WO2013077072A1 - Oxidation hair dye - Google Patents

Abstract

The present invention provides an oxidation hair dye which comprises a first agent containing an alkaline agent and a second agent containing an oxidizing agent, said first and second agents being to be mixed together, characterized by, immediately after mixing the first agent with the second agent, said oxidation hair dye containing a bicontinuous microemulsion phase or a lamellar liquid crystal phase. The purpose of the present invention is to acquire an oxidation hair dye, which can exert a good dyeing effect on both damaged hair (hair chemically damaged by the use of hair dyes, perming agents, etc. and hair mechanically damaged by friction, etc.) and non-damaged healthy hair, by using a base agent that contains a bicontinuous microemulsion phase or a lamellar liquid crystal phase.

Description

Oxidative hair dye

The present invention relates to an oxidative hair dye. More specifically, by incorporating a bicontinuous microemulsion phase or lamellar liquid crystal phase into the base, damaged hair (chemical damage such as hair dyes and permanents, physical damage such as friction) The present invention relates to an oxidative hair dye having excellent dyeability for both (received hair) and healthy hair that is not damaged.

In recent years, with the change in consumer awareness, the desire to lighten hair has increased, and the market for hair dyes has expanded.
Hair dyes can be dyed in a lighter tone than the original hair with a bleaching effect, and since the effect is sustained, oxidation hair dyes are particularly widely used. The oxidative hair dye is mainly a two-component type consisting of a first agent containing an alkaline agent and an oxidative dye and a second agent containing an oxidant, and this is the first agent during the treatment. The second agent is mixed, applied to the hair, allowed to stand for a certain period of time, and then rinsed for use.

Generally, the first component of the oxidative hair dye is blended with an oily component such as higher alcohol for the purpose of protecting the hair during hair dyeing. And the surfactant is mix | blended for emulsification of the oil-based component. In order to obtain a hair dye having excellent emulsification stability and excellent hair feel after treatment, in recent years, the type and amount of surfactants used in the hair dye have been studied.

For example, hair dyes (for example, see Patent Documents 1 to 3) in which a gel is formed by mixing a long-chain acylsulfonate type anionic surfactant and a long-chain alkyl alcohol (= aliphatic alcohol), or amphoteric surfactant Hair dye containing a colorant and a cationic surfactant (Patent Document 4), containing an anionic surfactant, substantially containing a nonionic surfactant, a cationic surfactant and an amphoteric surfactant Hair dyes that do not (Patent Document 5) are known.

The cuticle that covers the surface of the hair is composed mainly of a hydrophobic substance, and plays a role in protecting the hair in a healthy state by protecting the area inside the hair. However, hair is often damaged by chemical influences such as hair dyeing and decoloring treatments and physical influences such as ultraviolet rays, friction and heat. Damaged hair partially loses hydrophobic cuticles. Thus, in the part where the cuticle is lost, the hydrophobicity is lower than the surroundings. Further, the loss of the cuticle is not a phenomenon that occurs evenly throughout the hair, but occurs frequently in the vicinity of the hair tip that has been repeatedly subjected to chemical and physical effects.

Thus, chemically damaged hair such as hair dyes and permanent agents, and hair that has been physically damaged such as friction (damaged hair) is hydrophilic (easy to repel oil). On the other hand, the hair surface of healthy hair that is not damaged is hydrophobic (easy to repel water). Therefore, even when the same hair dye is used, the finished hair color is different between the vicinity of the damaged hair and the root part of healthy hair, or it is blended in the hair dye for the purpose of protecting the hair. Aqueous or oily treatment ingredients may not be able to fully exert their effects and may have a different finished feel.

For example, Patent Document 6 describes a technique for making a foam using a flexible porous material and dyeing the hair without color unevenness. The hydrophilicity and hydrophobicity are not considered. For this reason, it has been difficult for these conventional techniques to distort hair with various degrees of hydrophilicity from the root to the tip of the hair without causing uneven coloration.

On the other hand, the bicontinuous microemulsion phase is generally generated under conditions where the hydrophilic-hydrophobic balance is balanced, the oil-water interfacial tension is minimized, the number of associations of the surfactant increases, and the infinite association occurs. As a result, the solubilization amount of water and oil is dramatically improved, and the solubilization system has a unique structure in which water and oil form continuous channels.

In the bicontinuous microemulsion phase, it is very difficult to search for a combination of compounds that satisfy the generation conditions, and the generation range is said to be extremely narrow. Therefore, it is often observed as an oil phase / bicontinuous microemulsion phase / water phase coexisting with excess water and oil that are not solubilized (for example, Non-Patent Document 1), but a bicontinuous microemulsion. There are not many reports that the phases are observed as one state. For example, in Non-Patent Document 2, polyoxyethylene lauryl ether (4EO) is used as a surfactant, and isohexadecane is used as an oil. In Non-Patent Document 3, didecyldimethylammonium salt is used as a surfactant, and dodecane is used as an oil. By using non-patent document 4, it is reported that a bicontinuous microemulsion phase can be obtained by using soybean phospholipid as a surfactant, propanol as a surfactant, and triglyceride as an oil.

Patent Document 7 uses polyethylene glycol monolaurate (12EO) as a surfactant, lauryl alcohol and ethanol as a surfactant aid, and liquid isoparaffin as an oil component. Patent Document 8 discloses POE (8 as a surfactant). ) By using glyceryl isostearate, cetyl octanoate and liquid paraffin as the oil component, Patent Document 9 discloses imidazolinium betaine and POE lauryl ether sulfate as surfactants, mono fatty acid monoglycerin ester and monoalkyl monoester as oil components. It has been reported that a bicontinuous microemulsion phase can be obtained by using glyceryl ether.

Since the bicontinuous microemulsion phase has a unique structure in which both water and oil are continuous, it can contain a larger amount of oil and oily components than the micelle phase. Moreover, compared with a reverse micelle phase, a large amount of water and an aqueous component can be mix | blended. A detergent composition with excellent detergency and good rinsing properties for both oily and water-soluble soils by utilizing its water and oil-friendly properties and low interfacial tension. There are many report examples (see, for example, Patent Documents 7 to 11). However, at present, industrial utilization other than the purpose of cleaning has not been sufficiently performed.

The lamellar liquid crystal phase is one of liquid crystal aggregates having a structure in which both water and oil are continuous, like the bicontinuous microemulsion phase. Unlike the bicontinuous microemulsion phase, the bilayer film of the amphiphile has the regularity of the molecular arrangement. Therefore, small angle X-ray scattering (SAXS) measurement is performed to measure the spacing between the regular structures. Can be confirmed. Also, by placing a sample between two orthogonal polarizing plates and irradiating light through one polarizing plate, the light passes through the other polarizing plate, that is, confirming the optical rotation of the sample, The presence of the liquid crystal phase can be easily confirmed.
The formation of lamellar liquid crystals has been widely known for a long time (Non-patent Document 5 etc.), and there are reported examples of gel cosmetics for cleansing or massage (Patent Document 12 etc.).

Japanese Patent Laid-Open No. 05-271041 JP 2002-205923 A JP 2003-327518 A Japanese Patent Laid-Open No. 07-082123 JP 2003-171247 A JP 2010-215576 A JP 2004-217640 A JP 2005-194249 A JP 2007-077302 A Patent Publication No. 3684144 JP 2009-196909 A JP 2006-069979 A

Therefore, the problem to be solved by the present invention is to provide excellent dyeing for both damaged hair and healthy hair that has not been damaged by utilizing a bicontinuous microemulsion phase or a lamellar liquid crystal phase. An object of the present invention is to provide an oxidative hair dye having properties.

That is, the present invention provides an oxidative hair dye that mixes a first agent containing an alkali agent and a second agent containing an oxidant, and immediately after mixing the first agent and the second agent, The present invention provides an oxidation hair dye characterized by containing a microemulsion phase or a lamellar liquid crystal phase.

