JPH03176416A - Accumulation-type hair dye - Google Patents

Abstract

PURPOSE:To provide an accumulation-type hair dye containing a specific amount of a sulfur-containing substance such as sulfide or hydrosulfide, a metal- containing substance such as Mn and a color-developing substance as active components, effective in ameliorating the allergic symptom such as rush and applicable without damaging the hair. CONSTITUTION:The objective hair dye contains, as active components, 0.01-0.3wt.% (in terms of S) of one or more sulfur-containing substances selected from sulfide, hydrosulfide, polysulfide, solubilized sulfur and colloidal sulfur, 0.01-1.0wt.% (in terms of elemental metal) of one ore more kinds of metal- containing substances selected from compounds containing Mn, Co, Ni, Fe, Cr or Ag and 0.02-4wt.% of one or more kinds of color-developing substances selected from organic compounds capable of developing color when bonded with a metal component. The hair dye enables the coloring of hair to various colors extending from pure black color to brownish color.

Description

[Detailed Description of the Invention] 1. Technical Field The present invention relates to a drug for dyeing U (4%l), and is a technology that can be used in the cosmetics manufacturing industry that manufactures it and the hairdressing industry that uses it. be.

■0 Background of the invention Regarding Oshiyare dye and Shiraga dye to change the color tone of hair, there are various types described in the next section: ■ those using basic oxidation dyes, and ■ those using polyhydric phenol and iron. Some use salt. ! The A product type is not noticeable after one treatment, but gradually becomes darker after repeated treatments several times. Regarding item (1) above, there are improved products such as the acid type that does not damage the hair quality and the quick type that speeds up the processing time, but basic oxidation dyes have excellent dyeing properties, weather resistance, color development, etc. However, on the other hand, it has a major disadvantage in that it tends to cause allergic antigens such as rash, which requires caution as a biological reaction. Therefore, as the aging of the population progresses and attempts to rejuvenate gray hair by dyeing are increasing, there is a desire to develop hair dyes that are non-allergenic.

(1) Problems to be Solved by the Present Invention Currently published hair dyes are as follows, and they have advantages and disadvantages.

- In principle, hair dyes that are temporarily dyed with pigments or acid dyes are hair dyes that can be washed off when hair is washed, but there are products on the market that are dyed with tar pigments that do not wash off. Tar pigment dyes have a high concentration;
It has the disadvantage that it dyes not only the hair but also the living cell protoplasm of the skin.

-Hair dyeing using animal and plant materials For example, washing hair with chamomile, rhubarb, logwood, and henna extracts is practiced in Europe and the United States, but the degree of coloring is so light that even after several dyeings, it cannot come close to the black hair of Japanese people.

■The so-called Ohaguro type, which is dyed with ingredients extracted from animal and plant-derived raw materials, as well as polyhydric phenols and iron salts, is dyed with a relatively deep color, including fivefold, tannic acid, hematin, etc.
Pyrogallol is known and cumulative products are on sale, but the dyeing intensity is still not sufficient, and the color tone of these products is bluish to indigo, while Japanese hair color is brownish. However, there are some unnatural flaws.

- Hair dyes using basic oxidation dyes, such as para-ξ, can express each color tone freely and can be dyed in a controlled manner, so most of the dyes currently on the market belong to this category. The biggest disadvantage of this is that it is highly sensitizing and cannot be applied to people with allergic rashes, and its mutagenicity data are gradually becoming clearer.

(2) Metallic hair dyes include those that form sulfides in addition to the above-mentioned Ohaguro type. Ag is the only metal that can be colored. Mn, Fe, Co, Ni+C
U, Bi, and Pb can be colored by forming sulfides. (Refer to Japanese Patent Application No. 1-150853) There is also a document stating that the keratin molecules of the hair structure protein react with sulfur and become colored, but in the experiments of the present inventor, no dyeing occurred at all, and a preparation containing sulfur was required. be.

The use of toxic metals is questionable; for example, products containing lead acetate and sulfur are commercially available in the United States, but they will probably not be approved in Japan.

■In order to avoid the sensitization properties of basic oxidation dyes, new compounds such as pyridine-based, pyrrole-based, and hydroacetone-based compounds have recently been announced, but although there is no precedent for their use, it takes a huge amount of time to obtain permission from the Ministry of Health and Welfare. Requires testing by an official institution. Economically speaking, this type of R&D is wasteful, and the knowledge required for licensing has become an important technical problem-solving issue.

