WO2019163497A1

WO2019163497A1 - Hairdye

Info

Publication number: WO2019163497A1
Application number: PCT/JP2019/003830
Authority: WO
Inventors: 幸蔵佐藤; 佐藤　忠久
Original assignee: 株式会社Ｎｉｌ
Priority date: 2018-02-20
Filing date: 2019-02-04
Publication date: 2019-08-29
Also published as: JPWO2019163497A1; CN110573135A; TW201938224A; JP6624628B1; CN110573135B

Abstract

Provided is a hairdye which has excellent hair-dyeing properties, is easy to use, can dye the hair in a short time, and is highly safe for the hair and scalp. The hairdye comprises the following ingredient (1) and ingredient (2) together or separately: ingredient (1) is one or more colorants and/or precursors thereof, which are selected from the group consisting of colorants having a catechol structure, colorants having a pyrogallol structure, colorants having an α-hydroxycarbonyl structure, colorants having a β-hydroxycarbonyl structure, and precursors of these colorants; and ingredient (2) is an organotitanium compound and/or an organozirconium compound. Also provided is a method of hair dyeing, which comprises applying the ingredient (1) and the ingredient (2) to the hair at the same time or separately.

Description

Hair dye

The present invention relates to a hair dye having excellent hair dyeing properties and convenience, and excellent safety for hair and scalp.

Conventionally, oxidative hair dyes using paraphenylenediamines have been widely used. This hair dye contains a first liquid containing an intermediate of an oxidizing dye such as paraphenylenediamine and 2,5-diaminotoluene, an alkaline agent such as ammonia and ethanolamine, and a first liquid containing an oxidizing agent such as hydrogen peroxide. It consists of two liquids. Hair dyes using oxidative hair dyes have high hair dyeing power and fastness because the oxidative dye intermediate penetrates into the hair and dyes hair by oxidative coupling to form pigments. It is known to be excellent and less fading due to shampoo, rinse or light. In addition, melanin decolorization and hair dyeing can be performed simultaneously by the action of hydrogen peroxide, and there is an advantage that hair can be dyed even in bright colors.

However, the hair dyes using the above-mentioned oxidative hair dyes have a problem that the hair and scalp are damaged by the alkaline agent and hydrogen peroxide used for the hair dyeing treatment. In addition, it has been pointed out that intermediates of oxidation dyes such as paraphenylenediamine and 2,5-diaminotoluene cause skin allergies and are suspected to be mutagenic.

On the other hand, color treatments and hair manicures that adsorb acid dyes or basic dyes to the surface of hair have been proposed as hair dyes that are easy to use. However, when these are used for hair dyeing, the dyeing properties and shampoo resistance are not sufficient, so that it is necessary to frequently carry out hair dyeing and there is a problem of skin coloring. Furthermore, there was also a safety risk due to the nitro group and phenylenediamine structure contained in the dye.

Various proposals have been made to improve the safety of hair dyes. For example, naturally-occurring plant pigments such as henna and indigo have been used for hair dyeing since ancient times. However, the hair dyeing property is low, and effective hair dyeing requires hair dyeing conditions of 30 ° C. or more for one hour or more, and the color tone is very limited. In addition, many plant pigments used for dyeing plants have been used for dyeing since ancient times. However, these dyes are generally inferior in hair dyeing properties and are not practical. Therefore, as a technique for improving this, there are known methods in which a metal ion mordant is used in combination or a reducing agent such as thiols and an alkali agent are used in combination (Patent Documents 1 and 2).

JP 2002-138024 A JP 2013-133320 A

However, according to the metal ion-based mordant described in Patent Document 1, the hair dyeing property is surely improved. However, in the case of iron ions, the hue is limited to black, the saturation is low, and the smell unique to iron ions is present. There was a problem. In the case of copper ions, aluminum ions, tin ions, nickel ions, lead ions, chromium ions, etc., there are concerns about safety to the human body, hair coloring is still insufficient, and room for improvement in shampoo resistance. was there. On the other hand, the method of using a reducing agent such as thiols and an alkali agent together as described in Patent Document 2 has a problem that the hair dyeing process is complicated and damage to the hair and scalp is unavoidable. was there.

In view of the above prior art, an object of the present invention is to provide a hair dye that has excellent hair dyeing properties, is simple to use, can be dyed in a short time, and is excellent in safety for hair and scalp. There is.

As a result of intensive studies, the present inventors have found that an organic titanium compound and / or an organic zirconium compound is combined with a predetermined dye and / or a dye precursor thereof as a means for solving the above-described problems.

That is, the present invention firstly provides a hair dye containing the following component (1) and the following component (2) simultaneously or separately.
Component (1): one selected from the group consisting of a dye having a catechol structure, a dye having a pyrogallol structure, a dye having an α-hydroxycarbonyl structure, a dye having a β-hydroxycarbonyl structure, and a dye precursor thereof Or two or more dyes and / or dye precursors thereof Component (2): an organic titanium compound and / or an organic zirconium compound

In the hair dye, the component (1) is composed of hematein, hematoxylin, brazilein, brazirine, hydroxynaphthoquinone compound, curcumin, flavonoid compound, anthocyanidin compound, alizarin, lacyne dye, cochineal dye, caffeic acid derivative, gallic acid One or more naturally-derived pigments selected from the group consisting of acid derivatives and tannin compounds are preferred.

In the hair dye, the component (2) includes titanium and / or zirconium, a hydroxycarboxylic acid compound, a β-diketone compound, a β-ketoester compound, a reductone compound, a polyol compound, a polycarboxylic acid, It is preferably a complex in which one or more compounds selected from the group consisting of an acid compound, a nitrogen-containing heterocyclic carboxylic acid compound, an alkanolamine compound, and an amino acid are coordinated.