Further, the present invention contains the following components (a) to (c) that form a bicontinuous microemulsion phase or a lamellar liquid crystal phase in the first agent and / or the second agent. An oxidative hair dye is provided.
(A) ionic surfactant (b) amphiphile having a ratio of (inorganic value / organic value) ratio in the range of 0.8 to 1.5 (c) water

Furthermore, the present invention includes the following components (d) to (f) that form a bicontinuous microemulsion phase or a lamellar liquid crystal phase in the first agent and / or the second agent. An oxidative hair dye is provided.
(D) Nonionic surfactant (e) Oil (f) Water

In the present invention, the component (a) ionic surfactant contains an anionic surfactant, and further contains one or more selected from amphoteric surfactants and / or cationic surfactants. The above-mentioned oxidative hair dye characterized by the above is provided.

Furthermore, the present invention provides the component (a) ionic surfactant, wherein the mass ratio of the anionic surfactant to the amphoteric surfactant and / or the cationic surfactant is (anionic surfactant). : (Amphoteric surfactant and / or cationic surfactant) = 2: 8 to 8: 2 The above oxidative hair dye is provided.

The present invention also provides that the amphiphile having a component (b) (inorganic value / organic value) ratio within a range of 0.8 to 1.5 is a monoglycerin derivative, a diglycerin derivative, Providing the above oxidative hair dye characterized in that it is one or more selected from propylene glycol derivatives, butylene glycol derivatives, monoethanolamide derivatives, monoethanolamine derivatives, diethanolamide derivatives, diethanolamine derivatives It is.

Furthermore, the present invention provides the above-described oxidative hair dye, wherein the component (d) nonionic surfactant has an HLB in the range of 5-14.

According to the present invention, by utilizing the bicontinuous microemulsion phase and the lamellar liquid crystal phase, both the damaged hair and the undamaged healthy hair are dyeable (due to dyeing effect and dyeing). It is possible to provide an oxidative hair dye which is remarkably excellent in (non-color unevenness) and which is also excellent in the effect of suppressing discoloration by washing after hair dyeing.

FIG. 1 is an example of interfacial tension measurement for decane when the mixing ratio of amphoteric surfactant and anionic surfactant is changed. FIG. 2 shows the results of measurement of lightness difference (ΔL) and color difference (ΔE) before and after shampooing after hair dyeing.

Hereinafter, preferred embodiments of the present invention will be described.

First, each essential component that forms a bicontinuous microemulsion phase or a lamellar liquid crystal phase will be sequentially described.
"(A) Ionic surfactant"
The (a) ionic surfactant used in the present invention is a surfactant that is ionized in an aqueous solution and has a charge. Depending on the type of charge, the amphoteric surfactant, the cationic surfactant, and the anionic surfactant are used. are categorized.

The amphoteric surfactant has at least one cationic functional group and one anionic functional group, becomes cationic when the solution is acidic, and anionic when the solution is alkaline, and is close to a nonionic surfactant near the isoelectric point. It has properties.
Amphoteric surfactants are classified into carboxylic acid type, sulfate ester type, sulfonic acid type and phosphate ester type depending on the type of anionic group. The carboxylic acid type, sulfate type and sulfonic acid type are preferred in the present invention. Carboxylic acid types are further classified into amino acid types and betaine types. Particularly preferred is a betaine type.
Specifically, for example, imidazoline-based amphoteric surfactants (for example, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide) 1-carboxyethyloxy disodium salt); betaine surfactants (for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine, sulfone) Betaine) and the like.

Examples of the cationic surfactant include quaternary ammonium salts such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyldimethylhydroxyethylammonium chloride, stearyldimethylbenzylammonium chloride, and cetyltriethylammonium methylsulfate. Can be mentioned. Also, stearic acid diethylaminoethylamide, stearic acid dimethylaminoethylamide, palmitic acid diethylaminoethylamide, palmitic acid dimethylaminoethylamide, myristic acid diethylaminoethylamide, myristic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide, behenic acid dimethyl Aminoethylamide, stearic acid diethylaminopropylamide, stearic acid dimethylaminopropylamide, palmitic acid diethylaminopropylamide, palmitic acid dimethylaminopropylamide, myristic acid diethylaminopropylamide, myristic acid dimethylaminopropylamide, behenic acid diethylaminopropylamide, behenine Amidoamino such as dimethylaminopropylamide Compounds.

Anionic surfactants include fatty acid soap, N-acyl glutamate, carboxylate type such as alkyl ether acetic acid, sulfonic acid type such as α-olefin sulfonate, alkane sulfonate, alkylbenzene sulfonic acid, higher alcohol sulfate It is classified into a sulfate ester salt type such as an ester salt and a phosphate ester salt type. Carboxylate type, sulfonic acid type and sulfate ester type are preferred, and sulfate ester type is particularly preferred.
Specifically, for example, fatty acid soap (eg, sodium laurate, sodium palmitate, etc.), higher alkyl sulfate ester salt (eg, sodium lauryl sulfate, potassium lauryl sulfate), alkyl ether sulfate ester salt (eg, POE- Lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.), N-acyl sarcosine acid (eg, sodium lauroyl sarcosine, etc.), higher fatty acid amide sulfonate (eg, sodium N-myristoyl-N-methyltaurine, coconut oil fatty acid) Methyl taurine sodium, lauryl methyl taurine sodium, etc.), phosphoric ester salts (POE-oleyl ether sodium phosphate, POE-stearyl ether phosphoric acid etc.), sulfosuccinates (eg di-2-ethylhexyl) Sodium sulfosulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.), alkyl benzene sulfonates (eg, linear dodecyl benzene sulfonate sodium, linear dodecyl benzene sulfonate triethanolamine, linear Dodecylbenzenesulfonic acid, etc.), higher fatty acid ester sulfates (for example, hydrogenated coconut oil fatty acid sodium glycerol sulfate, etc.), N-acyl glutamates (for example, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, N- Myristoyl-L-glutamate monosodium), sulfated oil (eg funnel oil), POE-alkyl ether carbo Acid, POE-alkyl allyl ether carboxylate, α-olefin sulfonate, higher fatty acid ester sulfonate, secondary alcohol sulfate, higher fatty acid alkylolamide sulfate, sodium lauroyl monoethanolamide succinate, N -Palmitoyl aspartate ditriethanolamine, sodium caseinate and the like.

It is known that the amphoteric surfactants and anionic surfactants, or the cationic surfactants and the anionic surfactants, when mixed in an aqueous solution, reduce the interfacial tension with respect to oil.
When only one type of amphoteric surfactant, cationic surfactant and anionic surfactant is used, the interfacial tension is not sufficiently lowered, and a bicontinuous microemulsion phase cannot be obtained or obtained. Even in such a case, the generation region is narrow, and the stability may not be sufficiently satisfied in practical use.
Accordingly, in the present invention, (a) the ionic surfactant includes an anionic surfactant, and further includes one or more selected from an amphoteric surfactant and / or a cationic surfactant. preferable.
In the component (a) ionic surfactant, the mass ratio of the anionic surfactant to the amphoteric surfactant and / or the cationic surfactant is (anionic surfactant): (amphoteric interface). Activators and / or cationic surfactants) = 2: 8 to 8: 2.
On the other hand, the blending amount of the (a) ionic surfactant is preferably 0.1 to 50% by mass, more preferably 0.3 to 30% by mass with respect to the total amount of the first agent or the second agent. .