Disclosure of the Invention The present inventor has researched a formulation of a cumulative hair dye that is sure to be effective in both dyeing and toning, and hereby discloses the drug and dyeing method.

The main points are: ■S is a substance containing one or more of SH-, S', Sx'', solubilized sulfur, and colloidal sulfur, and 0.01 to 0.3-χ, and ■Mn, Go, N.
A substance containing one or more metal elements of i, F elCr, and AH as a metal element is 0.01"1.Od and ■
One or two organic compounds that combine with the above metal elements to form a color.
It is a preparation containing 0.02 to 4 wZ of at least one color-forming substance as an active ingredient. ■■O can be combined in the same preparation (l-dose product), two types can be combined (double-dose product), or three types can be combined separately (three-dose product). ), and the concentration in each case falls within the above-mentioned range in each formulation.

■The following substances are listed as substances containing sulfur. H
Hydrogen sulfide water containing 2S gas dissolved in water is commercially available.
Absorb this in NaOH to form Na5H, NazS+ Na,
Sx, and the alkali is K + L 11 Ca,
It can be replaced with Mg+NHa. Secondary alkali hydroxides, carbonates, and oxides melt with solid sulfur to form polysulfides, and when solid sulfur is added to an alkaline hydroxide solution and heated, a yellow polysulfide solution is obtained. Sulfur powder as surfactant,
When treated with a solvent, aqueous or oily solubilized sulfur is obtained. Colloidal sulfur is available commercially, and is also produced by the decomposition of sulfides and thionates. Thiram and thianthol are attracting attention as special ingredients that gradually precipitate sulfur content.

■Mn, Fe+Co+Ni+Cr, Ag as metal elements
Compounds containing nitrates, sulfates, chlorides, phosphates,
and organic acid salts such as acetic acid and citric acid.
In addition, complex salts with ammonium and potassium are water-soluble. Insoluble but moderately active substances, such as hydroxides, basic carbonates, hydrated phosphates, can be used, as can naturally occurring loess, pyrosite, hydrated laterite, and the like. There are few compounds containing metal elements that have a precedent for use under the Pharmaceutical Affairs Law, and although Cu*P b + 81 and the like are elements that easily stain, they probably will not be permitted. In this sense, iron sulfate, loess, bismuth oxychloride, chlorophyllin (Fe, Cu), cobalt titanate, etc. are very rare, but they can be found in a wide range if safety is guaranteed.

■There are many organic compounds that combine with metal elements to create color, but the one that can be applied to hair dyeing has OH in its molecule.
Many of them have a COOH group, an N H2 group, and an S Oa group. Specific examples include: - Cyclic compounds with OH groups such as phenol, cresol, hinokitiol, naphthol, oxyquinoline, oxypyridine, oxybenz, and chlorophenol.

・Polyhydric phenols such as catechol, pyrogallol, gallic acid, and tannic acid ・COOH such as salicylic acid, anthranilic acid, picranic acid, isacic acid, oxybenzoic acid, and methoxybenzoic acid
A cyclic compound with a group.

- Cyclic compounds with N Hz groups such as paramin, aminophenol, aminopyridine, aminobenzaldehyde, aminonitrophenol, aminobenzoic acid, and abbreviated tsucresol.

・crocetin, chlorophin, kurukukun, indigo,
laccaic acid, carbunate, berberine, hematin,
Typical examples include natural pigments such as rutin, quercetin, and azulene, photosensitive elements, and similar compositions, as well as their salts, isomers, glycosides, halogen groups, sulfophone groups, nitro groups, Those to which an amino group is added are also included.

The product of the present invention requires the three elements O and O mentioned above, and other elements such as a solvent, a surfactant, an oily component, a hair treatment agent, a humectant,
It is formulated by adding acid-alkali agents, thickeners, excipients, diluents, stabilizers, fragrances, colorants, and general cosmetic raw materials.

A pioneering document using the formulation of ■■■ as a hair dye is Japanese Patent Publication No. 32-5599, but the composition of this document is significantly different from that of the present invention, and its reducing effect on hair is strong. Therefore, there is a drawback that hair damage is significant.

@Japanese Patent Application No. 1-150853 is an invention of the present inventor, and although there are some approximate descriptions, the content is different.

