JP2018070503A - Nonaqueous hair dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide hair dyes which can be applied to the hair by hand, can be readily washed off and do not remain when washing after application, are excellent in dye-affinity of the hair without dyeing the skin or scalp, are excellent in storage stability, are not decolored even by shampooing, and have high resistance to ultraviolet light without fading.SOLUTION: The above subject can be solved by a nonaqueous hair dye characterized by containing 0.01 mass% or more of 5,6-dihydroxyindoles in a nonaqueous composition containing 20 to 60 mass% of a hydrocarbon oil, 1 to 20 mass% of a surfactant, 20 to 86 mass% of higher fatty acid polyhydric alcohol ester and/or higher alcohol polyhydric alcohol ether, and 3 to 20 mass% of higher fatty acid, to the entire nonaqueous hair dye. Provided that a+b+c+d+e+f=100 mass%. a: The content of hydrocarbon oil. b: The content of a surfactant. c: The content of higher fatty acid polyhydric alcohol ester and/or higher alcohol polyhydric alcohol ether. d: The content of higher fatty acid. e: The content of 5,6-dihydroxyindoles. f: Content of the optional component added optionally.SELECTED DRAWING: None

Description

  The present invention relates to a non-water dye, and more particularly, it is excellent in hair dyeing properties, but does not dye the skin and scalp of the body, and is used in hair dyes such as toilets, bathrooms, washbasins and clothes. It can be washed away even if it is attached to a place or equipment, so there is no problem of staining, and the storage stability of 5,6-dihydroxyindoles (hereinafter sometimes referred to as DHI) is excellent. Taste can be easily controlled over a wide range, and after application to hair, DHI penetrates into the hair and is dyed by air oxidation or ultraviolet rays, so even if shampooed, the color will not fade (hereinafter referred to as shampoo) It may be referred to as “stability”), and relates to a non-water dyeing hair material that has high UV resistance and does not cause color burn.

  Conventionally, one-component hair dye compositions and multi-component hair dye compositions using melanin precursors such as indoles (such as 5,6-dihydroxyindole or salts thereof) are known. However, in addition to being limited in the color obtained by these dyeing | staining compositions, there existed a problem that ensuring of stability of a agent and manufacture were difficult (refer patent documents 1-3).

Since this hair dye composition is easily oxidized, the agent is deteriorated during production and storage, and the production method and hair dyeing treatment become complicated, such as the oxidized dye coloring the production machine and making it difficult to clean. In addition, there is a problem that the dyed color cannot be easily controlled over a wide range, and the shampoo stability after dyeing is low, resulting in color fading.
In addition, conventionally, when hair is dyed, an appropriate amount of an oxidizing agent such as hydrogen peroxide is mixed with melanin precursor such as indole (5,6-dihydroxyindole or a salt thereof) in water in an oxidative polymerization. A pigment (a large melanin molecule) was generated and used for hair dyeing.
This method has the feature that it can be dyed in a short time, but the color range after dyeing is narrow and large melanin molecules do not penetrate inside the hair, and most of the dyed hair tends to stay only on the hair surface. There is a problem that if the hair stays only on the surface of the hair, the color will be discolored when shampooed, the shampoo stability after hair dyeing is low, the UV resistance is also low, and the color will be discolored.

In order to solve such a problem, a one-component hair dye composition in which a foaming agent and a propellant (propellant) are added to 5,6-dihydroxyindole or the like is stored under pressure in a sprayer. Proposals have been made to apply a foam generated under pressure during hair dyeing to the hair to dye the hair (see Patent Documents 4 to 7).
If the oxidizing substance is removed from the inside of the sprayer at the time of pressurization and sealed and quickly filled in the sprayer, oxidation of the dye can be suppressed, and deterioration of the agent can be suppressed at the time of manufacture and storage.
However, according to this hair dyeing method, when foam generated under pressure during hair dyeing is applied to hair, DHI immediately oxidatively polymerizes on the hair surface to form large melanin molecules and the hair is dyed. However, DHI does not penetrate into the hair, and most of the dyed hair tends to stay only on the hair surface. If most of the dyed hair stays only on the surface of the hair, the shampoo stability is low, the UV resistance is low, and there is a problem of discoloration. There is a problem that it stains and stains when it is attached to a hair dyeing place such as a bathroom, a washbasin or clothes.

  On the other hand, the indole is added in one or more anhydrous solvents selected from ethyl alcohol, isopropyl alcohol, tertiary butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and acetate of ethylene glycol monoethyl ether. A storage-stable dye solution used for a hair dyeing composition characterized by containing is proposed (see Patent Document 8).

  However, when the dye solution is used as a hair dye composition, it cannot be used as it is, and is used by introducing the dye solution into a cosmetic carrier that is commonly used for hair dyeing. Since it is used and dyes hair, the said problem was not able to be solved.

French Patent No. 1133594 French Patent No. 1166172 French Patent Publication No. 2659229 JP 2007-326810 A JP-A-63-258403 Japanese Patent No. 531162 Japanese Patent No. 5363701 Japanese Examined Patent Publication No. 62-12203

  As mentioned above, DHI is known to be stable in non-aqueous solvents, but it cannot withstand actual use, and only aerosol products that can be sealed with oxygen by being sealed in a sprayer are used. This is the current situation.