“(B) Amphiphilic substance having a ratio of (inorganic value / organic value) in the range of 0.8 to 1.5 (in the present specification, the amphiphilic substance is simply referred to as a surfactant aid). I have to say) "
In order for the (b) amphiphile used in the present invention to function as a surfactant (also called a cosurfactant), the balance between the lipophilic group and the hydrophilic group is important. As an index, there is a method of quantifying the balance between the lipophilicity and the hydrophilicity as the organic value and the inorganic value from the structure of the compound. In order to function as a surfactant aid in the present invention, the value of (inorganic value / organic value) ratio needs to be in the range of 0.8 to 1.5. When a mixture of several compounds is used, the (inorganic value / organic value) ratio of each compound is obtained, and the average value must be within the range of 0.8 to 1.5. . The range of 0.9 to 1.3 is particularly desirable.
Such amphiphilic substances (surfactant aids) having a ratio of (inorganic value / organic value) in the range of 0.8 to 1.5 are monoglycerin derivatives, diglycerin derivatives, propylene glycol. It can be appropriately selected from among derivatives, butylene glycol derivatives and the like.
In addition, the value of (inorganic value / organic value) ratio is a well-known concept called IOB value, and “inorganic value” and “organic value” corresponding to various atoms or functional groups are set, By integrating the “inorganic value” and “organic value” of all atoms and functional groups in the organic compound, the value (IOB value) of the (inorganic value / organic value) ratio of the organic compound is calculated. (See, for example, Fujita, “Chemical Field”, Vol. 11, No. 10, 1957, pp. 719-725). Hereinafter, in this specification, the value of (inorganic value / organic value) ratio may be referred to as an IOB value.

For example, as monoglycerin derivatives, specifically, monooctanoic acid monoglycerin ester, monooctyl monoglyceryl ether, monononanoic acid monoglyceryl ester, monononyl monoglyceryl ether, monodecanoic acid monoglyceryl ester, monodecyl monoglyceryl ether, Monoundecylenic acid monoglycerin ester, monoundecylenyl monoglyceryl ether, monododecanoic acid monoglycerin ester (monolauric acid monoglyceryl ester), monododecyl monoglyceryl ether (monolauryl monoglyceryl ether), monotetradecanoic acid monoglycerin ester (monomyristin) Acid monoglycerin ester), monohexadecanoic acid monoglycerin ester (monopalmitic acid monoglycerin ester) , Monooleate monoglycerol ester, monoisostearate monoglyceryl ester.

For example, as the diglycerin derivative, specifically, monooctanoic acid diglycerin ester, monooctyl diglyceryl ether, monodecanoic acid diglycerin ester, monodecyl diglyceryl ether, monoundecylenic acid diglycerin ester, monoundecylenyl diglyceride Glyceryl ether, monododecanoic acid diglycerin ester (monolauric acid diglycerin ester), monododecyl diglyceryl ether (monolauryl diglyceryl ether), monotetradecanoic acid diglycerin ester (monomyristic acid diglycerin ester), monohexadecanoic acid diglycerin ester (Monopalmitic acid diglycerin ester), monooleic acid diglycerin ester, monoisostearic acid diglycerin ester and the like.

For example, as propylene glycol derivatives, specifically, propylene glycol octoate, octyl propylene glycol, propylene glycol decanoate, decyl propylene glycol, propylene glycol dodecanoate (propylene glycol laurate), dodecyl propylene glycol (lauryl propylene glycol) And propylene glycol tetradecanoate (propylene glycol myristate), tetradecyl propylene glycol (myristyl propylene glycol) and the like.

For example, specific examples of the butylene glycol derivative include butylene glycol octoate, octyl butylene glycol, butylene glycol decanoate, decyl butylene glycol, butylene glycol dodecanoate (butylene glycol laurate), dodecyl butylene glycol (lauryl butylene glycol) , Tetradecanoic acid butylene glycol (myristic acid butylene glycol), tetradecyl butylene glycol (myristyl butylene glycol) and the like.

Examples include monoethanolamide derivatives, monoethanolamine derivatives, diethanolamide derivatives, and diethanolamine derivatives. Specifically, lauric acid diethanolamide, coconut oil fatty acid diethanolamide, undecylenic acid monoethanolamide, lauric acid monoethanolamide, coconut oil fatty acid monoethanolamide, coconut oil fatty acid (POE) 2 monoethanolamide, coconut oil fatty acid N -Methyl monoethanolamide, lauryl diethanolamine, coconut oil fatty acid dimethylaminopropylamide and the like.

The amount of amphiphilic substance (surfactant auxiliary agent) whose ratio of (inorganic value / organic value) ratio is in the range of 0.8 to 1.5 is based on the total amount of the first agent or the second agent. The content is preferably 0.1 to 50% by mass, and more preferably 0.3 to 30% by mass.

“(D) Nonionic surfactant”
The (d) nonionic surfactant used in the present invention is a surfactant that is not ionized in an aqueous solution and has no electric charge. As the hydrophobic group, a type using alkyl and a type using dimethyl silicone are known.
Specifically, as the former, for example, glycerin fatty acid ester, ethylene oxide derivative of glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, ethylene oxide derivative of propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, polyethylene glycol alkyl ether, Examples include polyethylene glycol alkylphenyl ether, polyethylene glycol castor oil derivatives, polyethylene glycol hydrogenated castor oil derivatives, and the like.
Examples of the latter include polyether-modified silicone and polyglycerin-modified silicone. A type using alkyl as a hydrophobic group is preferred.

Specific examples of the lipophilic nonionic surfactant used in the present invention include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, Sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexyl diglycerol sorbitan, tetra-2-ethylhexyl diglycerol sorbitan, etc.), glycerin polyglycerin fatty acids (eg mono cottonseed oil fatty acid glycerin, monoeruka Acid glycerin, sesquioleic acid glycerin, glyceryl monostearate, α, α'-oleic acid pyroglutamic acid glycerin, monostearic acid glycerin malic acid, etc.), propylene glycol And fatty acid esters (for example, propylene glycol monostearate), hardened castor oil derivatives, glycerin alkyl ethers and the like.

Furthermore, specific examples of the hydrophilic nonionic surfactant used in the present invention include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan). Monooleate, POE-sorbitan tetraoleate, etc.), POE sorbite fatty acid esters (for example, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.) , POE-glycerin fatty acid esters (for example, POE-glycerin monostearate, POE-glycerin monoisostearate, POE-glycerin triisostearate, etc.), POE-fatty acid esters (Eg POE-distearate, POE-monodiolate, ethylene glycol distearate, etc.), POE-alkyl ethers (eg POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2- Octyldodecyl ether, POE-cholestanol ether, etc.), pluronic types (eg, pluronic etc.), POE • POP-alkyl ethers (eg, POE • POP-cetyl ether, POE • POP-2-decyl tetradecyl ether, POE / POP-monobutyl ether, POE / POP-hydrogenated lanolin, POE / POP-glycerin ether, etc.), Tetra POE / tetra-POP-ethylenediamine condensates (eg, Tetronic, etc.) ), POE-castor oil hardened castor oil derivatives (for example, POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil mono Pyroglutamic acid monoisostearic acid diester, POE-hardened castor oil maleic acid, etc., POE-honey beeswax lanolin derivatives (eg POE-sorbit beeswax etc.), alkanolamides (eg coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, Fatty acid isopropanolamide, etc.), POE-propylene glycol fatty acid ester, POE-alkylamine, POE-fatty acid amide, sucrose fatty acid ester, alkylethoxydimethylamine oxide-trioleyl phosphoric acid and the like.