On the other hand, the present invention secondly provides a hair dyeing method in which the following component (1) and the following component (2) are applied to hair simultaneously or separately.
Component (1): one selected from the group consisting of a dye having a catechol structure, a dye having a pyrogallol structure, a dye having an α-hydroxycarbonyl structure, a dye having a β-hydroxycarbonyl structure, and a dye precursor thereof Or two or more dyes and / or dye precursors thereof Component (2): an organic titanium compound and / or an organic zirconium compound

In the hair dyeing method, the component (1) includes hematein, hematoxylin, brazilein, brazirine, hydroxynaphthoquinone compounds, curcumin, flavonoid compounds, anthocyanidins compounds, alizarin, lacyne dyes, cochineal dyes, caffeic acid derivatives, gallic acid One or more naturally-derived pigments selected from the group consisting of acid derivatives and tannin compounds are preferred.

In the hair dyeing method, the component (2) includes titanium and / or zirconium, a hydroxycarboxylic acid compound, a β-diketone compound, a β-ketoester compound, a reductone compound, a polyol compound, a polycarboxylic acid, It is preferably a complex in which one or more compounds selected from the group consisting of an acid compound, a nitrogen-containing heterocyclic carboxylic acid compound, an alkanolamine compound, and an amino acid are coordinated.

According to the present invention, since the organic titanium compound and / or the organic zirconium compound are combined with the predetermined dye and / or the dye precursor thereof, a hair dye having excellent hair dyeing properties can be obtained. This hair dye is easy to use, can be dyed in a short time, and has excellent safety for hair and scalp.

The present invention
Component (1): one selected from the group consisting of a dye having a catechol structure, a dye having a pyrogallol structure, a dye having an α-hydroxycarbonyl structure, a dye having a β-hydroxycarbonyl structure, and a dye precursor thereof Or two or more dyes and / or dye precursors thereof;
Component (2): an organic titanium compound and / or an organic zirconium compound;
Consists of

The dye constituting the component (1) and / or the dye precursor thereof is substantially light yellow to red, and the dye is an organic titanium compound and / or an organic zirconium compound constituting the component (2). Is formed into a dark and deep color (yellow, purple to black) pigment. By carrying out this reaction on the hair, the organotitanium compound and / or the organozirconium compound form a complex with the dye and interact with the carboxyl group, hydroxyl group, and amide group on the hair surface, thereby strongly dyeing the hair. Haired. As a result, high hair dyeing properties and excellent shampoo resistance are realized. Moreover, the compound which comprises the said component (1) and the said component (2) has high safety | security, and does not cause inflammation and allergy to a scalp. Furthermore, since hair is dyed without using an alkaline agent, there is no damage inside the hair due to the alkaline agent.

Examples of the component (1) include hematein, hematoxylin which is a precursor of hematein, brazilein, braziline which is a precursor of brazilein, hydroxynaphthoquinone compounds (lawson, juglone, shikonin, alkanine, acylated shikonin, dehydroshikonin, etc.), curcumin Flavonoid compounds (quercetin, rutin, luteolin, etc.), anthocyanidins compounds, alizarin, laccaine dye, cochineal dye, caffeic acid derivatives (caffeic acid, ethyl caffeate, chlorogenic acid, rosmarinic acid, esculetin, etc.), gallic acid derivatives ( And ethyl gallate, ellagic acid, digallic acid, etc.), tannin compounds (pentadium, taratannin, quebracho, epigallocatechin, strawberry astringent, etc.). These may be used alone or in combination of two or more.

The component (1) is preferably a naturally derived component. Specifically, for example, hematein is a pigment contained in logwood (Akaminoki), brazilein is a pigment contained in Suou, Lawson is henna, juglone is black walnut, shikonin derivatives are purple root or alkanna, and curcumin is a pigment contained in turmeric. In addition, flavonoid compounds such as quercetin, rutin, and luteolin are contained in various trees such as cicaceae plants (for example, myrobalan), various citrus fruits, berries, vegetables, and gallic acid derivatives are a kind of catechin. It is abundant in berries and tannins. Alizarin is abundant in Western and Indian cocoons, and caffeic acid derivatives are abundant in green coffee beans, sweet potato stalks and leaves, sunflower seeds, fruits and mugwort. Tannin compounds are contained in a wide range of plants, and are roughly classified into hydrolyzed and condensed forms. On the other hand, raccaine pigment and cochineal pigment are pigments derived from scale insects.

Among the above pigments, hematein and brazilein coexist with their reductants in the basic plant. That is, the hematin basic plant Akaminoki (logwood) contains a large amount of reduced hematoxylin, and the brazilein basic plant Su contains a large amount of reduced bradylin. In the present invention, a plant extract in which these reductants coexist can be used as it is. However, the extract is prepared in advance by using various oxidizing agents (oxygen, hydrogen peroxide, silver oxide, manganese dioxide, persulfate, persulfate, persulfate, It is desirable to use after treatment with iodic acid or the like, for example, to convert a reduced form such as hematoxylin or brazirine into an oxidized form such as hematein or brazilein and increasing the content thereof.

As a method for obtaining an extract from natural resources such as plants and insects, generally, the natural resources are dried and pulverized, and then with water, ethanol, isopropanol, propylene glycol, 1,3-butanediol or a mixed solvent thereof. An extraction method is adopted.

The above extracts often contain already oxidized pigments. Colored extracts containing these pigments can be further subjected to an oxidation process and a purification process as necessary to obtain high-purity pigment-containing materials, but it is also possible to use colored unrefined products as they are for hair dyeing. it can.

The component (1) may be non-naturally occurring. Specifically, hydroxyanthraquinone dyes (quinizarin (1,4-dihydroxyanthraquinone), 1,4,5,8-tetrahydroxyanthraquinone, etc.), hydroxynaphthoquinone dyes (naphthazarin, naphthopurine, 2,3-dihydroxy- 1,4-naphthoquinone, etc.). These may be used alone or in combination of two or more. In addition, it is preferably used for the purpose of diversifying the hue of the hair dye in combination with the above-mentioned naturally derived ones.