  The object of the present invention is to solve the conventional problems, for example, the hair dye can be applied to the hair by hand, and it can be easily washed if washed after washing, so that it does not remain in the hand and is excellent in hair dyeing properties. It does not stain the skin or scalp of the body, and it can be washed away even if it is attached to a hair dyeing place or equipment such as a washroom, a bathroom, a washbasin or clothes, etc., and there is no problem of staining, and the storage stability of hair dyes such as DHI In addition, it is possible to easily control the dyed color in a wide range by using a direct dye together, and after dyeing the hair, it can be dried with a drier so that the hands and clothes are not contaminated. It is intended to provide a non-water dye which does not lose color even when shampooed and has high UV resistance and does not cause color burn, since it penetrates and melanin is generated by air oxidation or ultraviolet rays.

  As a result of intensive studies, the present inventors have found that a uniform and stable non-aqueous composition comprising a predetermined amount of hydrocarbon oil, surfactant, higher fatty acid polyhydric alcohol ester and / or higher alcohol polyhydric alcohol ether, and fatty acid, respectively. The non-water dye containing a predetermined amount of DHI in the product is an air in which DHI, ascorbic acid or a salt thereof and alkanolamine are dissolved in a higher fatty acid polyhydric alcohol ester and / or a higher alcohol polyhydric alcohol ether. Since it is dispersed in hydrocarbons with low permeability, that is, excellent air blocking effect, non-water dyeing hair can be applied to hair by hand, and after application, it can be washed easily and will not remain, It has excellent hair dyeing properties, but it does not stain the skin or scalp of the body, and it does not stain the bathroom, bathroom, basin or clothes. It is found that it can be washed away even if it is attached to a place or device, and it is found that there is no problem of fouling, and DHI can be stably dissolved and stored. Does not oxidatively polymerize, and DHI penetrates well into the cortex inside the hair and oxidatively polymerizes to produce melanin, so it can be dyed well up to the cortex inside the hair. Since hair dyeing is performed at the same time, the color tone after dyeing can be easily controlled over a wide range, and shampoo stability after hair dyeing and UV resistance are high. The present invention has been achieved.

  Claim 1 of this invention for solving the said subject is 20-60 mass% of hydrocarbon oils, 1-20 mass% of surfactant, higher fatty acid polyhydric alcohol ester, and / or with respect to the whole non-water dyeing hair. Alternatively, the non-aqueous composition containing 20 to 86% by mass of higher alcohol polyhydric alcohol ether and 3 to 20% by mass of higher fatty acid contains 0.01% by mass or more of 5,6-dihydroxyindoles. It is a non-water dye.

However, a + b + c + d + e + f = 100 mass%
a: the content of hydrocarbon oil b: the content of surfactant c: the content of higher fatty acid polyhydric alcohol ester and / or higher alcohol polyhydric alcohol ether d: the content of higher fatty acid e: 5 , 6-dihydroxyindoles content f: content of optional components added as necessary

  A second aspect of the present invention is characterized in that in the non-water dye according to the first aspect, ascorbic acid or a salt thereof and / or an alkanolamine is blended.

Claim 3 of the present invention is the non-water dye according to claim 1 or 2,
It is characterized by blending a direct dye.

Claim 1 of the present invention relates to hydrocarbon oil 20 to 60% by mass, surfactant 1 to 20% by mass, higher fatty acid polyhydric alcohol ester and / or higher alcohol polyhydric alcohol ether based on the whole non-water dyeing hair A non-water dye comprising a non-aqueous composition containing 20 to 86% by mass and 3 to 20% by mass of a higher fatty acid containing 0.01% by mass or more of 5,6-dihydroxyindoles. Yes (however, a + b + c + d + e + f = 100 mass%. A: the content of hydrocarbon oil, b: the content of surfactant, c: higher fatty acid polyhydric alcohol ester and / or higher alcohol polyhydric alcohol ether. The content, d: the content of higher fatty acids, e: the content of 5,6-dihydroxyindoles, f: the content of optional components added as necessary. Amount),
A non-aqueous composition containing a predetermined amount of a hydrocarbon oil, a surfactant, a higher fatty acid polyhydric alcohol ester and / or a higher alcohol polyhydric alcohol ether, and a higher fatty acid, respectively, and a predetermined amount of 5,6-dihydroxyindoles. The non-water-dyed hair composition is an air-blocking effect with low air permeability in a state where DHI, ascorbic acid or a salt thereof and an alkanolamine are dissolved in a higher fatty acid polyhydric alcohol ester and / or a higher alcohol polyhydric alcohol ether. Since it is dispersed in a hydrocarbon that excels in hair, it can be applied to the hair by hand, and after application, it can be washed easily so it does not remain and is excellent in dyeing hair, If you put it on a hair dyeing place or equipment such as a washroom, bathroom, washbasin or clothes, wash it off. There is no problem that defile in the that exhibits the remarkable effect that.

  And it is excellent in the storage stability that DHI can be dissolved and stored stably, and even when applied to the hair surface in the air, it does not immediately undergo oxidative polymerization, and DHI penetrates well into the cortex inside the hair. Since melanin is generated by oxidative polymerization, hair can be dyed well up to the cortex inside the hair, and when using a direct dye, hair dyeing with the direct dye is also performed at the same time, so it is easy to control the color after dyeing. In addition, the shampoo stability after hair dyeing and UV resistance are high, and there is a remarkable effect that hair can be dyed without fading.

  The non-water dye of the present invention maintains a paste form (sometimes referred to as a semi-solid) in the normal temperature range, so it also has a function as a styling agent, has excellent usability and applicability, and can be easily applied. It has a remarkable effect that it can be applied, has a good feeling of application, is excellent in safety, can be carried, and can change its color tone.