In the present invention, (d) the HLB of the nonionic surfactant is preferably in the range of 5-14.
Specifically, for example, isostearyl glyceryl ether (HLB value 5), isostearic acid polyoxyethylene hydrogenated castor oil (HLB value 5), diisostearic acid PEG (6) (HLB value 5), dioleic acid PEG (6) (HLB) Value 5), polyglyceryl-3 diisostearate (HLB value 5), sorbitan distearate (HLB value 5), PEG-10 glyceryl triisostearate (HLB value 5), PEG-15 hydrogenated castor oil (HLB value) 5), POE (5) lauryl ether isostearate (HLB value 5), POE (2) cetyl ether (HLB value 5), PEG-3 glyceryl isostearate (HLB value 6), diisostearate PEG-8 (HLB value) 6), triisostearic acid POE (20) water Castor oil (HLB value 6), POE (3) cetyl ether (HLB value 6), POE (7) hydrogenated castor oil (HLB value 6), isostearic acid POE (15) hydrogenated castor oil (HLB value 7), Diisostearic acid POE (10) glyceryl (HLB value 7), dilauric acid POE (6) (HLB value 7), sorbitan sesquiisostearate (HLB value 7), triisostearic acid POE (30) hydrogenated castor oil (HLB value 7) ), Isostearic acid POE (3) (HLB value 7), isostearic acid POE (5) glyceryl (HLB value 8), isostearic acid POE (20) hydrogenated castor oil (HLB value 8), diisostearic acid POE (12) ( HLB value 8), POE (20) glyceryl triisostearate (HLB value 8), POE (5) isostearyl ester Tell (HLB value 8), POE (5) cetyl ether (HLB value 8), isostearic acid PEG-30 hydrogenated castor oil (HLB value 9), isostearic acid POE (6) (HLB value 9), hydrogenated lecithin ( HLB value 9), isostearic acid POE (10) glyceryl (HLB value 10), isostearic acid POE (8) glyceryl (HLB value 10), diisostearic acid POE (20) glyceryl (HLB value 10), triisostearic acid POE (30) ) Glyceryl (HLB value 10), POE (8) stearyl ether (HLB value 10), POE (7) cetyl ether (HLB value 10), monoisostearic acid POE (8) (HLB value 10), isostearic acid POE (40) ) Hydrogenated castor oil (HLB value 11), POE (10) isostearyl ether ( HLB value 11), isostearic acid POE (10) (HLB value 11), isostearic acid POE (15) glyceryl (HLB value 12), POE (15) isostearyl ether (HLB value 12), isostearic acid POE (20) glyceryl (HLB value 13), POE (20) isostearyl ether (HLB value 13), POE (60) hydrogenated castor oil (HLB value 14), isostearic acid POE (20) (HLB value 14), isostearic acid POE (40) Examples include glyceryl (HLB value 15), POE (25) isostearyl ether (HLB value 15), and the like.

(D) The blending amount of the nonionic surfactant is preferably 0.5 to 70% by mass, more preferably 1 to 50% by mass, based on the total amount of the first agent or the second agent.

“(E) Oil”
Examples of the (e) oil used in the present invention include hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, liquid oils, solid oils, waxes and the like that are usually used in cosmetics, quasi drugs, and the like. 1 type, or 2 or more types of oily components can be used.

Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, and microcrystalline wax.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) ) And the like.

Examples of higher alcohols include linear alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol), branched chain alcohols (eg, monostearyl glycerin ether (batyl alcohol)) -2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, octyldodecanol, etc.).

Synthetic ester oils include, for example, octyl octoate, nonyl nonanoate, cetyl octanoate, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, dimethyloctane Hexyldecyl acid, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl monoisostearate Glycol, neopentyl glycol dicaprate, tripropylene glycol pivalate, diisostearyl malate, di-2-heptyl unde Glyceryl acid, glyceryl diisostearate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, glyceryl trioctanoate, tri Glyceryl isopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate-2-ethylhexyl palmitate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleyl oleate, Acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, azide Di-2-heptyl undecylate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, succinic acid 2 -Ethylhexyl, triethyl citrate and the like.

Examples of the silicone oil include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.), cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexa Siloxane etc.) Silicone resin, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.), acrylic silicones forming a three-dimensional network structure Etc.

Examples of liquid oils and fats include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil-triglycerin and the like.

Examples of the solid fat include cacao butter, palm oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cattle Leg fats, moles, hydrogenated castor oil and the like.

Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, Examples include reduced lanolin, jojoballow, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, and POE hydrogenated lanolin alcohol ether.

(E) The blending amount of the oil is preferably 0.1 to 50% by mass, and more preferably 0.2 to 40% by mass with respect to the total amount of the first agent or the second agent.

“(C) or (f) Water”
The water contained in the oxidative hair dye of the present invention is not particularly limited, and specific examples thereof include purified water, ion exchange water, and tap water.
On the other hand, the amount of water of component (c) or component (f) is preferably 1 to 95% by mass, more preferably 5 to 80% by mass, based on the total amount of the first agent or the second agent.

By mixing the combination of the essential components (a) to (c) described above and the combination of the essential components (d) to (f) by the method described later, the bicontinuous microemulsion phase or It becomes a combination of essential components that form a lamellar liquid crystal phase.
Next, other essential components of the present invention will be described.

`` Alkaline agent ''
Examples of the alkaline agent contained in the first agent of the oxidative hair dye of the present invention include ammonia, ammonium salts such as ammonium hydrogen carbonate and ammonium phosphate, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, arginine and lysine. Basic amino acids such as guanidine, organic amines such as guanidine, 2-amino-2-methylpropane and monoisopropanolamine, and inorganic alkalis such as sodium hydroxide and potassium hydroxide can be used. Further, a buffer solution (for example, phosphoric acid-phosphoric acid sodium salt) in combination with these salts is used. Preferred alkali agents are ammonia, ammonium salts, and alkanolamines. These alkali agents can be used alone or in admixture of two or more.

The blending amount of the alkali agent is appropriately changed depending on the desired dyeing or bleaching effect, but the general blending amount is adjusted so that the pH of the first agent falls within the range of 8.0 to 13.0. Specifically, it is preferable to contain 0.1 to 10% by mass, particularly 0.5 to 5% by mass with respect to the entire composition when the first agent and the second agent are mixed. If the pH is less than 8, the bleaching effect may be inferior, and if it exceeds 13, the skin irritation and hair damage are severe, which is not desirable.

"Oxidative dye"
Examples of the oxidation dye blended in the first agent of the hair dye of the present invention include p-phenylenediamine, p-toluylenediamine, N-methyl-p-phenylenediamine, N, N-dimethyl-p-phenylene. Diamine, N, N-diethyl-2-methyl-p-phenylenediamine, N-ethyl-N- (hydroxyethyl) -p-phenylenediamine, chloro-p-phenylenediamine, 2- (2'-hydroxyethylamino) -5-aminotoluene, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, methoxy-p-phenylenediamine, 2,6-dichloro-p-phenylenediamine, 2-chloro-6-bromo- p-phenylenediamine, 2-chloro-6-methyl-p-phenylenediamine, 6-methoxy-3-methyl-p-phenyle One or more NH2-groups such as diamine, 2,5-diaminoanisole, N- (2-hydroxypropyl) -p-phenylenediamine, N-2-methoxyethyl-p-phenylenediamine, NHR -P-phenylenediamines having a group or NHR 2-group (R represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group); 2,5-diaminopyridine derivatives; p-aminophenol, 2-methyl- 4-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol, 2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4 -Aminophenol, 2,3-dimethyl-4-aminophenol, 2,5-dimethyl-4-aminophenol, 2,4-diaminophenol Nord, p- aminophenols such as 5-aminosalicylic acid, o- aminophenol, can be blended o- phenylenediamine and the like.

Further, a coupler can be blended, for example, α-naphthol, o-cresol, m-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol. 3,5-dimethylphenol, benzcatechin, pyrogallol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, 5- (2'-hydroxyethylamino) -4 -Methoxyphenol, hydroquinone, 2,4-diaminoanisole, m-toluylenediamine, 4-aminophenol, resorcin, resorcin monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone 1-phenyl-3-amino-5-pyrazolone, 1-phenyl-3,5-diketo Lazolidine, 1-methyl-7-dimethylamino-4-hydroxy-2-quinolone, m-aminophenol, 4-chlororesorcin, 2-methylresorcin, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 3,5-diaminotrifluoromethylbenzene, 2,4-diaminofluorobenzene, 3,5-diaminofluorobenzene, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-triaminopyrimidine, 2-amino -4,6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 4,6-diamino-2-hydroxypyrimidine and the like can be blended.

In addition to the above substances, substances described in “Quasi-drug standards” (Pharmaceutical Daily, published in June 1991) can be appropriately mixed. Furthermore, an acid dye, a basic dye, and an HC dye can be blended.
In addition, what does not mix | blend these dyes in this invention is used as hair bleach.

The blending amount of the oxidation dye is preferably 0.001 to 5% by mass, and more preferably 0.01 to 3% by mass, based on the total amount of the first agent.