The component (2) is a complex in which titanium or zirconium is bonded to an organic ligand. For example, a complex with a hydroxycarboxylic acid compound, a complex with a β-diketone compound, a complex with a β-ketoester compound A complex with a reductone compound, a complex with a polyol compound, a complex with a polycarboxylic acid compound, a complex with a nitrogen-containing heterocyclic carboxylic acid, a complex with an alkanolamine compound, a complex with an amino acid, and the like. Usually, titanium is tetravalent 6-coordinate and zirconium is tetravalent 8-coordinate, and a plurality of ligands can be bonded to the component (1) and the hair by a covalent bond or a coordinate bond. Hair dyeing properties and excellent shampoo resistance can be imparted. The use of titanium compounds as a mordant has been known for a long time, but the known titanium mordants are strongly acidic titanium sulfate aqueous solutions or titanium chloride aqueous solutions containing high-concentration sulfuric acid or hydrochloric acid, and they are applied to human hair dyeing. It was impossible to do. The organotitanium compound constituting the component (2) is a substantially neutral compound and has sufficiently high stability in an aqueous solution. On the other hand, zirconium has hardly been used as a mordant for plant dyeing. Its chemistry is very similar to titanium.

As a chemical property common to titanium and zirconium, complexes with unstable ligands with weak binding power are easily hydrolyzed in water and decomposed into titanium oxide or zirconium oxide, thus obtaining a stable complex in water. For this, selection of the ligand is extremely important. Preferred hydroxycarboxylic acid ligands include glycolic acid, lactic acid, mandelic acid, citric acid, tartaric acid, malic acid, salicylic acid, sulfosalicylic acid, etc. Preferred β-diketones or β-ketoester ligands include acetylacetone and benzoylacetone , Dibenzoylmethane, ethyl acetoacetate, etc., as preferred reductone ligands, ascorbic acid, erythorbic acid, dihydroxyacetone, erythrulose, etc., as preferred polyol ligands, ethylene glycol, propylene glycol, butylene glycol, isoprene glycol, Preferable polycarboxylic acid ligands such as glycerin, catechol, and tyrone include oxalic acid, malonic acid, maleic acid, glutamic acid, and the like, and preferable nitrogen-containing heterocyclic carboxylic acid ligands include pyridyl. Preferred alkanolamine ligands such as 2-carboxylic acid, imidazole-2-carboxylic acid, imidazole-4-carboxylic acid, 5-pyrrolidone-2-carboxylic acid, pyrazine-2-carboxylic acid, etc. include ethanolamine and diethanolamine Examples of preferable amino acid ligands such as triethanolamine include serine, glycine, alanine, glutamic acid, lysine, histidine and the like.

The present invention provides a hair dye containing the component (1) and the component (2) simultaneously or separately. Hereinafter, for convenience, the form containing the component (1) will be referred to as the composition (A), the form containing the component (2) will be referred to as the composition (B), or the components (1) and (2). A form containing both components is represented as a composition (C), and an embodiment in which they are provided as a hair dye will be described in more detail.

The composition (A) or the composition (B) or the composition (C) is not particularly limited in its form, and from the viewpoint of ease of application to the hair, a solution, a suspension, Preferred examples include emulsions, creams, foams, gels, pastes and the like. There are no particular limitations on the type of solvent for providing these forms, for example, water, methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, isoprene glycol, Xylene glycol, ethyl carbitol, glycerin, diglycerin, polyethylene glycol, polypropylene glycol and the like can be used. These solvents may be used alone or in combination of two or more. It is preferable to use water alone or a mixture of water and the above organic solvent.

However, from the viewpoint of hair dyeability and shampoo resistance, it is preferable that the component (1) and the component (2) are provided in different forms. For example, among the above-mentioned forms, it is particularly preferable to provide a solution-like composition (A) and a solution-like composition (B) filled in different containers. Moreover, it can also provide with the form enclosed with the propellant in the aerosol container under pressure.

On the other hand, the form which contains the said component (1) and the said component (2) simultaneously is demonstrated, when the said component (1) and the said component (2) are mixed, complex formation will advance, and in many cases, water or an organic solvent A slightly colored precipitate is formed. When the precipitate is formed, the hair dyeing property is generally remarkably lowered. Therefore, it is necessary to take a prescription in which no precipitate is formed. Specifically, measures such as optimizing the combination of component (1) and component (2), using an auxiliary solvent solubilizing the colored precipitate, and optimizing the solvent ratio in the mixed solvent are applied. Is done. The embodiment containing the component (1) and the component (2) at the same time is particularly preferably used for hair dyeing in a short time when going out because the operation of hair dyeing is simple.

The amount of the component (1) used is not particularly limited, but when preparing a composition (A) such as a solution containing the component (1), 0.03% by mass to 5% by mass in the composition is used. About 0.1% by mass to about 3% by mass is particularly preferable. For example, the color tone at the time of hair dyeing can be widely changed by changing the concentration of the component (1) pigment or mixing a plurality of pigments.

Although the usage-amount of the said component (2) is not specifically limited, When preparing composition (B), such as a solution form containing a component (2), the solubility to water of a component (2) is 0.1. The thing of the mass% or more is preferable and the thing of 1.0 mass% or more is especially preferable. Further, the composition preferably contains about 0.05% by mass to 10% by mass, particularly preferably about 0.1% by mass to 5% by mass. And, for example, by changing the ligand and concentration of the titanium compound or zirconium compound of component (2), the molar ratio with the pigment of component (1), etc., the hue, lightness, and saturation of the hair after dyeing Etc. can be changed greatly.

The pH of the component (1) and the component (2) is not particularly limited, but from the viewpoint of hair dyeing properties, when preparing a composition (A) such as a solution containing the component (1), the components described above When preparing a composition (B) such as a solution containing (2), or when preparing a composition (C) such as a solution containing the above component (1) and component (2), those compositions The pH of the product (A), the composition (B) or the composition (C) is preferably in the range of 3 to 10, and particularly preferably in the range of 3 to 8. From the viewpoint of suppressing hair damage, the pH is preferably 9 or less, and particularly preferably in the range of 3.5 to 6.5.

The pH may be adjusted as appropriate using a pH adjuster comprising an acid or a base.