  Claim 2 of the present invention is characterized in that in the non-water dye according to claim 1, ascorbic acid or a salt thereof and / or an alkanolamine is dissolved and blended, and the DHI is more stable. Thus, it has a further remarkable effect that it can be dissolved and stored.

  Claim 3 of the present invention is characterized in that in the non-water dye according to claim 1 or claim 2, the direct dye is blended, and since hair dyeing with a direct dye is performed simultaneously, There is a further remarkable effect that the dyed color can be easily controlled over a wider range.

The non-water dye of the present invention has a DHI in a non-aqueous composition containing a predetermined amount of hydrocarbon oil, surfactant, higher fatty acid polyhydric alcohol ester and / or higher alcohol polyhydric alcohol ether and higher fatty acid. It is contained in a fixed amount, and DHI, ascorbic acid or a salt thereof and alkanolamine are dissolved in a higher fatty acid polyhydric alcohol ester and / or a higher alcohol polyhydric alcohol ether, and have an excellent air blocking effect with low air permeability. It is a non-water dye which is dispersed together with higher fatty acids in hydrocarbons (however, a + b + c + d + e + f = 100 mass%. A: the content of hydrocarbon oil, b: the content of surfactant, c: Higher fatty acid polyhydric alcohol ester and / or higher alcohol polyhydric alcohol ether Yuryou, d: the content of the higher fatty acid, e: 5,6-said content dihydroxy indoles, f: the content of the optional components that are added as necessary).
Each component used for the non-water dye of the present invention is an anhydride.

The hydrocarbon oil used in the present invention is a hydrocarbon oil having a low air permeability and excellent air blocking effect. Specifically, for example, liquid paraffin, isoparaffin, polyisobutene, polybutene, petrolatum, squalane and the like can be mentioned. Can do.
The blending amount of the hydrocarbon oil is 20 to 60% by mass, preferably 20 to 50% by mass with respect to the whole non-water dyeing hair, and if it is less than 20% by mass, the air blocking effect may not be exhibited. Exceeding the above range, the content of the higher fatty acid polyhydric alcohol ester and / or higher alcohol polyhydric alcohol ether in the non-water dyeing hair of the present invention decreases, so that the dissolving power of DHI, ascorbic acid or salts thereof and alkanolamines is reduced. Since it falls, it is not preferable.

The surfactant used in the present invention is a surfactant that dissolves in water or disperses in white turbidity, and is a highly polar higher fatty acid polyhydric alcohol ester in which DHI, ascorbic acid or a salt thereof and alkanolamine are dissolved, Used to uniformly dissolve and disperse alcohol polyhydric alcohol ethers, higher fatty acids, and hydrocarbon oils, and also to impart appropriate water dispersibility to non-aqueous compositions It is.
As the surfactant used in the present invention, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant and the like can be used, but a surfactant having a long chain is preferable, for example, the number of carbon atoms. A surfactant having an alkyl chain of 12 or more and 22 or less, particularly preferably a surfactant containing no water.

Examples of the nonionic surfactant include polyoxyethylene addition type nonionic surfactants, sucrose fatty acid esters, polyglycerin fatty acid esters, and tripolyoxyethylene alkyl ether phosphate.
Specifically, examples of the polyoxyethylene (POE) addition type nonionic surfactant include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, and polyoxyethylene sterol series. .
As polyglycerin fatty acid esters, specifically, many types having a glycerin chain length of 1 to 10 and different degrees of esterification are known.
Sucrose fatty acid esters are also commercially available in many different degrees of esterification and fatty acid chain length.

Anionic surfactants include fatty acid alkali salts, alkyl phosphates, alkyl sulfate salts, alkylmethyl taurate salts, acyl glutamic acids, alkyl ether carboxylic acids, alkyl sulfosuccinates, polyoxyethylene alkyl sulfosuccinates, etc. Can be mentioned.
Specifically, sodium laurate, sodium myristate, sodium stearate, various other alkali salts, sodium lauryl sulfate, sodium lauryl ether sulfate, sodium cetyl sulfate, sodium cetyl ether sulfate, lauryl sulfosuccinate Acid disodium, polyoxyethylene alkyl ether sulfosuccinate disodium, lauryl phosphate, sodium lauryl phosphate, lauryl ether phosphate, lauryl ether phosphate, lauroyl sarcosine sodium, cetearoyl sarcosine sodium, stearoyl sarcosine sodium, And so on.
Examples of commercially available anionic surfactants that do not contain water include alkyl phosphates, alkyl sulfates, stearoyl methyl taurate, acyl glutamates, and alkyl ether carboxylic acids.

Specific examples of the cationic surfactant include alkyl trimethyl ammonium salts, alkyl PG trimethyl ammonium salts, alkyl benzyl ammonium salts, and alkyl amide salts. Examples of the alkyltrimethylammonium salt type include stearyltrimonium salt, behenyltrimonium salt, and lauryltrimethylammonium salt.
Examples of commercially available cationic surfactants that do not contain water include stearyl trimonium salts, behenyl trimonium salts, stearoylamidoamines, and alkylamines.

Examples of the amphoteric surfactant include an alkylbetaine type, an alkylamide betaine type, an amino acid-based amphoteric surfactant type, and an amine oxide type.
Specifically, coconut oil alkyl betaine, lauryl dimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, N-lauroilu N-hydroxyethylethylenediamine sodium solution, lauryl dimethylamine oxide solution, coconut oil fatty acid monoethanolamide, isostearamide And propylbetaine.
The compounding quantity of surfactant is 1-20 mass% with respect to the whole non-water dyeing hair, Preferably it is 5-15 mass%. If it is less than 1% by mass, the washability is inferior and it is difficult to form a uniform system, which may result in a non-uniform system. If it exceeds 20% by mass, the hygroscopicity is increased and the stability of DHI may be impaired.