"Oxidant"
Examples of the oxidizing agent blended with the second agent include hydrogen peroxide, urea peroxide, persulfate, perborate, percarbonate, bromate, periodate, and the like. It is preferable to use hydrogen.
The content of the oxidizing agent is preferably 0.1 to 12% by mass in the second agent, and more preferably 1 to 9% by mass. If it is less than 0.1% by mass, the hair bleaching effect is inferior, and if it exceeds 12% by mass, no further effect can be expected, and skin irritation and damage to the hair become serious.

The oxidative hair dye of the present invention can be used by mixing the first agent and the second agent at an arbitrary ratio, but the mixing mass ratio is the first agent: second agent = 2: 1 to 1: 5. It is preferable that the dyeing power or the bleaching effect is more exhibited when the ratio is 1: 1 to 1: 3.

Further, in the present invention, one or both of the first agent and the second agent are other components used in normal cosmetics, for example, oily components other than those described above, surfactants, silicones, aromatic alcohols, many Alcohols such as monohydric alcohols, amino acids, conditioning agents, thickeners, pH adjusters, moisturizers, animal and plant extracts, vitamins, dyes, fragrances, pigments, preservatives, UV absorbers, sequestering agents, reductions One or two or more kinds of agents and the like can be appropriately blended within a range not impairing the effects of the present invention. Below, the arbitrary component which can be mix | blended of this invention is illustrated concretely.

"Alcohols"
You may mix | blend various water-soluble alcohol with the oxidative hair dye of this invention.
Water-soluble alcohols include lower alcohols, polyhydric alcohols, polyhydric alcohol polymers, dihydric alcohol alkyl ethers, dihydric alcohol ether esters, glycerin monoalkyl ethers, sugar alcohols, monosaccharides, oligosaccharides, polysaccharides and derivatives thereof. It is 1 type, or 2 or more types chosen from.

Examples of lower alcohols include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.

Examples of the polyhydric alcohol include dihydric alcohols (eg, dipropylene glycol, 1,3-butylene glycol, ethylene glycol, trimethylene glycol, 1,2-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, Pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.), trihydric alcohol (eg, glycerin, trimethylolpropane, etc.), tetrahydric alcohol (eg, diglycerin, 1,2, , 6-hexanetriol, etc.), pentahydric alcohol (eg, xylitol, triglycerin, etc.), hexahydric alcohol (eg, sorbitol, mannitol, etc.), polyhydric alcohol polymer (eg, diethylene glycol) Dipropylene glycol-triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin-triglycerin, tetraglycerin, polyglycerin, etc.), dihydric alcohol alkyl ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol) Monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Djibouti Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc.) Tellester (eg, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazinate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.), glycerin monoalkyl ether (eg, chimyl alcohol, ceralkyl alcohol) Batyl alcohol, etc.), sugar alcohols (eg maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, amylolytic sugar reducing alcohol, etc.), glycolide, tetrahydrofurfuryl alcohol, POE- Examples include tetrahydrofurfuryl alcohol, POP-butyl ether, POP / POE-butyl ether tripolyoxypropylene glycerin ether, POP-glycerin ether, POP-glycerin ether phosphate, POP / POE-pentaneerythritol ether, polyglycerin and the like.

Examples of monosaccharides include tricarbon sugars (eg, D-glyceryl aldehyde, dihydroxyacetone, etc.), tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-threose, erythritol, etc.), pentose sugars (eg, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc., hexose (eg, D-glucose, D-talose, D -Bucicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.), pentose sugar (eg, aldheptose, heprose, etc.), octose sugar (eg, octulose, etc.), deoxy sugar ( For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy- -Mannose, etc.), amino sugar (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.), uronic acid (eg, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D -Galacturonic acid, L-iduronic acid, etc.).

Oligosaccharides include, for example, sucrose, guntianose, umbelliferose, lactose, planteose, isoliquinoses, α, α-trehalose, raffinose, lycnose, umbilicin, stachyose verbus courses, and the like.

Examples of the polysaccharide include cellulose, quince seed, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate-tragacanth gum, keratan sulfate, chondroitin, xanthan gum, guar gum, dextran, kerato sulfate, locust bean gum, saxino glucan, etc. Is mentioned.

Other polyols include polyoxyethylene methyl glucoside (Glucam E-10), polyoxypropylene methyl glucoside (Glucam P-10) and the like.

"Thickener"
Various thickeners may be added to the oxidative hair dye of the present invention.
Examples of thickeners include gum arabic, carrageenan, colored yam, gum tragacanth, carob gum, quince seed (malmello), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose, CMC, hydroxyethylcellulose, hydroxypropyl Cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, cellulose dialkyldimethylammonium sulfate, xanthan gum, magnesium aluminum silicate, bentonite, hectorite, AlMg silicate (Beegum), Examples thereof include laponite and silicic anhydride.

Examples of natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, colored yam, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid), microbial polymers (eg, xanthan gum, dextran, succinoglucan, pullulan, etc.), animal polymers (eg, collagen, casein, albumin, gelatin, etc.), etc. Is mentioned.

Examples of semi-synthetic water-soluble polymers include starch polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.), cellulose polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate). Hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, etc.), alginic acid polymers (for example, sodium alginate, propylene glycol alginate, etc.) and the like.

Examples of the synthetic water-soluble polymer include vinyl polymers (for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer, etc.) and polyoxyethylene polymers (for example, polyethylene glycol 20,000, 40). , 000, 60,000, etc.), acrylic polymers (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.), polyethyleneimine, cationic polymers and the like.

"UV absorber"
You may mix | blend various ultraviolet absorbers with the oxidative hair dye of this invention.
Examples of the water-soluble ultraviolet absorber include 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4 '-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2 -Benzophenone UV absorbers such as ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, phenylbenzimidazole-5-sulfone Acid and its salts Benzimidazole ultraviolet absorbers such as phenylene-bis-benzimidazole-tetrasulfonic acid and its salts, 3- (4′-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanin Examples include acid and urocanic acid ethyl ester.

Examples of oil-soluble ultraviolet absorbers include paraaminobenzoic acid (PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, Benzoic acid UV absorbers such as N-dimethyl PABA butyl ester; Anthranilic acid UV absorbers such as homomenthyl-N-acetylanthranilate; Amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate , Salicylic acid ultraviolet absorbers such as p-isopropanolphenyl salicylate; octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate Ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p- Methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α -Cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, 3-methyl-4- [methylbis (trimethylsiloxy) silyl] butyl 3,4,5-trimethoxycinnamate Cinnamic acid UV absorption Agents: 2-phenyl-5-methylbenzoxazole, 2,2′-hydroxy-5-methylphenylbenzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2 '-Hydroxy-5'-methylphenylbenzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-tert-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentane- Examples include 2-one and octocrylene.

"Powder ingredient"
Various powder components may be blended in the oxidative hair dye of the present invention.
Examples of the powder component include inorganic powders (for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid. Aluminum, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder , Metal soap (eg, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc.), organic powder (eg, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, Styrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.), inorganic white pigment (eg, titanium dioxide, zinc oxide, etc.), inorganic red pigment (eg, , Iron oxide (Bengara), iron titanate, etc.), inorganic brown pigments (eg, γ-iron oxide), inorganic yellow pigments (eg, yellow iron oxide, ocher), inorganic black pigments (eg, black) Iron oxide, low-order titanium oxide, etc.), inorganic purple pigments (eg, mango violet, cobalt violet, etc.), inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.), inorganic blue pigments (eg, For example, ultramarine, bitumen, etc.), pearl pigments (eg, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated tar) , Colored titanium oxide coated mica, bismuth oxychloride, fish scale foil, etc.), metal powder pigments (eg, aluminum powder, copper powder, etc.), organic pigments such as zirconium, barium or aluminum lake (eg, red 201, red 202) No., Red 204, Red 205, Red 220, Red 226, Red 228, Red 405, Orange 203, Orange 204, Yellow 205, Yellow 401, and Blue 404 Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3 and Blue No. 1), natural pigments (eg, chlorophyll, β-carotene, etc.) and the like.