Examples of the acid used as a pH regulator include acetic acid, lactic acid, tartaric acid, malic acid, citric acid, glycolic acid, pyrrolidone carboxylic acid, levulinic acid, fumaric acid, succinic acid, oxalic acid, maleic acid, mandelic acid, asparagine. Examples include acids, organic acids such as adipic acid and nicotinic acid, and phosphoric acid. Of these, organic acids such as acetic acid, lactic acid, tartaric acid, malic acid, citric acid, glycolic acid, fumaric acid, succinic acid, maleic acid, mandelic acid, aspartic acid, and adipic acid are preferably used. Further, salts of these acids (sodium salt, potassium salt, ammonium salt, etc.) may be used as a pH regulator.

Examples of the base used as a pH adjuster include ammonia, ethanolamine, diethanolamine, triethanolamine, imidazole, tetramethylammonium hydroxide, sodium bicarbonate, sodium acetate, sodium lactate and the like. Among these, it is preferable to use ethanolamine, diethanolamine, triethanolamine, imidazole and the like.

The above pH adjusters may be used alone or in combination of two or more. The blending amount of the pH adjuster is not particularly limited, but for example, it is preferably used in the range of 0.01% by mass to 15% by mass with respect to the total mass when using the hair dye, and 0.1% by mass to More preferably, it is used in the range of 10% by mass, and particularly preferably in the range of 0.5% by mass to 5% by mass.

On the other hand, a pH buffer solution is preferably used for pH adjustment. Examples of the pH buffer solution include acetate buffer solution, phosphate buffer solution, citrate buffer solution, citrate phosphate buffer solution, borate buffer solution, tartaric acid buffer solution, Tris buffer solution and the like. In particular, it is preferable to use an acetate buffer, a phosphate buffer, a citrate buffer, a citrate phosphate buffer, or the like.

When preparing a composition (A) such as a solution containing the component (1), preparing a composition (B) such as a solution containing the component (2), or the component (1) and the component When preparing a composition (C) such as a solution containing (2), a surfactant is added to the composition (A), the composition (B), or the composition (C) as necessary. You may mix | blend. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. In particular, it is preferable to use a nonionic surfactant.

Nonionic surfactants include fatty acid alkanolamides, polyvinyl pyrrolidones, polyethylene oxides, polyethylene oxide monoalkyl ethers, polyethylene oxide diethers, polyethylene oxide monophenyl ethers, polypropylene oxides, polypropylene oxide monoalkyl. Examples include ethers, polypropylene oxide dialkyl ethers, polyethylene oxide fatty acid esters, glycerin fatty acid esters, glycerin monoethers, sorbitan fatty acid esters and the like.

The above surfactants may be used alone or in combination of two or more. The blending amount of the surfactant is not particularly limited. For example, it is preferably used in the range of 0.01% by mass to 20% by mass with respect to the total mass when using the hair dye, and 0.1% by mass to It is more preferable to use in the range of 5 mass%.

When preparing a composition (A) such as a solution containing the component (1), preparing a composition (B) such as a solution containing the component (2), or the component (1) and the component When preparing a composition (C) such as a solution containing (2), an oil component is blended in the composition (A), the composition (B), or the composition (C) as necessary. May be. The oil component is not particularly limited as long as it can be dissolved or dispersed in the composition (A), the composition (B), or the composition (C). By blending the oil component, it is possible to suppress damage to the hair after dyeing and to impart gloss and moisture. Examples of the oil component include silicones, hydrocarbons, fats and oils, waxes, and higher fatty acid esters.

The above oily components may be used alone or in combination of two or more. The blending amount of the oil component is not particularly limited, but for example, it is preferably used in the range of 0.01% by mass to 5% by mass with respect to the total mass when using the hair dye, and 0.05% by mass to 3% by mass. It is more preferable to use in the range.

When preparing a composition (A) such as a solution containing the component (1), preparing a composition (B) such as a solution containing the component (2), or the component (1) and the component When preparing a composition (C) such as a solution containing (2), a higher alcohol is blended in the composition (A), the composition (B) or the composition (C) as necessary. May be. The higher alcohol is not particularly limited as long as it can be dissolved or dispersed in the composition (A), the composition (B), or the composition (C). Examples include myristyl alcohol, cetanol, oleyl alcohol, stearyl alcohol and the like. These higher alcohols may be used alone or in combination of two or more. The blending amount of the higher alcohol is not particularly limited, but for example, it is preferably used in the range of 0.01% by mass to 5% by mass with respect to the total mass when the hair dye is used, and 0.03% by mass to 3%. It is more preferable to use in the range of mass%.

When preparing a composition (A) such as a solution containing the component (1), preparing a composition (B) such as a solution containing the component (2), or the component (1) and the component When preparing a composition (C) such as a solution containing (2), a polymer compound is added to the composition (A) or the composition (B) or the composition (C) as necessary. You may mix | blend. The polymer compound is not particularly limited as long as it can be dissolved or dispersed in the composition (A), the composition (B), or the composition (C). Examples thereof include a cationic polymer compound, an amphoteric polymer compound, an anionic polymer compound, and a nonionic polymer compound.

Examples of the cationic polymer compound include cationized cellulose (eg, O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethyl cellulose chloride, O- [2-hydroxy-3- (lauryldimethylammoni chloride). E) propyl) hydroxyethyl cellulose), cationic starch, cationized guar gum, polydimethyldiallylammonium salt and the like.

Examples of the anionic polymer compound include a copolymer polymer of acrylic acid or methacrylic acid and other vinyl monomers, carboxymethyl cellulose, and the like.

Nonionic polymer compounds include, for example, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethylpropyl cellulose, guar gum, hydroxypropyl xanthan gum, agar, starch, polyacrylate, Examples include polymethacrylic acid ester, polyacrylamide, polymethacrylamide, polyethylene glycol, polypropylene glycol and the like.

Other useful polymer compounds include, for example, gum arabic, carrageenan, white jellyfish polysaccharide, galactan, quince seed gum, locust bean gum, tragacanth gum, pectin, mannan, xanthan gum, dextran, curdlan, gellan gum, succinoglucan, Examples include natural polymer compounds such as gelatin, tamarind gum, and casein.

