JPS62195319A - Hair dye - Google Patents

Abstract

NEW MATERIAL:A naphthalene derivative expressed by the formula (R is CnH2n+1; n is 0-4). EXAMPLE:4,6-Bis(butylamino)2,3-dihydro-8-hydroxynaphthalene-1,5-dione. USE:An excellent hair dye, capable of well dyeing the hair in a very low concentration and under milk condition and stably coloring with almost no influence of dyeing condition and having good preservation stability. PREPARATION:3,5-Diamino(or bisalkylamino)-8-hydroxynaphthoquinone is reduced with an reducing agent, e.g. Na2S2O6, etc., in the presence of an alkali, e.g. KOH, NaOH or Na2CO3, etc., in water, alcohol or a mixture solution of water with alcohol or reduced in the presence of zinc in an aqueous solution of hydrochloric acid to afford the aimed compound expressed by the formula. The amount of the compound expressed by the formula to be blended is >=0.05wt%, preferably >=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, one of the benzene derivatives, such as p-phenylenediamine and p-tolylenediamine, was used as a developer.
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 henna, 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 inventor has focused on vat dyes as one of the potential new hair dyes, and has been continuing research on hair dyes. The inventors have now completed the present invention by discovering that hair can be dyed under certain conditions, with excellent safety, good storage stability, and sufficient color development.

[Means for Solving the Problems] That is, the present invention is a hair dye characterized by containing a naphthalene derivative represented by the following general formula (1).

[In formula (1), R is Cn H1n+l, where n=0~
Represents 4. ] (The following is a blank space) The above naphthalene derivatives are new compounds synthesized for the first time by the present inventors, and these are the corresponding 3-, 5-
Diamino (or bisalkylamino)-8-hydroxynaphthoquinone is reacted with water, alcohol, or alcohol using a reducing agent such as sodium dithionate in the presence of an alkali such as potassium hydroxide, sodium hydroxide, or sodium carbonate.
It can be obtained by reduction in a water-alcohol mixed solution or 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 5% by weight or more, preferably 0.1% by weight or more. There is no particular upper limit, but if it exceeds 2% by weight, the dyeing power will gradually reach a plateau, so it should be blended in an amount exceeding 5% by weight. It doesn't make much sense.

[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.

1lelind developed by Ca5sel la company
On YellowR is a naphthoquinone dye having a condensed Carbazole ring, and is a yellow vat dye for wool, but 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 can produce 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 a high temperature.
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]

A synthesis example of a naphthalene derivative represented by n=4 as a representative example of an alkylamino group in general formula (1) is shown below.

Synthesis Example 1 Naphthazarine 1 in n-butylamine 100+wmol
An ethanol solution containing 0 m+mol of 80-mol was slowly added, and the mixture was stirred at a temperature of 0°C for 4 hours. Next, the reaction system was stirred at reflux temperature for 2 hours. After the reaction was completed, it was treated in a conventional manner and purified by silica gel column chromatography using benzene as a solvent to obtain 2.152 g (yield: 68.0%) of the desired crystals. This product was confirmed to be 3,5-bis(butylamino)-8-hydroxynaphthoquinone based on the following analytical values.

Mass spectrum M”-316 Elemental analysis value C-68,36 (calculated value 68.33 >H
-7,66 (calculated value 7.65) N-8,76 (calculated value 8.85) Nuclear magnetic resonance spectrum (CDCL, , δl, 1ll)
I II-NMR14,50 (IH,0HSS), 9
．． 90 (Ill, NO, broad), 6.90
-7.30 (2HSaros,,q), 6.25
(IH, Nll, broad), 5.60 (
IH.