"Moisturizer"
You may mix | blend various moisturizers with the oxidative hair dye of this invention.
Examples of the humectant include chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salt, DL-pyrrolidone carboxylate, short chain soluble collagen, diglycerin (EO) PO adduct, Izayoi rose extract, Achillea millefolium extract, Merirot extract and the like.

"Metal sequestering agent"
You may mix | blend various metal ion sequestering agents with the oxidative hair dye of this invention.
Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate. Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate and the like.

"amino acid"
Various amino acids may be added to the oxidative hair dye of the present invention.
Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.), basic amino acids (eg, hydroxylysine, etc.), and the like. Examples of amino acid derivatives include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione and the like.

"Organic amine"
Various organic amines may be blended in the oxidative hair dye of the present invention.
Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, morpholine, tetrakis (2-hydroxypropyl) ethylenediamine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino Examples include -2-methyl-1-propanol.

"Polymer emulsion"
You may mix | blend various polymer emulsions with the oxidative hair dye of this invention.
Examples of the polymer emulsion include an acrylic resin emulsion, a polyethyl acrylate emulsion, an acrylic resin liquid, a polyacryl alkyl ester emulsion, a polyvinyl acetate resin emulsion, and a natural rubber latex.

`` PH adjuster ''
You may mix | blend various pH adjusters with the oxidative hair dye of this invention.
Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

"Vitamins"
Various vitamins may be added to the oxidative hair dye of the present invention.
Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.

"Antioxidant"
You may mix | blend various antioxidant with the oxidation hair dye of this invention.
Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.
Examples of the antioxidant assistant include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

Other ingredients that can be blended include, for example, preservatives (methylparaben, ethylparaben, butylparaben, phenoxyethanol, etc.), anti-inflammatory agents (for example, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.), Whitening agents (eg, placenta extract, yukinoshita extract, arbutin, etc.), various extracts (eg, buckwheat, auren, shikon, peonies, assembly, birch, sage, loquat, carrot, aloe, mallow, iris, grape, yokoinin , Loofah, lily, saffron, senkyu, ginger, hypericum, onionis, garlic, pepper, chimpi, toki, seaweed, etc.), activator (eg, royal jelly, photosensitizer, cholesterol derivative, etc.), blood circulation promoter (eg, , Nonyl acid wallenyl amide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, tannic acid, α-borneol, nicotinic acid tocopherol, inositol hexanicotinate, cyclandrate, cinnarizine, Trazoline, acetylcholine, verapamil, cephalanthin, γ-oryzanol, etc.), antiseborrheic agents (eg, sulfur, thianthol, etc.), anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.).

The oxidative hair dye of the present invention comprises the above-mentioned alkaline agent, oxidant, oxidative dye (but not blended in the case of hair bleach), and components (a) to (a) to form a bicontinuous microemulsion phase or lamellar liquid crystal phase. An oxidative hair dye comprising the first agent and the second agent, which contains (c) or components (d) to (f) and other components are added as necessary within a range not impairing the effects of the present invention. Yes, the first agent and the second agent are mixed, and contain a phase showing a bicontinuous microemulsion phase or a lamellar liquid crystal phase immediately after shaking.

The bicontinuous microemulsion phase and the lamellar liquid crystal phase, which are requirements of the present invention, are in a thermodynamic equilibrium state and are generated regardless of the order of addition of the essential blending components. Therefore, any order of addition can be produced.
However, in order to reach the equilibrium state most quickly, a water-soluble substance such as water, a surfactant, or an alkali agent is mixed to prepare an aqueous solution having a sufficiently low interfacial tension, and then a surfactant assistant (copolymer). Surfactant) and oil-soluble substances are preferably added gradually with stirring.

In order to produce an oxidative hair dye containing a bicontinuous microemulsion phase or a lamellar liquid crystal phase, it can be conveniently produced by the following steps.
(1) An ionic surfactant mixture in which the mixing ratio of an anionic surfactant and an amphoteric surfactant and / or a cationic surfactant is changed is prepared, and component (c) water is added to each.
(2) Finding a mixing range of an anionic surfactant exhibiting a low interfacial tension, an amphoteric surfactant and / or a cationic surfactant. This mixing range is a range of about ± 2 on both sides centering on the mixing ratio with the lowest interfacial tension. An example of interfacial tension measurement is shown in FIG. Figure 1 shows the surface tension against decane using 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine as the amphoteric surfactant and polyoxyethylene (2 mol) sodium lauryl ether sulfate as the anionic surfactant. It is measured. FIG. 1 shows that the mixing ratio of the component (A) and the component (B) is 5: 5 to 9: 1, which is the mixing range where the interfacial tension is low.
(3) Add other water-soluble additives to the ionic surfactant mixed aqueous solution having the mixing ratio obtained in (2), and stir and mix.
(4) Component (b) surfactant (cosurfactant) is gradually added to (3) while applying a relatively strong stirring force.
(5) Add other oil-soluble additives and stir and mix.
Whether or not the composition produced in the above process contains a bicontinuous phase and / or a lamellar liquid crystal phase is confirmed by the following steps.
(6) The final mixed composition obtained in (5) is put into a screw test tube (sample tube), shaken vigorously, and left in a constant temperature water bath at 25 ° C. or centrifuged. Visually confirm that each composition solution is separated into a transparent, translucent and uniform phase (first determin step).
(7) Thereafter, the composition is held while the two polarizing plates are combined with a phase difference of 90 degrees, and the light transmittance is confirmed (second determin step).
(8) Further, the viscosity of each phase of this sample is visually confirmed by gently shaking the screw cap test tube (third determin step).

If it is a uniform transparent or translucent phase in the first determin step and light transmission is observed in the second determin step, it is considered to be a liquid crystal phase. The following methods 1 to 5 are effective for distinguishing between a lamellar liquid crystal phase and another optically anisotropic liquid crystal phase.
On the other hand, when it is a uniform transparent phase in the first determin step and no light transmission is observed in the second determin step, it is considered to be a microemulsion phase. In order to distinguish between the bicontinuous microemulsion phase and the other micelle aqueous solution or reverse micelle oil solution which are optically isotropic phases, the following methods 2 to 5 are effective.

Whether the composition obtained by the above method contains a bicontinuous microemulsion phase or a lamellar liquid crystal phase is: 1. Observation with polarizing microscope and X-ray structural analysis 2. creation of phase equilibrium diagram; 3. Electrical conductivity measurement 4. Measurement of self-diffusion coefficient by NMR; This can be determined by electron microscope observation of a replica prepared using the freeze fracture method. It may be determined by any method.
"1. Observation with polarizing microscope and X-ray structural analysis"
According to observation with a polarizing microscope and X-ray structure analysis, when an anisotropic band-like pattern is observed and a scattering peak corresponding to the layer interval appears, it is considered to be a lamellar liquid crystal phase. In the third determinating step, it can be confirmed that a planar lamellar liquid crystal phase is obtained if the liquid is low viscosity, and a concentric lamellar liquid crystal is used if the liquid is slightly high viscosity.
Further, when an anisotropic streak pattern is observed and a sharp scattering peak appears in the hexagonal rod-like micelle interval period, it is considered to be a hexagonal liquid crystal phase. When it is a dark field by polarization microscope observation and a spot with cubic symmetry appears, it is considered to be a cubic liquid crystal phase.
“2. Creation of phase equilibrium diagram”
When a phase equilibrium diagram of a three-component system composed of water / oil component / surfactant (oil component includes cosurfactant surfactant) is created, the bicontinuous microemulsion phase is isotropic and transparent. Viscosity is a one-phase region and is not a region that is continuous from both water and oil peaks, and the concentration range in which a lamellar liquid crystal phase is generated is a region that is adjacent to an aqueous micellar phase or a bicontinuous microemulsion phase. However, this feature differs depending on the system (component) to be constructed.
“3. Electrical conductivity measurement”
It is known that the conductivity of the bicontinuous microemulsion phase takes about 2/3 that of the aqueous micellar phase obtained in the same system. The liquid crystal phase has characteristic electrical properties due to the fluidity, structural continuity, and anisotropy of each phase, so information on the phase can be obtained by conducting conductivity measurement under appropriate conditions. Is possible.
“4. Self-diffusion coefficient measurement by NMR”
Lindman et al. Colloid Interface Sci. , 1981, 83, 569 and the like.
"5. Electron microscope observation by freeze fracture method"
According to the electron microscope observation of the phase sample prepared using the freeze fracture method, the bicontinuous microemulsion phase can obtain an image in which both water and oil are continuous, and the lamellar liquid crystal phase has an image of a layered structure. It is possible to obtain. This method is described in the literature Colloid polym. Sci. 1994, 272, 604.