Higher fatty acid polyhydric alcohol ester and higher alcohol polyhydric alcohol ether used in the present invention are not soluble in water, and are used as a solubilizing agent such as DHI, ascorbic acid and salts thereof, alkanolamines, stabilized, form It has the effect of maintaining the feeling and adjusting the feel.
The higher fatty acid and higher alcohol are compounds having 8 or more carbon atoms and a saturated, unsaturated, branched alkyl chain, and the polyhydric alcohol is a divalent or higher polyol, such as ethylene glycol, propylene glycol, glycerin, diglycerin, Sorbitan and the like, and polymers thereof.

Specific examples of the higher fatty acid polyhydric alcohol ester include glyceryl monocaprate, propylene glycol monolaurate, ethylene glycol monolaurate, glyceryl monooleate, ethylenelene glycol monooleate, propylene glycol monooleate, and monoglyceride undecylenate. And diglyceryl monoisostearate, diglyceryl monooleate, hexaglyceryl monostearate and the like.
Specific examples of the higher alcohol polyhydric alcohol ether include oleyl glyceryl ether, cetyl glyceryl ether, stearyl glyceryl ether, isostearyl glyceryl ether, and decyl glyceryl ether.

  The blending amount of the higher fatty acid polyhydric alcohol ester and / or higher alcohol polyhydric alcohol ether used in the present invention is 20 to 86% by mass, preferably 25 to 60% by mass with respect to the whole non-water dyeing hair. . If it is less than 20% by mass, it is difficult to dissolve DHI, ascorbic acid and its salts, alkanolamines and the like, and the stability may be impaired. If it exceeds 86% by mass, the hygroscopicity is increased and the stability of DHI is inhibited. There is a fear.

The higher fatty acid used in the present invention has DHI stabilization and the thickening effect of the non-water dye of the present invention. In a trace amount of alkali combined system, it exhibits the stabilization effect of the non-water dye of the present invention.
The higher fatty acid used in the present invention is a saturated, unsaturated, branched fatty acid having 12 or more carbon atoms or a fatty acid having a hydroxyl group, preferably a fatty acid having 14 or more carbon atoms. Specific examples include myristic acid, isostearic acid, oleic acid, stearic acid, myristic acid, behenic acid, hydroxystearic acid, polyhydroxystearic acid, and polyricinoleic acid.
The compounding quantity of the higher fatty acid used by this invention is 3-20 mass% with respect to the whole non-water dyeing hair, Preferably it is 3-15 mass%. If it is less than 3% by mass, the stability of DHI may be impaired, and if it exceeds 20% by mass, the viscosity may be too high.

DHI used in the present invention is 5,6-dihydroxyindole and its salts. As salts of 5,6-dihydroxyindole, hydrochloride, hydrobromide, phosphate, sulfate, acetate are usually used. Lactate, citrate and the like are used, and among these, at least one salt selected from hydrochloride, phosphate, sulfate and lactate can be preferably used.
DHI used by this invention is 0.01 mass% or more with respect to the whole non-water dyeing hair material of this invention, Preferably it is 0.01-5 mass%. If it is less than 0.01% by mass, it is difficult to dye black and the hair may be insufficient. If it exceeds 5% by mass, the economical efficiency is deteriorated, and there is a possibility that the non-water dye of the present invention does not dissolve.

  Specific examples of the alkanolamine used in the present invention include monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, and ammonia. Preferably it is 0.01-2 mass% with respect to the whole non-water dyeing hair material of this invention, Most preferably, it is 0.05-1 mass%. If it is less than 0.01% by mass, the effect may not be obtained, and if it exceeds 2% by mass, the stability of DHI may be impaired.

  Ascorbic acid and salts thereof used in the present invention are 0.01 to 5% by mass, preferably 0.1 to 5% by mass, based on the entire non-water dye of the present invention. If it is less than 0.01% by mass, the stability of DHI may be impaired, and if it exceeds 5% by mass, applicability may be impaired.

Examples of the direct dye used in the present invention include blue No. 1, purple No. 401, black No. 401, orange No. 205, red No. 227, red No. 106, yellow No. 203, acidic orange 3, and the like, 2-nitro Paraphenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, 4-nitroorthophenylenediamine, 4-amino-3-nitrophenol, 4-hydroxypropylamino- 3-nitrophenol, HC blue 2, HC orange 1, HC red 1, HC yellow 2, HC yellow 4, HC yellow 5, HC red 3, N, N-bis- (2-hydroxyethyl) -2-nitropara Nitro dyes such as phenylenediamine, disperse dyes such as disperse purple 1, disperse blue 1, disperse black 9, basic blue 99, basic brown 16, basic brown 17, basic red 76 Basic red 51, basic yellow 57, Basic Yellow 87, and basic dyes such as basic orange 31 and the like.
Among them, direct dyes include 2-nitroparaphenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, 4-nitroorthophenylenediamine, 4-amino-3- At least one nitro dye selected from nitrophenol, 4-hydroxypropylamino-3-nitrophenol, HC blue 2, HC orange 1, HC red 1, HC yellow 2, HC yellow 4, HC yellow 5, HC red 3 It is preferable because it penetrates well into the hair and the dyed color can be easily controlled over a wide range. The HC means a hair color.
Selection of the kind of the direct dye used in the present invention and the amount of the direct dye are determined in advance by testing so as to obtain a desired dyed color.