That is, in the present invention, an appropriate range for cumulative hair dyeing has been determined in terms of the amount of ingredients.
The reason for selecting 0.01 to 0.3-χ is that when the content of this ingredient is 0.01% or less, the extent of hair dyeing is small, and when it is 0.3 or more, the product emits a bad odor that cannot be used as a cosmetic, and hair dyeing is This is because the t0 damage is a major drawback, and on the other hand, as a result of hair dyeing, even if it is sold in mass quantities, there is no noticeable tendency to improve the density.

As an experimental example, the results shown in Figure 1 are as follows:
z2'! and Na2S as S and 70~IL Plllo,
White wool was immersed in 5) for 15 minutes, then immersed in the second solution (iron sulfate as Fe, 1.OxPH 4,0') for 15 minutes, and the color difference ΔE of the dyed wool was measured after washing with water and drying.
In the figure, 1, 2.3.4 are the measured values when the previous treatment was repeated 1 to 4 times.

Next, ■The reason for setting the metal element to 0.01 to 2.0wχ is
When this component is 0.01% or less, the degree of hair dyeing is small; 2.
This is because when it is 0% or more, there are drawbacks such as precipitation of salt due to solubility and lack of stability in terms of formulation, and on the other hand, there is no tendency for the concentration to increase, which affects the hair dyeing results.

As an experimental example, the results shown in Figure 2 are as follows:
z and Na, S is 0.15χ, PI+10.5)
The color difference ΔE of the dyed wool was measured after soaking white wool for 15 minutes, then immersing it in a second solution (O~4X with iron sulfate as Fe, PH 4,0) for 15 minutes, washing with water, and drying. The numbers in the middle indicate the number of times of staining.

Furthermore, the reason why the 07 color substance was set at 0.02 to 4 W% is that when this component is less than 0.02%, the extent of hair dyeing is small, and when it is more than 4%, there is no noticeable tendency to improve the density. be.

As an experimental example, the results shown in Figure 3 are as follows: The first solution (Na2S as S, 70.15%, pyrogallol as O~4χ, pH 10
, 5) for 15 minutes, then immersed in the second liquid (1.0X with iron sulfate as Fe, Pl+ 4.0) for 15 minutes, and measured the color difference ΔE of the dyed wool after washing with water and drying. The numbers in the figure are the number of times of staining.

■Example Example ■.

b Iron acetate (MW 246) 0.4
gC Catechol 0.5a Colloidal Sulfur 0.2 Glycerin
6.0 cetanol
5.0 Beeswax 5
．． 0 Vaseline 15.5 Liquid paraffin 7.5 Polyoxyethylene cetyl ether 9.0 Sorbitan monostearate 3.3 Anhydrous sodium sulfite
0.2 acetic acid (P11→4.0)
0.5 fragrance 0.5 essence
46.4 familiarization 100. Og Combine the above ingredients and heat mix to make a cream. The main island is painted, treated with a heating cap at an average temperature of 40°C for 15 minutes, and washed with warm water. It was possible to dye it black by treating it several times every other day.

Example 2 Part A yellow ammonium sulfide liquid (S=13.5%) 0.7
5svχC pyrogallol 0. lO
C piclagonic acid 0.05 ammonia water (28χ) 0.20 polyoxyethylenenonyl 5.00 phenyl ether purified water res as part B sulfuric acid-'-7 Kel (6 parts g) 3.5
0wχb cobalt sulfate (7AR)
3.50b copper sulfate (58g) 0
．． 5 Ammonia water (28X) 12.5
0 4Na edetate 2.50 Purified water 78.00 Shampoo your hair with Part A, lightly drain the water, then apply Part B, comb thoroughly, and then wash your hair. Shiraga's hair is dyed reddish-brown. If you do it a few times, you will almost have a 30's color tone. After that, the treatment will be done about twice a month.

