dye.

Until now, there have been no examples of applying vat dyes to hair dyes, and this is the first example of synthesizing and isolating a leuco compound that produces good color without including a reducing agent in the dye bath and applying it to hair dyes. .

Furthermore, when conventional vat dyes are used, sufficient dyeing cannot be expected unless they are added to the dye bath at a concentration of about 5% and dyed at high temperatures.
It exhibits a dyeing power that can withstand practical use at a low temperature of 40° C. or lower with an extremely low concentration of about 1%. Also, this product does not damage the hair or irritate the scalp.

[Synthesis example]

In general formula (1), a synthesis example of a 6-hydroxyethylamino naphthalene derivative represented by n=2 and R=H as a representative example of a 6-hydroxyalkylamino group, and a representative example of a 6-alkoxyalkylamino group n=2, R=
A synthesis example of a 6-medoxyethylaminonaphthalene derivative represented by CH3 is shown below.

Synthesis Example 1 An ethanol solution containing 10 mmol of naphthazarine in 200 m of 2-aminoethanol + WO I was slowly added to the mixture and stirred for 3.5 hours at a temperature of 0 to 2°C. After the reaction was completed, the reactant was poured into a dilute aqueous hydrochloric acid solution, and the precipitate was filtered and dried under reduced pressure. This dried product was subjected to fractionation and purification using columnar mudgraphy using silica gel as a filler and benzene as a solvent, and 1.571 g of crystals (
(Yield: 62.7%) and further recrystallized from ethanol. This product was confirmed to be 2-(2"-hydroxyethylamino-5,8-dihydroxynaphthoquinone) by the following analytical values.

Mass spectrum M = 249 Elemental analysis value C-57,77 (calculated value 57.83) H
-4,41 (calculated value 4.45 > N-5,58 (calculated value 5.62) Nuclear magnetic resonance spectrum (DMSO-d, , δ, ppm
)IH-NMR13,60(LH,0R1S),
11.65 (LH,0H1S), 7.73 (LH
, NH, broad ), 7.10-7.40 (
2H, arom, , m ), 5.68 (IH, q
uinone.

s), 4.85 (LH,NOH5broad)
, 3.10-3.70 (40 for ethyl g
roup) 13C-NMR carbonyl grow
p 186.1.183.5 Synthesis Example 2 2-(2'-hydroxyethylamino) obtained in Synthesis Example 1
-600 mg of 5,8-dihydroxynaphthoquinone, 600 mg of sodium carbonate, 1600 mg of sodium dithionate
mg and an ethanol aqueous solution (ethanol 15, water 2
0) 35- and stirred at reflux temperature for 3 hours under an argon atmosphere. The solution turned yellowish brown, confirming that the reduction had progressed sufficiently, and after cooling to room temperature, it was filtered, and the crystals were thoroughly washed with diluted water. The crystals were dried under reduced pressure to obtain 450 mg (yield 75.8%) of the desired product, which was further recrystallized from ethanol under an argon atmosphere.

There are several possible tautomers of this substance, but as seen in the analysis values below, the chemical left of the carbonyl group in C-NMR is observed to be significantly lower in the magnetic field than that of quinones. It is thought that a methyl group or methylene group exists adjacent to the carbonyl group, and 6-(2
'-hydroxyethylamino)-2,3-dihydro-5
, 8-dihydroxynaphthalene-1,4-dione.

Mass spectrum M-251 Elemental analysis value C-57,33 (calculated value 57.37 >H
-5,28 (calculated value 5.22) N = 5.64 (calculated value 5.58) Nuclear magnetic resonance spectrum (DMSO-d6, δ, ppm) I Fl
-NMR13,08 (18,OR,S), 12.5
5 (IH, OH, S), 6.59 (IH, NH,
broad ), 6.59 (LH% NH, broad
d), 6.31 (11% arom, ,3)
, 4.57 (18, NOH5broad) , 2.
95 (4H, -(CH2) 2-1t), 2.9
4-3.66 (48 for ethyl grou
p) 13C-NMR carbony) group
203.8.197.6 Synthesis Example 3 Ethanol solution 80d containing 10mmo I of naphthazarin in 200m2-methoxyethanolamine+nol
was slowly added and stirred at a temperature of 0 to 2°C for 5.5 hours.