  Non-water dyes of the present invention include various alcohols such as higher alcohols, alkylamines, alkylamides, animal and vegetable oils, mineral oils, waxes such as paraffin wax, beeswax, carnauba wax, and candelilla wax, and esters. Various cosmetic ingredients can be blended.

  In order to improve the conditioning effect, it is preferable to further contain silicone. Examples of silicone include dimethylpolysiloxane, methylphenylpolysiloxane, amino-modified silicone, polyether-modified silicone, polysilicone-9, and cyclic silicone. Among these, amino-modified silicone is preferred from the viewpoint of dyeability and conditioning effect. These can use 1 type (s) or 2 or more types, Content is 0.01-10 mass% with respect to the whole non-water dyeing hair material of this invention, Furthermore, 0.1-6 mass%, Especially It is preferable that it is 0.3-3 mass%.

  The non-water dye of the present invention can be in various forms such as liquids, creams, gels or other forms suitable for dyeing human hair. Any container can be used, including bags, bottles, pump-type containers, tubes, and spray cans.

  In addition to the above-mentioned components, the non-water dye of the present invention includes components usually used in hair cosmetics, for example, thickeners such as carboxymethyl cellulose, hydroxyethyl cellulose, cationized cellulose, xanthan gum, succinoglucan, hydroxypropyl Guar gums such as guar gum and cationized guar gum, stabilizers, buffers, fragrances, vitamins, touch improvers, chelating agents such as EDTA, EDTA-2Na, EDTA-4Na, hydroxyethanediphosphonic acid, solubilizers, parabens , Antiseptics such as methylisothiazolinone, UV absorbers, antioxidants, bactericides, pearlizing agents, pigments such as ultrafine titanium black, protein hydrolysates, etc., within a range that does not impair the effects of the present invention. Depending on the purpose, it can be appropriately blended.

  The description of the above embodiment is for explaining the present invention, and does not limit the invention described in the claims or reduce the scope. Moreover, each part structure of this invention is not restricted to the said embodiment, A various deformation | transformation is possible within the technical scope as described in a claim.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention in detail, unless it deviates from the main point of this invention, it is not limited to these Examples.

In (Examples 1 and 2), the stability of DHI is evaluated when butanol is used instead in the case of using the non-water dye of the present invention and in (Comparative Examples 1 and 2).

Example 1
A predetermined amount of each component (anhydride) of the following (composition of non-aqueous composition) is weighed in a beaker, heated to 80 ° C., uniformly dissolved, cooled with stirring and left at 30 ° C., A non-aqueous composition was prepared.
1 g of DHI was dissolved in 99 g of the produced non-aqueous composition to prepare the non-water dye of the present invention.
And the stability of DHI when the non-water dye of this invention was allowed to stand according to the following stability test method was evaluated. The evaluation results are shown in Table 1.

(Composition of non-aqueous composition)
Tripentaoxyethylene cetyl ether phosphoric acid 10.0 g
(Nikko Chemical Co., Ltd. NIKKOL TCP-5)
Isostearic acid monoglyceride 30.0g
(NIKKOL MGIS-V manufactured by Nikko Chemical)
Monolauric acid propylene glycol ester 20.0g
(Rikenmar PL-100 manufactured by Riken Vitamin)
Hydroxystearic acid 5.0g
(Manufactured by KF TRADING)
Liquid paraffin 35.0g
(Carnation 70 made by Shima Trading)
Total 100.0g

(Stability test method)
The non-water dye of the present invention was placed in a 20 cc brown bottle with air replaced with nitrogen and sealed. The sealed sample was placed in a constant temperature bath at 40 ° C. for 2 weeks, and then the remaining DHI was quantified by HPLC, and the stability of DHI was determined by the following formula (1).
Formula (1):
Stability (mass%) = {mass g of residual DHI / mass g of DHI at the time of preparation} × 100

(Example 2)
The stability of DHI was evaluated in the same manner as in Example 1 except that 5 g of DHI was dissolved in 95 g of the non-aqueous composition prepared in Example 1 to prepare the non-water dye of the present invention. The evaluation results are shown in Table 1.

(Comparative Example 1)
Example 1 was used except that n-butanol (anhydride) was used instead of the non-aqueous composition prepared in Example 1 and 1 g of DHI was dissolved in 99 g of n-butanol to prepare a comparative composition. Thus, the stability of DHI was evaluated. The evaluation results are shown in Table 1.

(Comparative Example 2)
Example 1 was used except that n-butanol (anhydride) was used instead of the non-aqueous composition prepared in Example 1, and 5 g of DHI was dissolved in 95 g of n-butanol to prepare a comparative composition. Thus, the stability of DHI was evaluated. The evaluation results are shown in Table 1.

  From Table 1, it can be seen that Examples 1 and 2 have very high and high DHI stability, but Comparative Examples 1 and 2 using butanol have very low DHI stability.

In (Examples 3 to 6) and (Comparative Examples 3 to 5), the effect of the blending amount of liquid paraffin is evaluated.

(Examples 3 to 6)
Each component (anhydride) and blending amount (g) described in Table 2 were weighed in a beaker in the same manner as in Example 1, heated to 80 ° C., uniformly dissolved, cooled with stirring, and 30 A non-aqueous composition (99 g in total) was prepared by allowing to stand at 0 ° C., and 1 g of DHI was dissolved in 99 g of the prepared non-aqueous composition to prepare the non-water dye of the present invention. Placed in a bottle and sealed.
And by visually observing the appearance of the non-water dye of the present invention of Examples 3-6, it is determined whether it is solid, semi-solid (jelly-like) or liquid, and the following evaluation items (DHI change degree, DHI dissolution) Table 2 shows the results obtained by testing the properties, water washability, and substrate stability) and evaluating in accordance with the following evaluation criteria.