Add 5 parts and dissolve, add 0.07 part of powdered sulfur and boil, the sulfur will dissolve and a yellow liquid will be obtained. Add 0.2 parts of anhydrous sodium sulfite, 0.5 parts of sodium thioglycolate, and water to make a total of 50 parts (a) and dissolve. Adjust P to 0.5±0.2 with hydrochloric acid and lactic acid. Separately, 10 parts of polyoxyethylene coconut oil fatty acid monoethanolamide, 0.1 part of Keltrol, and 0.1 part of CMC were added to 40 parts of water by heating and dissolved, and 0.0 part of fragrance was added thereto.
3 parts were added to obtain 100.3 parts of liquid C. [Sulfur content 0.2
wχ] Solution D: Dissolve 1 part of chromium ammonium bread, 1 part of iron (IT) ammonium sulfate (12 parts g), 1 part of manganese ammonium sulfate (6 parts g), and 2 parts of citric acid in 50 parts of purified water. , adjust Pl+ to 3.0 to 3.5 using Trieno. (b) Separately, dissolve 0.5 part of polyvinyl alcohol in 5 parts of alcohol, 5 parts of glycerin, and 30 parts of water, add to the preliquid (mouth), add 0.5 part of fragrance, and make 100.5 parts of D liquid.
I got the department. (Metal components 0.06w, E liquid niltin 0.01 part, hematin 0.01 part, hinokitiol 0.01 part, camellia oil 3 parts, silicone 0.01
1 part, 80 parts of alcohol, 10 parts of polyethylene glycol, and 10 parts of water, and adjusted to pH 7.0 with a trace amount of NaOH.
±0.5 and 0.3 part of fragrance was added to obtain 100 parts of liquid E.

How to use the main island: Shampoo your hair with Part 20, rinse with water, use Part D as a rinse, rinse lightly with water, and towel dry. Solution E is then used daily as a tonic. The hair gradually turns black.

Example 4゜1 part of calcilum sulfide (335,22) powder, 2 parts of pentagram powder, 5 parts of loess (Fe25.9χ), 40 parts of bentonite
10 parts of the product of the present invention was obtained by mixing 12 parts of anhydrous sodium sulfate, 20 parts of chalk powder, and 20 parts of wheat flour. Honjima is packaged in a sealed package, and before use, add an equal amount of water, knead it, apply it to your hair, and wash your hair after about 30 minutes.

Example 5 First solution: Add 10 g of water and 1.5 g of 28x ammonia water to 0.67 g of iron chloride and dissolve, add 30 g of alcohol, and add water to make 100 g.

Second liquid: Add 702 alcohol to dissolve 0.5 part of S2χ-containing water-soluble sulfur (Kotobuki Kagaku Niyu Sulfal), 0.05 part of salicylic acid, 0.05 part of pyrogallol, and 0.1 part of fragrance to make 100 g. . The first liquid and the second liquid are alternately sprayed on the hair to dye the hair.

Example 6 Glycyrrhizylic acid 0.1 Camphor 0.3 Thianthol 0.2 Sodium thiosulfate 0.5 f Sodium sulfide (9saki) 0.1 Iron 00 firin Na O, 1 Edetate 4N
a O,2 resorcin
0. l Glycerin 3.0 Alcohol 40.0 Purification 55.5 Stock solution Total 100.0 120 g of the stock solution was filled into an aluminum can, and 5 g of CO2 gas was pressurized to create a hair dyeing spray.

■0 Effects of the invention Unlike basic oxidation dye hair dyes that are currently inferior, even when the above dye is used as the component (C) of the invention, the active group bonds with the metal salt. By doing so, you can expect the effect of reducing allergic symptoms such as rash. In addition, the current version of hair dye, commonly known as Ohaguro type hair dye, is extremely damaging to the hair texture, but the composition of the present invention solves this problem. It is now possible to dye with pigment.

After middle age, the appearance of chilera gradually increases, but the process of gradually turning black through several treatments to make it less noticeable is called the cumulative type, and is used as a hair tonic in the composition of the present invention. Since raw materials can also be used, applying for a permit can be convenient.

[Brief explanation of drawings]

In determining the component range of the present invention, Figure 1 shows the sulfur component, Figure 2 shows the metal component, and Figure 3 shows the amount (-χ) of the coloring organic compound component, and the amount of the dyed hair. Color difference (Δ
This is a graph obtained by experimentally determining the relationship between E) and E). Above (a) W% th

Claims (1)

[Claims] A sulfur-containing substance selected from one or more of sulfides, hydrosulfides, polysulfides, solubilized sulfur, and colloidal sulfur is 0.01 to 0.3 w% as S, Mn, Co, Ni,
0.01 to 1.0 as a metal element, a metal-containing substance selected from one or two of compounds containing Fe, Cr, and Ag.
w% and a color-forming substance selected from one or two organic compounds that combine as the metal component to form a color.
4w% as an active ingredient in the formulation.