After the reaction was completed, the reactant was poured into a dilute aqueous hydrochloric acid solution, and the precipitate was filtered and dried under reduced pressure. This dried product was fractionated and purified by column chromatography using silica gel as a filler and benzene as a solvent to obtain the desired crystal, 1.63
11 g (yield: 61.6%) was obtained, which was further recrystallized from ethanol. This product is 2-(2
It was confirmed that it was '-methoxyethylamino)-5,8-dihydroxynaphthoquinone.

Mass spectrum M = 263 Elemental analysis value C = 59.38 (calculated value 59.31
) H-4,97 (calculated value 4.98') N-5,28 (calculated value 5.32 > Nuclear magnetic resonance spectrum (CDC13, δ, ppn+)
IH-NMR13,33(LH,OH,S), 1
1.68 (IH, OR, S ), 7.78 (IH,
NHSbroad), 7.12-7.38 (2
H,arom, ,q ) ,5.76 (LH,qu
inone.

s), 3.28 (3H1OMe, s),
3.30-3.55 (4Hfor ethyl
group ) 13C-NMR carbonyl gr
oup 186.4.183.6 Synthesis Example 4 2-(2'-methoxyethylamino)- obtained in Synthesis Example 3
1.007g of 5,8-dihydroxynaphthoquinone, 1.017g of sodium carbonate, 2.5g of sodium dithionate
00g was dissolved in 60% of an ethanol aqueous solution (20% of ethanol, 40% of water), and the mixture was stirred at reflux temperature for 3 hours under an argon atmosphere. After the reaction was completed, it was filtered and the crystals were thoroughly washed with degassed water. Dry the crystals under reduced pressure to obtain the target object 900
mg (yield: 88.7%), which was further recrystallized from ethanol under an argon atmosphere.

There are several possible tautomers of this and of, but C-
It was confirmed from NMR data etc. that it was 6-(2'-methoxyethylamino')-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione.

Mass spectrum M-265 Elemental analysis value C=58.85 (, calculated value 58.86
)H=5.58 (calculated value 5.70 >N=5
．． 21 (calculated value 5.28) Nuclear magnetic resonance spectrum (CDCI, , δ, ppm) I H-NMR13,
01 (18, OH, S), 12.54 (IH, OH
, S ), 6.58 (18,NH,broad)
, 6.31 (11Sarom, , s ), 3.0
1 (3H,OMe Ss), 2.95 (48,-
(CH2) 2-1t), 3.14-3.66 (4H
for ethyl group)”C-NMRca
rbonyl group 203,8.197.5
[Example] Next, the hair dye material containing the naphthalene derivative of the present invention will be specifically described with reference to Examples.

Example 1 6-hydroxyethylamino-2.3- obtained in Synthesis Example 2
Dihydro-5,8-dihydroxynaphthalene-1,4-
Dione 20n+g each with ammonia content θ%, 0.7%
, 1.0%, 1.5%, and 2.0% in 20 g of water to prepare a dyeing solution. Immerse 1.0g of gray hair (untreated) purchased from Abeille Co., Ltd. in the dyeing solution at 30°C.
Shaking staining was carried out for 45 minutes at a temperature of . Thereafter, the dyed hair was washed with 200° C. of water for 5 minutes at 30° C. to obtain hair with no gray hair in any case.

The color tone of the dyed hair became bluish as the ammonia concentration increased, but was approximately reddish brown to brown.

The obtained dyed hair was washed using a commercially available shampoo,
Further rinsing was performed, but in each case, there was very little discoloration and no change in color tone was observed.