(Evaluation item)
1. Degree of change in DHI:
The degree of coloration of the non-water-dyed hair material of the present invention, which is taken out from the brown bottle and allowed to stand at room temperature for one day, is determined visually.
(Evaluation criteria)
○: No change.
Δ: Slightly changed.
X: Changed greatly.

2. Solubility of DHI:
1 g of the non-water dye of the present invention taken out from the brown bottle was applied onto the filter paper, and this filter paper was left standing at room temperature for 1 day. Then, the state of black spreading generated by air oxidation was visually judged.
(Evaluation criteria)
X: It does not spread.
(Triangle | delta): It does not spread uniformly.
○: Spreads uniformly.

3. Washability:
The non-water dye of the present invention taken out from the brown bottle was taken on both palms, rubbed together, and washed with tap water. The coloration state of the palms of both hands was judged visually.
(Evaluation criteria)
X: It remained black so that it could be understood well in the palm.
Δ: Remains inconspicuous.
◯: Not black at all.

4). Substrate stability:
After leaving the non-water dyeing hair of the present invention sealed in a 20 cc brown bottle at room temperature for one day, leaving it in a thermostatic bath at 40 ° C. for 2 weeks, taking it out from the brown bottle, and removing the non-water dyeing of the present invention. The appearance of the hair was visually determined.
(Evaluation criteria)
X: Separated.
Δ: Liquid oil oozes out slightly in the upper layer.
Y: No change

(Comparative Examples 3-5)
With each component (anhydride) and blending amount (g) described in Table 2, a non-aqueous composition for comparison (total 99 g) was prepared in the same manner as in Example 1, and 99 g of the prepared non-aqueous composition was prepared. A non-water dye for comparison was prepared by dissolving 1 g of DHI, placed in a 20 cc brown bottle in air and sealed.
The results evaluated in the same manner as in Examples 3 to 6 are shown in Table 2.

  From Table 2, the non-water dyes of the present invention of Examples 3 to 6 having liquid paraffin of 20% by mass or more are excellent in the stability of the base material, and (DHI change degree, DHI solubility) , Water washability) is excellent with ◯. On the other hand, the non-water dye for comparison in Comparative Examples 3 to 4 has no or little liquid paraffin, so that the stability Δ of the base material and the degree of change X in DHI are inferior. It can be seen that non-water dyes contain a large amount of liquid paraffin, so that the amount of esters (monolauric acid propylene glycol ester and isostearic acid monoglyceride) used is small, and the solubility x of DHI is poor.

In (Examples 7 to 10) and (Comparative Examples 6 to 8), the effect of the blending amount of the higher fatty acid polyhydric alcohol ester is evaluated.

(Examples 7 to 10)
Using each component (anhydride) and blending amount (g) listed in Table 3, a non-aqueous composition (total 99 g) was prepared in the same manner as in Example 1, and 1 g of DHI was dissolved in 99 g of the prepared non-aqueous composition. Then, the non-water dye of the present invention was prepared, put in a 20 cc brown bottle in the air, and sealed.
And the result evaluated like Example 3-6 is shown in Table 3.

(Comparative Examples 6-8)
Each component (anhydride) and blending amount (g) described in Table 3 were prepared in the same manner as in Example 1 to prepare a non-aqueous composition for comparison (total 99 g). A non-water dye for comparison was prepared by dissolving 1 g of DHI, placed in a 20 cc brown bottle in air and sealed.
And the result evaluated like Example 3-6 is shown in Table 3.

  From Table 3, in Comparative Examples 6 and 7, the total blending amount of isostearic acid monoglyceride and propylene glycol laurate or a single blending amount is small, and the blending amount of squalane is large. In Example 8, the total amount of isostearic acid monoglyceride and propylene glycol laurate is large, and the amount of squalane is small. It can be seen that the hair material is excellent in all of (degree of change in DHI, solubility of DHI, water washability, stability of base material).

In (Examples 11 to 15) and (Comparative Examples 9 to 10), the effect of the blending amount of the surfactant is evaluated.

(Examples 11 to 15)
Using each component (anhydride) and blending amount (g) listed in Table 4, a non-aqueous composition (total 99 g) was prepared in the same manner as in Example 1, and 1 g of DHI was dissolved in 99 g of the prepared non-aqueous composition. Then, the non-water dye of the present invention was prepared, put in a 20 cc brown bottle in the air, and sealed.
And the result evaluated like Example 3-6 is shown in Table 4.
Manufacturers of surfactant components in Table 4 are as follows:
Tripentaoxyethylene cetyl ether phosphoric acid: NIKKOL TCP-5 manufactured by Nikko Chemicals
Stearyl trimonium salt: manufactured by Toho Chemical Co., Ltd. Katchinal STC-70ET
POE glyceryl ether triisostearate: NIKKOL TGI-20 manufactured by Nikko Chemicals
Decaglycerin monoisostearate: NIKKOL Decaglyn1-IS manufactured by Nikko Chemicals

(Comparative Examples 9 to 10)
A non-aqueous composition for comparison (total 99 g) was prepared in the same manner as in Example 1 using each component (anhydride) and blending amount (g) described in Table 4, and the prepared non-aqueous composition 99 g A non-water dye for comparison was prepared by dissolving 1 g of DHI, placed in a 20 cc brown bottle in air and sealed.
And the result evaluated like Example 3-6 is shown in Table 4.