The above polymer compounds may be used alone or in combination of two or more. The blending amount of the polymer compound is not particularly limited, but for example, it is preferably used in the range of 0.01% by mass to 10% by mass with respect to the total mass when using the hair dye, and 0.05% by mass to 5% by mass. It is more preferable to use in the range of%.

When preparing a composition (A) such as a solution containing the component (1), preparing a composition (B) such as a solution containing the component (2), or the component (1) and the component When preparing a composition (C) such as a solution containing (2), a thickener is added to the composition (A) or the composition (B) or the composition (C) as necessary. You may mix | blend. Examples of the thickener include sodium alginate, gum arabic, cross-linked acrylic acid polymer, cellulose derivative, xanthan gum and the like. These thickeners may be used alone or in combination of two or more. The blending amount of the thickener is not particularly limited. For example, it is preferably used in the range of 0.01% by mass to 5% by mass with respect to the total mass when using the hair dye, and 0.05% by mass to 0.00%. More preferably, it is used in the range of 5% by mass.

When preparing a composition (A) such as a solution containing the component (1), preparing a composition (B) such as a solution containing the component (2), or the component (1) and the component When preparing a composition (C) such as a solution containing (2), a fragrance is blended in the composition (A), the composition (B) or the composition (C) as necessary. May be. As a fragrance | flavor, even if it is a synthetic product and a natural product, it is used arbitrarily, but essential oil (essential oil) is used preferably especially.

When preparing a composition (A) such as a solution containing the component (1), preparing a composition (B) such as a solution containing the component (2), or the component (1) and the component When preparing a composition (C) such as a solution containing (2), the composition (A) or the composition (B) or the composition (C) may be dyed as necessary. Various additives may be blended for the adjustment of the above. Examples of additives for controlling hair coloring include aliphatic carboxylic acids (for example, acetic acid, propionic acid, lactic acid, glycolic acid, levulinic acid, fumaric acid, maleic acid, succinic acid, tartaric acid, malic acid, citric acid). Acid) and amino acids (eg glycine, α-alanine, β-alanine, valine, leucine, isoleucine, phenylalanine, proline, serine, threonine, aspartic acid, glutamic acid, arginine, histidine, tryptophan, methionine, etc.) Can do.

When preparing a composition (A) such as a solution containing the component (1), preparing a composition (B) such as a solution containing the component (2), or the component (1) and the component When preparing a composition (C) in the form of a solution containing (2), the composition (A) or the composition (B) or the composition (C), particularly the organic titanium compound and / or organic If necessary, the composition (B) containing a zirconium compound may contain a metal ion other than titanium or zirconium as a mordant. As described above, metal ions other than iron are concerned with safety to the human body, but can be blended at a low concentration. Usable metal ions include copper ions, aluminum ions, zinc ions and the like. On the other hand, iron ions have a problem, but when black hair is dyed, they can be used in combination with an organic titanium compound and / or an organic zirconium compound. Examples of preferable iron ion raw materials include ferrous lactate, ferric lactate, ferrous acetate, ferric acetate, ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, and the like. Is mentioned. The blending amount when iron ions are blended is preferably in the range of 0.001% by mass to 0.3% by mass.

In the present invention, various water-soluble metal salts can be added to the above components. By adding the metal salt, the hair dyeability and shampoo resistance can be improved and the hue can be finely adjusted. As the metal salt, alkali metal halide, alkali metal sulfate, alkaline earth metal halide, water-soluble aluminum salt, water-soluble copper salt and the like are useful. Preferred examples include sodium chloride, potassium chloride, sodium bromide. , Magnesium chloride, magnesium bromide, aluminum acetate, aluminum lactate, aluminum sulfate, alum, cupric acetate, cupric lactate and the like.

When preparing a composition (A) such as a solution containing the component (1), preparing a composition (B) such as a solution containing the component (2), or the component (1) and the component When preparing a composition (C) such as a solution containing (2), the composition (A) or the composition (B) or the composition (C), in particular the dye and / or the dye precursor thereof A known pigment / dye can be added to the composition (A) containing the body, if necessary, for the purpose of adjusting the color tone. Known pigments / dyes include, for example, HC yellow 1, HC yellow 2, HC yellow 3, HC yellow 4, HC orange 1, HC red 1, HC red 2, HC red 3, HC blue 1, HC blue 2, Dispersed purple 1, dispersed blue 3, etc. As direct dyes, black 401, blue 1, blue 2, blue 201, blue 202, blue 203, blue 403, blue 404, purple 201, purple 401, Red 102, Red 106, Red 201, Red 202, Red 203, Red 204, Red 205, Red 206, Red 207, Red 208, Orange 201, Orange 203 , Orange 205, Orange 206, Orange 207, Yellow 201, Yellow 203, Yellow 204, Yellow 205, Yellow 401, Yellow 402, Yellow 403, Natural dyes such as chlorophyll dye, spirulina dye Gardenia yellow, gardenia blue pigment, guaiazulene, guaiazulene sulfonate, and the like.

When preparing a composition (A) such as a solution containing the component (1), preparing a composition (B) such as a solution containing the component (2), or the component (1) and the component When preparing a composition (C) such as a solution containing (2), other substances should be added to the composition (A), the composition (B), or the composition (C). Can do. Other substances are not particularly limited as long as they do not decrease hair dyeing properties and can be dissolved or dispersed in the composition (A), the composition (B), or the composition (C). Preferred examples include collagen, keratin, elastin, fibroin, conchiolin, sodium pyrrolidonecarboxylate, sodium lactate, sorbitol, hyaluronic acid, benzyl alcohol, phenethyl alcohol, benzyloxyethanol, N-methylpyrrolidone, N-ethylpyrrolidone, ethylene carbonate , Urea, hydroxyethylurea, cyclohexane-1,4-dicarboxylic acid bisethoxydiglycol, propylene carbonate, paraben, ultraviolet absorber and the like.

The hair dye having the above constitution according to the present invention can be used for hair coloring of human or animal hair such as hair or body hair, animal hair, etc., preferably human hair coloring. It can be used for hair coloring of pets such as dogs and cats, particularly preferably for hair coloring of human hair.