Quinon, S), 3.00-3.50. (4
11,2XCH2NH,ta), 1.20-1.90
(8) 1.2X-(CH2)-1Hm), 0.
80-1.10 (611,2XCH3,1iket)
13C-NMR carbonyl group 18
6.7.176.8 Synthesis Example 2 3,5-bis(butylamino)-8 obtained in Synthesis Example 1
-350 mg of hydroxynaphthoquinone was dissolved in 40 cc of aqueous ethanol along with 248 mg of sodium carbonate and 390 mg of sodium dithionate, and the mixture was heated and stirred at 80° C. for 5 hours under an argon atmosphere. The solution changed from purple to brown, confirming that the reduction had progressed sufficiently, and after cooling to room temperature, it was filtered, and the crystals were thoroughly washed with degassed water. All these operations were performed under an argon atmosphere. The crystals were dried under reduced pressure to obtain 232.6 mg of the target product (yield: 6
6.0%), which was further recrystallized from ethanol under an argon atmosphere. There are several possible tautomers of this substance, but from the results of the analysis values below, 4.6-bis(
It was confirmed to be 2,3-dihydro-8-hydroxynaphthalene-1,5-dione (butylamino).

Mass spectrum M-316 (under oxidation in ZT-column) Elemental analysis C
-67,85 (calculated value 67.90') H-8,26 (
Calculated value 8.23) N-8,89 (calculated value 8.80') Nuclear magnetic resonance spectrum (CDCL3, δ, ppm)
II-NMR15,15 (IHlNll, broad
), 13.85 (IH10■, S ”), 6.
10 (IHSNll, broad), 5.95 (
IH, arom, , S ), 3.403.65 (
2H1CH2NHlm), 3.08' 3.35
(2H,CH2NH,q)2.60 2.80 (
2H, activecH2,d), 2.80-3.
00(2HSactivecH2,'d), 1.
20-1.90 (8H.

2X-(CI+2)-1m), 0.82 1.10
(6H, 2XCH3, 1iket) 13C-NMRcarbonyl group 19
3.0, 168.6 [Example] Next, an example of staining using the naphthalene derivative of the present invention will be shown.

Example 1 4,6-bis(butylamino)2.3- obtained in Synthesis Example 2
Dihydro-8-hydroxynaphthalene-1,5-dione 2h+g each with ammonia content 0%, 0.7%, 2.0
The solution dissolved in 20g of water is used as a dyeing solution. Gray hair (untreated) purchased from Abeille Co., Ltd. 1.
0 g was immersed in the dyeing solution and dyed with shaking at a temperature of 30° C. for 45 minutes. After that, the dyed hair was soaked with water 200-3
After washing at 0° C. for 5 minutes, hair with no gray hair was obtained in all cases.

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 10 g of 1.0% and 2.0% water and 10 g of benzyl alcohol to obtain a dyeing solution. Example 1
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 the same naphthalene derivatives as those used in Example 1 were mixed with monoethanolamine content 0%,
It is dissolved in a mixed solution consisting of 10 g of 0.7%, 1.0%, and 2.0% water, 5 g of benzyl alcohol, and 5 g of propylene glycol 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 4 Hair was dyed and washed in the same manner as in Example 3, except that hair was previously bleached with 5% hydrogen peroxide solution at 30°C for 45 minutes, and the hair was dyed well 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. 1, Indication of the case Patent Application No. 37123 of 1988 2, Name of the invention Hair dye 3, Person making the amendment Relationship with the case ``Detailed description of the invention'' in the patent applicant's specification ” Column 5, content of amendment +11 In the 7th line of page 6 of the specification, “Indusrene” will be corrected to “Ingensulen”.

(2) Correct the statement r7.30J on page 9, line 5 of the specification to r7.20J.

(5) Ming 111F 113th! Line 15 of L [Correct the phrase ``hair j that cannot be recognized'' to ``purple hair that cannot be felt.''

(6) In the 4th line of page 13 of the specification, the words "Good workmanship" will be corrected to "Good quality."

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.▼ [In formula (I), R is CnH_2_n_+_1, but n
= represents 0 to 4. ]