The present invention is an oxidative hair dye characterized by mixing a first agent and a second agent and containing a phase showing a bicontinuous microemulsion or a lamellar liquid crystal phase immediately after shaking. Therefore, the 1st agent and 2nd agent before mixing may contain the phase which shows a bicontinuous microemulsion phase or a lamellar liquid crystal phase, and does not need to contain it.
Once the composition of the final composition (after mixing of the first and second agents) is determined by the above method, a component that forms a bicontinuous microemulsion phase or a lamellar liquid crystal phase in consideration of the pH stability of various components It is desirable that the essential components (a) to (c) or the components (d) to (f) are appropriately distributed to the first agent or the second agent.

Next, the present invention will be described in more detail with reference to examples. Note that the present invention is not limited to this. A compounding quantity represents the mass%.

First, the evaluation method used in each test example will be described.

Evaluation (1): Association state The association state of 10 g of the dye solution in which the first agent and the second agent were mixed was evaluated. The above-described method was used to determine the meeting state.
L3: contains a bicontinuous microemulsion phase Lα: contains a lamellar liquid crystal phase ×: contains neither a bicontinuous microemulsion phase nor a lamellar liquid crystal phase

Evaluation (2): Dyeing effect 10 g of the dyeing solution in which the first agent and the second agent are mixed is uniformly applied to a human hair bundle having a weight of 3 g and a length of 15 cm, left for 20 minutes, and then thoroughly washed. It was dried and evaluated based on the following criteria by seven professional subjects.
A: Very good (the number of subjects who answered that the staining effect was high was 6-7 out of 7)
○: Good (the number of subjects who answered that the staining effect was high was 4-5 out of 7)
Δ: Slightly bad (The number of subjects who answered that the staining effect was high was 2 to 3 of 7)
×: Poor (the number of subjects who answered that the staining effect was high was 0 to 1 out of 7)

Evaluation (3): Color unevenness after dyeing 10 g of a dye solution in which the first agent and the second agent are mixed is uniformly applied to a human hair bundle having a weight of 3 g and a length of 15 cm, and left for 20 minutes. After washing, it was dried and evaluated by 7 professional subjects based on the following criteria.
A: Very good (the number of subjects who answered that there was little color unevenness after dyeing was 6 to 7 out of 7)
○: Good (the number of subjects who answered that there was little color unevenness after dyeing was 4-5 out of 7)
△: Slightly bad (2 to 3 of 7 subjects answered that there was little color unevenness after staining)
×: Poor (the number of subjects who answered that there was little color unevenness after staining was 0 to 1 of 7 subjects)

In evaluation (2) and evaluation (3), the following three types of human hair bundles were evaluated.
Healthy hair: Black hair bundle Damaged hair: Healthy hair subjected to bleach treatment at room temperature for 20 minutes High-damaged hair: Healthy hair subjected to bleach treatment at room temperature for 45 minutes

"Formation of ionic surfactant"
The oxidative hair dye of the Example which consists of a mixing | blending composition described in the following Table 1 was manufactured, and the evaluation test was done about said evaluation (1)-(3).

(The total of one agent and two agents is 100% by mass.)
* Average value of 5% by mass of mono-octyl monoglyceryl ether (IOB value 1.048) and 5% by mass of propylene glycol laurate (IOB value 0.53), which are amphiphiles

From the results shown in Table 1, the test example 1-3 containing no ionic surfactant (comparative example containing neither the lamellar liquid crystal phase nor the bicontinuous microemulsion phase), the dyeing effect on damaged hair, particularly high-damaged hair, and The hair feel was inferior.
On the other hand, Test Example 1-1 (Example of the present invention) containing an ionic surfactant contained a lamellar liquid crystal phase when one agent and two agents were mixed, and Test Example 1-2 (Example of the present invention) was It contained a bicontinuous microemulsion phase, and was excellent in dyeing effect and feel of hair after dyeing for healthy hair, damaged hair, and high-damaged hair.

<Color loss evaluation by shampoo after hair dyeing>
Test Examples 1-1 and 1-2 and the following Comparative Example 1 (Comparative Example 1 contains a nonionic surfactant and an oil component, but its blending amount and HLB are not properly adjusted. The hair dye which does not contain a nuus microemulsion phase and a lamellar liquid crystal phase.) The hair was uniformly applied to a human hair bundle having a weight of 3 g and a length of 15 cm, left for 20 minutes, and then thoroughly washed and dried. Further, shampoo washing was performed twice thereafter, and the brightness difference (ΔL) and color difference (ΔE) before and after shampooing were measured. The measurement results are shown in FIG.
“Comparative Example 1 (1 agent: 2 agent mixing ratio = 1: 2)” <1 agent>
Alkyltrimethylammonium chloride 2
Deodorized cetanol 6
(E) Liquid paraffin 2
Propylene glycol 5
Glycerin 5
(D) Polyoxyethylene cetyl ether (HLB14) 1
(D) Polyoxyethylene oleyl ether (HLB16) 0.5
Ammonia water (28%) 8
2-Amino-2-methyl-1-propanol 0.5
Paraphenylenediamine 0.4
Resorcin 0.2
5-Aminoorthocresol 0.2
Paraaminophenol (oxidative dye) 1
Hydrochloric acid 2,4-diaminophenoxyethanol 0.04
Sodium hydrosulfite 0.1
L-ascorbic acid 0.6
Edetate disodium 0.2
(F) Purified water remainder (total 100% by mass)
<2 agents>
Hydrogen peroxide solution (30%) 5
Phosphoric acid 0.24
Disodium hydrogen phosphate 0.3
Phenoxyethanol appropriate amount edetate disodium appropriate amount (f) purified water remainder

It is known that fading occurs due to shampooing after hair dyeing. As shown in FIG. 2, Test Example 1-1 containing the lamellar liquid crystal phase and Test Example 1-2 containing the bicontinuous microemulsion phase immediately after shaking after mixing the first agent and the second agent are: It was confirmed that the color difference before and after the shampoo was small as compared with Comparative Example 1 in which neither the lamellar liquid crystal phase nor the bicontinuous microemulsion phase was contained.
The oxidative hair dye of the present invention containing a phase showing a bicontinuous microemulsion or a lamellar liquid crystal phase immediately after shaking is mixed with the first agent and the second agent has little color fading due to shampoo after hair dyeing, excellent It was found to be a base.

"Surfactant additive"
The oxidation hair dye of the test example which consists of a mixing | blending composition described in the following Table 2 was manufactured, and the evaluation test was done about evaluation (1)-(3).

(The total of one agent and two agents is 100% by mass.)
* Average value of 5% by mass of monodecyl monoglyceryl ether (IOB value 0.88) and 5% by mass of propylene glycol laurate (IOB value 0.53), which are amphiphiles

From the results shown in Table 2, Test Example 2-2 containing no surfactant assistant (Comparative Example containing neither the lamellar liquid crystal phase nor the bicontinuous microemulsion phase) is inferior in the dyeing effect and hair feel to healthy hair. It was a thing.
On the other hand, Test Example 2-1 (Example of the present invention) containing a surfactant aid contains a lamellar liquid crystal phase when mixed with one agent and two agents, and can be used for healthy hair, damaged hair, or high-damaged hair. However, the dyeing effect and the feel of the hair after dyeing were excellent.

"Blend ratio of anionic / amphoteric surfactant"
The oxidation hair dye of the test example which consists of a mixing | blending composition described in the following Table 3 was manufactured, and the evaluation test was done about evaluation (1)-(3).