In the case of performing hair dyeing using the hair dye having the above constitution according to the present invention, the application order of the component (1) and the component (2) is not particularly limited, and can be applied in an arbitrary order. it can. For example, after applying the composition (A) containing the component (1) to a hair or the like and applying it to the hair or the like, the composition (B) containing the component (2) is applied to the hair or the like. The composition (B) containing the above component (2) may be applied to the hair or the like, and then applied to the hair or the like and then applied to the hair, etc., and then the solution containing the above component (1), etc. The composition (A) may be applied to the hair or the like. Alternatively, a solution-like composition (A) containing the component (1) and a solution-like composition (B) containing the component (2) are simultaneously applied to hair or the like. Alternatively, a mixture obtained by mixing the two just before use may be applied to hair or the like. Furthermore, a composition (C) such as a solution containing both the component (1) and the component (2) may be prepared and applied to hair or the like.

Among these, after applying the composition (B) containing the component (2) to a hair or the like and applying it to the hair, the composition (A) containing the component (1) is applied to the composition (A). A method of applying to hair or the like is particularly preferable. The organotitanium compound and / or organozirconium compound constituting the component (2) has a property of strongly interacting with hair keratin protein and the like. This is because high hair dyeing properties can be obtained. That is, for example, after the composition (B) is applied to the hair, the composition (A) is applied after standing for a while. The standing time is not particularly limited, but is preferably 3 to 30 minutes, for example, and more preferably 5 to 20 minutes. Further, it is preferable to leave the composition (A) for a while after application. The standing time is not particularly limited, but is preferably 5 to 30 minutes, for example, and more preferably 10 to 20 minutes. The hair dyeing treatment can be performed at a temperature of about 20 ° C. to 40 ° C., for example. Although the usage-amount of composition (A), such as a solution containing the said component (1), and composition (B), such as a solution containing the said component (2), is not specifically limited, As a volume ratio of both, it is 3/1. A range of ˜1 / 3 is preferred. The application method of the composition (A) or the composition (B) is not particularly limited, and any method such as applying the composition to hair or the like, or immersing hair or the like in the composition, or the like. Can be adopted. After dyeing, it can be treated with shampoo and rinse. Then, it is preferable to dry by an appropriate method.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited by the following examples.

<Preparation Example 1> (Preparation of Solution A1)
2.84 g of titanium tetraisopropoxide (manufactured by Tokyo Chemical Industry) was dropped into a mixture of 10 mL of butylene glycol, 5 mL of isopropanol and 2.70 g of lactic acid under ice cooling, and then stirred at room temperature for 1 hour. Separately, 1.0 g of hydroxyethyl cellulose was dissolved in 70 mL of purified water, and this solution was gradually added to the titanium lactate solution to obtain a slightly viscous colorless transparent solution (A1).

<Preparation Example 2> (Preparation of Solution A2)
In a mixture of 10 mL of butylene glycol, 5 mL of n-propanol and 2.70 g of lactic acid, 5.54 g of a 70% propanol solution of zirconium tetrapropoxide (manufactured by Tokyo Chemical Industry) was added dropwise under ice cooling, and then stirred at room temperature for 1 hour. did. Separately, 1.0 g of hydroxyethyl cellulose was dissolved in 70 mL of purified water, and this solution was added little by little to a solution of zirconium lactate to obtain a slightly viscous colorless transparent solution (A2).

<Preparation Example 3> (Preparation of Solution B1)
0.60 g of hematein and 0.57 g of luteolin were added to a mixture of 5 g of butylene glycol and 10 g of aminone C-11S (manufactured by Kao) and dissolved by heating at 50 ° C. Next, 100 g of a 2% hydroxyethyl cellulose aqueous solution was added, and the mixture was vigorously stirred at 50 ° C. for 30 minutes using a homogenizer, and then allowed to cool to obtain an orange-red cream-like solution (B1).

<Preparation Example 4> (Plant pigment extraction method 1)
100 g of dried myobalan chips (Tanaka Dye Store) were added to 1 L of 50% ethanol solution and heated at reflux for 2 hours. After cooling, the mixture was filtered, and the solvent was distilled off from the filtrate under reduced pressure to obtain 6.5 g of extract containing luteolin as a main component. This method is the most common method for extracting plant pigments.

<Preparation Example 5> (Plant pigment extraction method 2)
100 g of dried Akaminoki chips (Tanaka Dye Store) was added to 1 L of a 50% ethanol solution and heated at reflux for 2 hours. After cooling, the mixture was filtered, and 1.16 g of silver oxide was added to the filtrate, followed by stirring at room temperature for 2 hours. Insoluble matter was filtered off, and the solvent was distilled off from the filtrate under reduced pressure to obtain 8.2 g of an extract containing hematein as a main component. This method is preferably employed also when brazilein is obtained from Suou.

<Preparation Example 6> (Preparation of Solution B2)
Add 1.0 g of Myrobalan extract of Preparation Example 4 and 1.2 g of Akaminoki extract of Preparation Example 5 to a mixture of 5 g of butylene glycol, 5 g of purified water and 15 g of Aminone C-11S (manufactured by Kao), and dissolve by heating at 60 ° C. I let you. Next, 100 g of a 2% hydroxyethyl cellulose aqueous solution was added, and the mixture was vigorously stirred at 60 ° C. for 30 minutes using a homogenizer, and then allowed to cool to obtain a dark red cream solution (B2).

<Preparation Example 7> (Plant pigment extraction method 3)
100 g of soft purple root dried chips (produced in Shaanxi Province, China) were finely pulverized, 1 L of 95% ethanol solution was added, and the mixture was stirred at 50 ° C. for 2 hours. After cooling, the mixture was filtered and the solvent was distilled off from the filtrate under reduced pressure. Dissolve the residue in 100 mL of ethyl acetate, wash 3 times with 100 mL of 3% aqueous sodium hydrogen carbonate solution to remove coexisting intermediate fatty acids, further wash with 1% aqueous lactic acid solution, and dry over anhydrous magnesium sulfate. By distilling off, 3.1 g of crude shikonin mainly composed of acylshikonin was obtained.