  From Table 4, Comparative Example 9 does not contain a surfactant and is inferior in DHI change degree ×, water washability × and base stability ×, and Comparative Example 10 is a total amount of surfactant. Since there is too much, the hygroscopicity is increased, or the degree of change in DHI x is impaired. On the other hand, it can be seen that the non-water dyes of the present invention of Examples 11 to 15 are all excellent in (DHI change degree, DHI solubility, washability, and substrate stability).

In (Examples 16 to 21) and (Comparative Example 11), the effect of the blending amount of higher fatty acids is evaluated.

(Examples 16 to 21)
With each component (anhydride) and blending amount (g) listed in Table 5, a non-aqueous composition (total 99 g) was prepared in the same manner as in Example 1, and 1 g of DHI was dissolved in 99 g of the prepared non-aqueous composition. Then, the non-water dye of the present invention was prepared, put in a 20 cc brown bottle in the air, and sealed.
And the result evaluated like Example 3-6 is shown in Table 5.
(Comparative Example 11)
A non-aqueous composition for comparison (total 99 g) was prepared in the same manner as in Example 1 with each component (anhydride) and blending amount (g) listed in Table 5, and the prepared non-aqueous composition 99 g A non-water dye for comparison was prepared by dissolving 1 g of DHI, placed in a 20 cc brown bottle in air and sealed.
And the result evaluated like Example 3-6 is shown in Table 5.

  From Table 5, Comparative Example 11 does not contain a higher fatty acid, and the degree of change in DHI × and the stability of the base × are inferior. On the other hand, it can be seen that the non-water dyes of the present invention of Examples 16 to 21 are all excellent in (DHI change degree, DHI solubility, washability, and substrate stability).

(Example 22)
Each component (anhydride) of the following (composition of non-aqueous composition) is weighed in a beaker, heated to 80 ° C., uniformly dissolved, cooled with stirring, and allowed to stand at 30 ° C. A product (99.7 g in total) was produced.
To the prepared non-aqueous composition, 0.1 g of DHI, 0.1 g of ascorbic acid, and 0.1 g of fragrance were dissolved at room temperature to prepare a non-water dye (a leave-on treatment having a white hair dyeing effect) of the present invention.
The non-water dye of the present invention was placed in a 20 cc brown bottle in air and sealed.

(Composition of non-aqueous composition)
Squalane 44.7g
(Sugar Squalane made by Nikko Chemicals)
Tripentaoxyethylene cetyl ether phosphoric acid 5.0 g
(Nikko Chemicals Corporation NIKKOL TCP-5)
Monolauric acid propylene glycol ester 15.0g
(Rikenmar PL-100 manufactured by Riken Vitamin)
Isostearic acid monoglyceride 30.0g
(NIKKOL MGIS-V manufactured by Nikko Chemical)
Hydroxystearic acid 5.0g
(Manufactured by KF TRADING)

  Using the non-water-dyed hair material of the present invention, 10 elderly male panel members take a 1 g sample of the non-water-colored hair material of the present invention at the fingertips after the bath, and evenly apply it to the white hair region. After gently rubbing one hair and one hair, and combing it 5 times with a comb so as to apply evenly, drying with a hand-held dryer was continued every day for one week.

  After 1 week, the dyed state of the white hair part, the state of soiling of the hand when washing after application, and the degree of soiling of the towel after 1 week when sleeping with a predetermined towel on the pillow were examined. The results were as follows.

Test results:
Clearly stained people: 7/10 people (3 people are slightly dyed)
People who can't see the dirt on their hands: 10/10 People who can't confirm the level of dirt on the towels: 8/10 (2 people could see some dirt)
Persons whose gray hair became inconspicuous after one week: 10/10 The result was that white hair became inconspicuous without being attached to fingers or clothes.

(Shampoo stability)
The hair bundle dyed by the above hair dyeing method was immersed in a 15% by mass aqueous solution of Na lauryl sulfate, left in a thermostatic bath at 50 ° C. for 1 hour, washed with water, and naturally dried at room temperature.
The color difference ΔE between the hair before and after treatment was measured with a color difference meter (model number: CM-2500D / manufactured by Konica Minolta Co., Ltd.) and the shampoo stability was evaluated visually.
Color difference ΔE of hair before treatment: 37.4
Color difference ΔE of hair after treatment: 36.7
As described above, it was found that the difference in color difference ΔE before and after the treatment was small, it was difficult to visually distinguish between before and after the treatment, and the shampoo stability was high.

(UV resistance)
The hair bundle dyed by the above-described hair dyeing method was tested based on the third exposure method of “JIS L0842 Test Method for Color Fastness to Ultraviolet Carbon Arc Lamp Light”.
Equipment manufacturer: Suga Test Instruments Co., Ltd., Model U48AU
Light source: UV carbon arc lamp,
Black panel temperature: 63 ° C
Humidity generation system mounted After the irradiation with ultraviolet rays, the hair bundle was taken out, and the difference in color between the portion irradiated with ultraviolet rays and the portion not irradiated with ultraviolet rays was compared with a blue fading (JIS L0842), and visually judged.

Judgment criteria:
○: The color of the hair bundle irradiated with ultraviolet rays does not change, and is excellent in ultraviolet resistance.
(Triangle | delta): Although the color of the hair | bristle bundle which received ultraviolet rays has changed a little, it can be said that it is excellent in ultraviolet-ray resistance practically.
X: The color of the hair | bristle bundle which irradiated the ultraviolet-ray has changed, and cannot be used.