Example 2 20 mg each of the same naphthalene derivatives as those used in Example 1 were mixed with ammonia contents of 0%, 0.7%,
It is dissolved in a mixed solution consisting of 1.0%, 1.5%, and 2.0% water (10 g) and propylene glycol Log to obtain a staining solution. The hair was dyed and washed in the same manner as in Example 1, and in both cases, hair was dyed to a bright color tone that was almost the same as that obtained in Example 1, with no gray hair being felt at all.

Example 3 20 mg each of 6-methoxyethylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione obtained in Synthesis Example 4 was added to ammonia contents of 0%, 0.7%, 1
．． A staining solution is prepared by dissolving it in a mixed solution consisting of 20 g of 0%, 1.5%, and 2.0% water and 10 mg of an anionic activator. The hair was dyed and washed in the same manner as in Example 1, and in both cases, hair was dyed to a bright color tone that was almost the same as that obtained in Example 1, with no gray hair being felt at all.

Example 4 20 mg each of the same naphthalene derivatives as the naphthalene derivative used in Example 3 were mixed with ammonia contents of 0%, 0.7%,
A staining solution is obtained by dissolving in a mixed solution consisting of 1.0%, 1.5%, and 2.0% water Log, 10 g of propylene glycol, and 10 mg of an anionic activator. The hair was dyed and washed in the same manner as in Example 1, and in both cases, hair was dyed to a bright color tone that was almost the same as that obtained in Example 1, with no gray hair being felt at all.

Example 5 20 mg each of the same naphthalene derivatives as the naphthalene derivative used in Example 1 were mixed with ammonia contents of 0%, 0.7%,
It is dissolved in a mixed solution consisting of 1.0%, 1.5%, and 2.0% water Log and ethanol Log to obtain a staining solution. The hair was dyed and washed in the same manner as in Example 1, and in all cases, beautiful hair was obtained with no gray hair at all and dyed in a much lighter color than that obtained in Example 1.

Example 6 20 mg each of the same naphthalene derivatives as the naphthalene derivative used in Example 2 were mixed with ammonia content of 0%, 0.7%,
A staining solution is prepared by dissolving in a mixture of 1.0%, 1.5%, and 2.0% water (10 g), ethanol (2 g), propylene glycol (8 g), and anionic activator (10 mg). The hair was dyed and washed in the same manner as in Example 1, and in both cases, hair was dyed to a bright color tone that was almost the same as that obtained in Example 1, with no gray hair at all.

Example 7 Hair was dyed and washed in the same manner as in Example 6, except that hair was previously bleached with 5% hydrogen peroxide solution at 30°C for 45 minutes, and the hair was dyed to a good quality in both cases. .

〔Effect of the invention〕

The hair dye containing the naphthalene derivative according to the present invention can dye hair well at extremely low concentrations and under mild conditions, and the color development is stable, hardly affected by dyeing conditions, and has storage stability. It can be said that it is an excellent hair dye with good quality.

Patent Applicant: Shiseido Co., Ltd. Procedural Amendment (Voluntary) Date of Q, 1985 1, Case details 1985 Patent Application No. 42930 2, Name of invention Hair dye 3, Person making the amendment Case and Relationship between patent applicant 4, Detailed explanation of the invention column 5 of the specification to be amended, contents of the amendment (1) On page 3, line 16 of the specification, “the present inventors” has been replaced with “the present inventors” I am corrected to "person".

(2) rNOHJ on page 9, line 5 of the specification,
rN (CH2CH2)Odan”.

(3) r6.59 on page 10, line 14 of the specification (
IHSNHlbroad), delete J.

(4) Correct rNOHJ on page 10, line 16 of the specification to rN (CH20H2)OHJ.

(5) Correct the text "r C-NMRJ" on page 12, line 14 of the specification to r13cmNMRJ.

that's all

Claims (1)

[Scope of Claims] A hair dye characterized by containing a naphthalene derivative represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In formula (I), R represents hydrogen, methyl or ethyl group, and n represents a number from 1 to 3. ]