<Preparation Example 8> (Plant pigment extraction method 4)
100 g of dry turmeric (India) was finely pulverized, 1 L of a 95% ethanol solution was added, and the mixture was stirred at 50 ° C. for 2 hours. After cooling, the mixture was filtered and the solvent was distilled off from the filtrate under reduced pressure. The residue was dissolved by heating in 200 mL of ethyl acetate, and the insoluble material was filtered off. Ethyl acetate was distilled off under reduced pressure from the filtrate to obtain 6.5 g of crude curcumin.

[Test Example 1] (Hair dyeing test 1)
20 g of the solution A1 of Preparation Example 1 was applied to 2 g of human white hair (100%) bundle (manufactured by Beaulux) with a brush and allowed to stand for 10 minutes. Next, 20 g of the creamy solution B1 of Preparation Example 3 was applied with a brush and left for another 10 minutes. The hair bundle was thoroughly washed with warm water, shampooed and rinsed, and dried using a dryer. The hair bundle was dyed blackish brown. When the hair density after hair dyeing was measured for the hair density (ΔE: color difference compared with before hair dyeing) using a color difference meter (CR-400 manufactured by Konica Minolta Sensing), ΔE was 50.2. there were.

[Test Example 2] (Hair dyeing test 2)
20 g of the solution A1 of Preparation Example 1 was applied to 2 g of human white hair (100%) bundle (manufactured by Beaulux) with a brush and allowed to stand for 10 minutes. Next, 20 g of cream-like solution B2 of Preparation Example 6 was applied with a brush and allowed to stand for 10 minutes. The hair bundle was thoroughly washed with warm water, shampooed and rinsed, and dried using a dryer. The hair bundle was dyed dark brown. When the hair density (ΔE) of the hair bundle after dyeing was measured using a color difference meter, ΔE was 48.5.

[Test Example 3] (Hair dyeing test 3)
20 g of the solution A2 of Preparation Example 2 was applied to 2 g of human white hair (100%) bundle (manufactured by Beaulux) with a brush and allowed to stand for 10 minutes. Next, 20 g of cream-like solution B2 of Preparation Example 6 was applied with a brush and allowed to stand for 10 minutes. The hair bundle was thoroughly washed with warm water, shampooed and rinsed, and dried using a dryer. The hair bundle was dyed dark brown. When the hair density (ΔE) of the hair bundle after dyeing was measured using a color difference meter, ΔE was 45.2.

[Test Example 4] (Hair dyeing test 4)
A hair dyeing test was conducted according to Test Examples 1 to 3 by appropriately combining the solution A group and the creamy solution B group. The results are shown in Table 1. As the solution A group, a method according to Preparation Example 1 or Preparation Example 2, specifically, the molar ratio of titanium or zirconium to a ligand is 1: 2, and a tetraalkoxide of titanium or zirconium is coordinated. A complex compound of titanium or zirconium with the ligands shown in Table 1 was prepared by adding the mixture to a mixture of the styrene and isopropanol or propanol under water cooling. In addition, as the creamy solution group B, a method according to Preparation Examples 4 to 5, specifically, 100 g of dried ground plant to be extracted was added to 1 L of 50% or 95% ethanol and stirred for 2 hours. After heating at reflux, insoluble matters were filtered off, and the solvent was removed from the filtrate under reduced pressure to extract pigments from various plants. A cream-like solution was prepared by a method similar to Preparation Example 6.

[Test Example 5] (Hair dyeing test 5)
20 g of cream solution B1 of Preparation Example 3 was applied to 2 g of human white hair (100%) bundle (manufactured by Beaulux) with a brush and allowed to stand for 10 minutes. Next, 20 g of the solution A1 of Preparation Example 1 was applied with a brush and allowed to stand for 10 minutes. The hair bundle was thoroughly washed with warm water, shampooed and rinsed, and dried using a dryer. The hair bundle was dyed blackish brown. When the hair density (ΔE) of the hair bundle after dyeing was measured using a color difference meter, ΔE was 45.8. From this result, it was found that in the case of this test example, even if the application order of the solution A and the solution B was changed, there was no significant difference in the hair dyeability.

[Test Example 6] (Hair dyeing test 6)
20 g of the solution A1 of Preparation Example 1 and 20 g of the cream solution B1 of Preparation Example 3 were uniformly applied to 2 g of human white hair (100%) bundle so as to be mixed on the hair using a brush. After standing for 30 minutes, the hair bundle was thoroughly washed with warm water, shampooed and rinsed, and dried using a dryer. The hair bundle was dyed brown. When the hair density (ΔE) of the hair bundle after dyeing was measured, ΔE was 28.7. From this result, it was found that when the solution A and the solution B were applied to the hair at the same time, the hair dyeability was lowered.

[Test Example 7] (Hair dyeing test 7)
20 g of solution A1 of Preparation Example 1 and dye solution B12 (1.0 g of crude shikonin and 1.0 g of hydroxyethylurea dissolved in 100 mL of 95% ethanol) and 20 g of human hair were mixed using a brush. 100%) It was uniformly applied to 2 g of the bundle. After standing for 30 minutes, the hair was thoroughly washed with warm water, shampooed and rinsed, and dried using a dryer. The hair bundle was dyed brown. When the hair density (ΔE) of the hair bundle after dyeing was measured, ΔE was 41.7. From this result, it was found that, depending on the combination of the solution A and the solution B, even when both are mixed at the time of use and applied to the hair, the hair dyeability does not deteriorate.