  As a result of visual judgment, it was found that the color of the hair bundle irradiated with ultraviolet rays did not change and was excellent in ultraviolet resistance.

(Example 23)
In the same manner as in Example 22, a non-water dye (the leave-on treatment having a white hair dyeing effect) of the present invention having the following composition was prepared.
Then, in a predetermined container, 0.5 g of the non-water dye of the present invention described below was uniformly blended with 3 g of the following hair styling agent to prepare a new hair styling.

Non-water dye of the present invention:
Ceteth diphosphate 10g
(Toho Chemical Phosphanol RL-210)
Cetyl alcohol 5g
20g of isostearic acid
Oleic acid monoglyceride 40g
POE glyceryl ether triisostearate 3g
(Nikko Chemicals Corporation NIKKOL TGI-20)
Hemis squalene 20g
(Nikko Chemicals)
DHI 2g%

Hairdressing agent:
Stearyltrimonium chloride 1.0% by mass
Cetanol 5.0% by mass
Pentahydroxystearic acid ester 0.3% by mass
(NIKKOL Decaglyn 5HS, manufactured by Nikko Chemicals)
POE glyceryl ether triisostearate 0.3% by mass
(Nikko Chemicals Corporation NIKKOL TGI-20)
Cetyl isooctanoate 1.0% by mass
(NIKKOL CIO manufactured by Nikko Chemicals)
Straw oil 1.0% by mass
Sorbitol 2.0% by mass
Purified water remaining

Using the prepared new hair dressing, application to the hair every morning by 10 elderly male panel members was continued as in Example 22.
Test results: All members did not attach to fingers, clothes, etc., and gray hair became inconspicuous.

(Example 24)
When the non-water dye of the present invention used in Example 23 was used, a treatment in which 5% by mass of the following color treatment was mixed well was continuously applied every day after bathing.
Non-water dye of the present invention (Example 23) 5.0 mass%
The following color treatment 95.0% by mass

Color treatment:
Behenyltrimonium chloride 1.0% by mass
Cetanol 6.0% by mass
Decagulin 5HS 0.3% by mass
Starform DOS 2.0% by mass
Tricetyl phosphate 0.5% by mass
Cetylisooctanoic acid ester 1.0% by mass
Hemis squalene 3.0% by mass
Straw oil 1.0% by mass
Total amount of purified water is 100.0% by mass
Furthermore, the following direct dyes were blended.
Red 227 0.067 mass%
HC Blue 2 0.4% by mass
HC Yellow 4 0.18% by mass

Using this treatment, 10 elderly female panel members took 1g of treatment to the application area of 40cm ² on their fingertips after taking a bath, carefully applied to the whole hair, and then combed 5 times with a comb. Thereafter, drying with a dryer was continued to be applied daily for one week.
The dyeing state of the white hair part after one week, the state of hand dirt when handwashed after application, and the degree of dirtiness of the towel after one week when sleeping with a predetermined towel on the pillow were examined. The results were as follows.

Test results:
People who can't see the dirt on their hands: 10/10 People who can't confirm the level of dirt on the towels: 8/10 (2 people are slightly dirty)
People whose gray hair area is not noticeable: 8/10 people (2 people are slightly dyed)
The hair did not stick to fingers and clothes, and the gray hair became inconspicuous.

  The non-water dye of the present invention is a non-aqueous composition containing a predetermined amount of hydrocarbon oil, surfactant, higher fatty acid polyhydric alcohol ester and / or higher alcohol polyhydric alcohol ether, and higher fatty acid, respectively. -Non-water dye containing a predetermined amount of dihydroxyindoles, in which DHI, ascorbic acid or a salt thereof and alkanolamine are dissolved in higher fatty acid polyhydric alcohol ester and / or higher alcohol polyhydric alcohol ether Because it is dispersed in hydrocarbons with low air permeability and excellent air barrier effect, non-water dyeing hair can be applied to hair by hand, and after application it can be washed easily and will not remain, so hair It has excellent dyeing properties, but it does not stain the skin or scalp of the body, and it can also be used for hair dyeing places such as toilets, bathrooms, washbasins and clothes. It has a remarkable effect that it can be washed off even if it is attached to an appliance, etc., and it has a remarkable effect that it can be stored by dissolving and storing DHI stably, and even when applied to the hair surface in the air Oxidative polymerization does not occur immediately, and DHI penetrates well into the cortex inside the hair and oxidatively polymerizes, so it can be dyed well up to the cortex inside the hair. Since it is performed at the same time, the color tone after dyeing can be easily controlled over a wide range, and the shampoo stability after hair dyeing and UV resistance are high, and it is possible to produce hair that does not lose color. Therefore, the industrial utility value is very large.

Claims (3)

Hydrocarbon oil 20 to 60% by mass, surfactant 1 to 20% by mass, higher fatty acid polyhydric alcohol ester and / or higher alcohol polyhydric alcohol ether 20 to 86% by mass, higher fatty acid A non-water dye comprising a non-aqueous composition containing 3 to 20% by mass of 0.01% by mass or more of 5,6-dihydroxyindoles.
However, a + b + c + d + e + f = 100 mass%
a: the content of hydrocarbon oil b: the content of surfactant c: the content of higher fatty acid polyhydric alcohol ester and / or higher alcohol polyhydric alcohol ether d: the content of higher fatty acid e: 5 , 6-dihydroxyindoles content f: content of optional components added as necessary   The non-water dye according to claim 1, comprising ascorbic acid or a salt thereof and / or an alkanolamine.   The non-water dye according to claim 1 or 2, wherein a direct dye is blended.