(The total of one agent and two agents is 100% by mass.)
* The average value of 3.8% by mass of amphiphilic substance monodecyl monoglyceryl ether (IOB value 0.88) and propylene glycol decanoate (IOB value 0.62)

From the results of Table 3, Test Examples 3-1 and 3-6 in which the mass ratio of the anionic surfactant to the amphoteric surfactant is 10: 0 and 0:10 (the lamellar liquid crystal phase is also a bicontinuous microemulsion phase) Comparative Example), which also contains no hair, was inferior in dyeing effect and hair feel to healthy hair.
On the other hand, Test Examples 3-2 to 5 (Examples of the present invention) in which the mass ratio of the anionic surfactant to the amphoteric surfactant is 2: 8 to 8: 2 is a lamellar liquid crystal when one agent and two agents are mixed. It contained a phase and was excellent in dyeing effect and feel of hair after dyeing for healthy hair, damaged hair, and high-damaged hair.

"Concentration of surfactant / surfactant aid"
The oxidation hair dye of the test example which consists of a mixing | blending composition described in the following Table 4 was manufactured, and the evaluation test was done about evaluation (1)-(3).

(The total of one agent and two agents is 100% by mass)
* Average value of amphiphile monooctyl monoglyceryl ether (IOB value 1.048) and propylene glycol laurate (IOB value 0.53)

From the results shown in Table 4, Test Example 4-4 (Comparative Example containing neither a lamellar liquid crystal phase nor a bicontinuous microemulsion phase) having a low blending concentration of ionic surfactant and surfactant is particularly effective for healthy hair. The dyeing effect and hair feel were inferior.
On the other hand, Test Examples 4-1 to 3 (Examples of the present invention) in which the blending concentrations of the ionic surfactant and the surfactant aid are suitable contain a lamellar liquid crystal phase when mixed with one agent and two agents, and healthy hair The dyeing effect and the hair feel after dyeing were excellent for both damaged hair and high-damaged hair.

"Nonionic surfactant formulation"
The oxidation hair dye of the test example which consists of a mixing | blending composition described in the following Table 4 was manufactured, and the evaluation test was done about evaluation (1)-(5).

(The total of one agent and two agents is 100% by mass.)

From the results of Table 5, Test Example 5-3 (Comparative Example in which the lamellar liquid crystal phase does not contain the bicontinuous microemulsion phase) is inferior in dyeing effect and hair feel to damaged hair, particularly high-damaged hair. there were.
On the other hand, Test Example 5-1 (Example of the present invention) in which the association state of the surfactant was appropriately controlled by blending the nonionic surfactant and the oil component was a bicontinuous microemulsion when mixing one agent and two agents. Test Example 5-2 (Example of the present invention) contains a lamellar liquid crystal phase, and has a dyeing effect on the healthy hair, damaged hair, and high-damaged hair, and the feel of the hair after dyeing. It was excellent.

The following are examples of formulating the oxidative hair dye of the present invention. The obtained oxidative hair dye was excellent in hair dyeing property, had good safety and use feeling, and had high base stability.

"Example: Oxidative hair dye"
<1 agent>
(A) Lauryldimethylaminoacetic acid betaine 18
(A) Polyoxyethylene lauryl ether sulfate triethanolamine 6
Dodecylbenzenesulfonic acid triethanolamine 6
Isopropanol 9.5
Propylene glycol 10
Octyl octoate 2
Strong ammonia water (28%) 8.6
Ethanolamine 2.4
Hydrosulfite sodium 0.1
Ascorbic acid 0.3
Cationized silk protein 0.1
Edetic acid disodium 0.2
Resorcin 1
Perfume Appropriate amount (c) Purified water remainder (total 100% by mass)
<2 agents>
Hydrogen peroxide solution (30%) 18
(B) Monooctyl monoglyceryl ether 8
(B) Propylene glycol laurate 7
Phosphoric acid 0.2
Sodium monohydrogen phosphate 0.2
Sodium stannate 0.02
Paraoxybenzoic acid ester appropriate amount (c) purified water remainder (total 100% by mass)
* PH of 1 agent = 11.1, pH of 2 agents = 3.01
* The ratio of (inorganic value / organic value) of the amphiphile is 0.81 {8% monooctyl monoglyceryl ether (IOB value 1.048) and propylene glycol laurate (IOB value 0.53) 7 % Average value}

"Example: Oxidative hair dye"
<1 agent>
1,3-butylene glycol 5
(D) Polyoxyethylene (10EO) cetyl ether 15
(D) Polyoxyethylene glyceryl oleate (8EO) 15
O- [2-hydroxy-3- (trimethylammonio) propyl] chloride
Hydroxyethyl cellulose 0.5
Strong ammonia water (28%) 15
Ethanolamine 2
Ascorbic acid 0.6
DL-pyrrolidonecarboxylate sodium solution 0.1
Hydroxyethanediphosphonic acid tetrasodium 0.3
Resorcin 0.15
Perfume Appropriate amount (f) Purified water remaining (total 100% by mass)
<2 agents>
(E) Liquid paraffin 5
Cetostearyl alcohol 2
Sodium lauryl sulfate 0.1
Hydrogen peroxide solution (30%) 18
Phosphoric acid 0.1
Anhydrous sodium monohydrogen phosphate 0.1
Sodium stannate 0.02
P-Hydroxybenzoate ester (f) Purified water Residual (100% by mass in total)
* PH of 1 agent = 11.02, pH of 2 agents = 3.0
* The HLB of the nonionic surfactant is 10.5 {polyoxyethylene (10EO) cetyl ether (HLB = 11) 15% which is a nonionic surfactant and polyoxyethylene glyceryl oleate (8EO) (HLB = 10) Average value of 15%}

According to the present invention, by incorporating a bicontinuous microemulsion phase or a lamellar liquid crystal phase into the base, damaged hair (chemical damage such as hair dyes and permanent agents, physical damage such as friction) It is possible to provide an oxidative hair dye excellent in dyeability for both damaged hair) and healthy hair that is not damaged.
Moreover, according to this invention, it is possible to provide the oxidation hair dye which is excellent also in the inhibitory effect of the discoloration by the washing | cleaning after hair dyeing.

Claims (7)

1. In the oxidative hair dye which mixes the 1st agent containing an alkali agent and the 2nd agent containing an oxidizing agent, immediately after mixing the said 1st agent and a 2nd agent, a bicontinuous microemulsion phase or a lamellar liquid crystal Oxidative hair dye characterized by containing a phase.
2. The oxidative dyeing according to claim 1, wherein the first agent and / or the second agent contain the following components (a) to (c) that form a bicontinuous microemulsion phase or a lamellar liquid crystal phase. Hair agent.
   (A) ionic surfactant (b) amphiphile having a ratio of (inorganic value / organic value) ratio in the range of 0.8 to 1.5 (c) water
3. The oxidative dyeing according to claim 1, wherein the first agent and / or the second agent contain the following components (d) to (f) that form a bicontinuous microemulsion phase or a lamellar liquid crystal phase. Hair agent.
   (D) Nonionic surfactant (e) Oil (f) Water
4. The component (a) ionic surfactant contains an anionic surfactant, and further contains one or more selected from amphoteric surfactants and / or cationic surfactants. 2. Oxidative hair dye according to 2.
5. In the component (a) ionic surfactant, the mass ratio of the anionic surfactant to the amphoteric surfactant and / or the cationic surfactant is (anionic surfactant): (amphoteric surfactant) And / or a cationic surfactant) = 2: 8 to 8: 2.
6. The amphiphilic substance whose component (b) (inorganic value / organic value) ratio is in the range of 0.8 to 1.5 is a monoglycerin derivative, diglycerin derivative, propylene glycol derivative, butylene glycol. The oxidative hair dye according to claim 2, wherein the hair dye is one or more selected from a derivative, a monoethanolamide derivative, a monoethanolamine derivative, a diethanolamide derivative, and a diethanolamine derivative.
7. The oxidative hair dye according to claim 3, wherein the component (d) nonionic surfactant has an HLB in the range of 5 to 14.

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