[Test Example 8] (Hair dyeing test 8)
A mixture of 50 mg of crude shikonin of Preparation Example 7, 60 mg of crude curcumin of Preparation Example 8, 100 mg of benzyl alcohol, 50 mg of hydroxyethylurea, 1.0 g of purified water and 9.0 g of ethanol was heated and stirred at 50 ° C. to give an orange-red dye solution Was prepared. On the other hand, 2.84 g of titanium tetraisopropoxide was added to a mixture of 5 mL of butylene glycol, 5 mL of ethanol and 2.70 g of lactic acid under ice cooling, and then stirred at room temperature for 1 hour to prepare a titanium lactate solution. 150 mg of titanium lactate solution was added to the above dye solution to prepare a brown dye / titanium complex solution. This solution was stable without precipitation after standing overnight.
The above solution was uniformly applied to 0.2 g of white hair (100%) bundle using a hair mascara mini brush. After standing at room temperature for 1 hour, the hair bundle was thoroughly washed with warm water, further shampooed, and dried with a dryer. The hair bundle was dyed dark brown immediately after dyeing. Further, no decrease in concentration was observed after washing with warm water. Furthermore, when the hair density of the hair bundle after shampooing was compared with the hair density immediately after hair dyeing, the decrease in density was only 10%. From this result, it was found that a stable dye / titanium complex solution having high hair dyeability and shampoo resistance can be obtained by appropriately combining the dye solution and the titanium solution.

[Test Example 9] (Comparative hair dyeing test 1)
20 g of creamy solution B1 of Preparation Example 3 was applied to 2 g of human white hair (100%) bundle (manufactured by Beaulux) with a brush and wrapped with a polyethylene film, and left in a thermostatic bath at 35 ° C. for 30 minutes. did. The hair bundle was thoroughly washed with warm water, shampooed and rinsed, and dried using a dryer. The hair bundle was dyed light reddish brown. When the hair density (ΔE) of the hair bundle after dyeing was measured using a color difference meter, ΔE was 10.3. From this result, it can be seen that the hair dyeability is significantly reduced without the titanium compound.

[Test Example 10] (Comparative hair dyeing test 2)
Preparation Example 6 using 2 hours of human white hair (100%) bundle (manufactured by Beaulux) extracted from yellowfin as in Preparation Example 4 and extracted from yellowfin berberine that does not form a complex with titanium. In the same manner as above, a creamy solution B was prepared, 20 g of which was applied with a brush, and allowed to stand for 30 minutes. The hair bundle was thoroughly washed with warm water, shampooed and rinsed, and dried using a dryer. The hair bundle was dyed light yellow. When the hair density (ΔE) of the hair bundle after dyeing was measured using a color difference meter, ΔE was 12.2.

[Test Example 11] (Comparative hair dyeing test 3)
Apply 20 g of the solution A1 of Preparation Example 1 to 2 g of human white hair (100%) bundle (manufactured by Beaulux) with a brush, leave it for 10 minutes, and then apply 20 g of the cream solution of the above extract of yellowfin extract. It was applied and left for 30 minutes. The hair bundle was thoroughly washed with warm water, shampooed and rinsed, and dried using a dryer. The hair bundle was dyed light yellow. When the hair density (ΔE) of the hair bundle after dyeing was measured using a color difference meter, ΔE was 11.8. From this result, it can be seen that plant dyes that do not form a complex with titanium have a marked decrease in hair dyeing properties even in the presence of a titanium compound.

[Test Example 12] (Shampoo resistance test)
The hair dye samples obtained in Test Examples 1 to 3 were repeatedly shampooed five times using a general-purpose shampoo containing an amino acid detergent, and the hair density before and after the shampoo (ΔE) was measured. The results are shown in Table 2.

From the results in Table 2, it can be seen that the hair dye of the present invention has high shampoo resistance.

[Test Example 13] (Irritation test to scalp)
The hair dye comprising solution A1 and cream-like solution B2 used in Test Example 2 was applied to the hair dye of 10 human monitors that cause scalp allergy to the oxidative hair dye. As a result, there were no monitors where allergies occurred. In addition, after one month, the same monitor was again subjected to a hair coloring test, but no allergy was observed. From this result, it can be seen that the hair dye of the present invention does not cause scalp allergy.

Claims

A hair dye comprising the following component (1) and the following component (2) simultaneously or separately.
Component (1): one selected from the group consisting of a dye having a catechol structure, a dye having a pyrogallol structure, a dye having an α-hydroxycarbonyl structure, a dye having a β-hydroxycarbonyl structure, and a dye precursor thereof Or two or more dyes and / or dye precursors thereof Component (2): an organic titanium compound and / or an organic zirconium compound
The component (1) includes hematein, hematoxylin, brazilein, brazirine, hydroxynaphthoquinone compounds, curcumin, flavonoid compounds, anthocyanidins compounds, alizarin, lacyne dyes, cochineal dyes, caffeic acid derivatives, gallic acid derivatives, and tannin compounds The hair dye according to claim 1, wherein the hair dye is one or more naturally derived pigments selected from the group consisting of:
The component (2) is composed of titanium and / or zirconium, hydroxycarboxylic acid compound, β-diketone compound, β-ketoester compound, reductone compound, polyol compound, polycarboxylic acid compound, nitrogen-containing heterocyclic carboxylic acid The hair dye according to claim 1 or 2, wherein the hair dye is a complex in which one or more compounds selected from the group consisting of a compound, an alkanolamine compound, and an amino acid are coordinated.
A hair dyeing method in which the following component (1) and the following component (2) are applied to hair simultaneously or separately.
Component (1): one selected from the group consisting of a dye having a catechol structure, a dye having a pyrogallol structure, a dye having an α-hydroxycarbonyl structure, a dye having a β-hydroxycarbonyl structure, and a dye precursor thereof Or two or more dyes and / or dye precursors thereof Component (2): an organic titanium compound and / or an organic zirconium compound
The component (1) includes hematein, hematoxylin, brazilein, brazirine, hydroxynaphthoquinone compounds, curcumin, flavonoid compounds, anthocyanidins compounds, alizarin, lacyne dyes, cochineal dyes, caffeic acid derivatives, gallic acid derivatives, and tannin compounds The hair dyeing method according to claim 4, which is one or more naturally derived pigments selected from the group consisting of:
The component (2) is composed of titanium and / or zirconium, hydroxycarboxylic acid compound, β-diketone compound, β-ketoester compound, reductone compound, polyol compound, polycarboxylic acid compound, nitrogen-containing heterocyclic carboxylic acid The hair dyeing method according to claim 4 or 5, which is a complex in which one or more compounds selected from the group consisting of a compound, an alkanolamine compound, and an amino acid are coordinated.