JP2022030540A - Hair dye composition - Google Patents

Abstract

To provide a hair dye composition containing an oxidation dye, where the hair dye composition hardly stains skin but is excellent in a dyeing performance and in emulsion stability.SOLUTION: A hair dye composition contains (A) 1-10 mass% of an ascorbic acid or an erythorbic acid or their salt or ester, and (B) an oxidation dye comprising a sulfate of a compound represented by a general formula (1) in the figure, where R represents a C1-6 linear or branched alkyl group, a C2-6 linear or branched mono- or polyhydroxyalkyl group, or a linear or branched mono- or polyaminoalkyl group.SELECTED DRAWING: None

Description

The present invention relates to a hair dye composition for dyeing hair and the like. More specifically, the present invention relates to a hair dye composition containing a dye, which has less background stain, is excellent in hair dyeing power, and is also excellent in emulsification stability.

As a composition for dyeing hair, there is a hair dye composition using an oxidative dye. Although the hair dye composition has excellent hair dyeing power, it also has an aspect of causing skin stains.

For example, Patent Document 1 discloses that an oxidative hair dye containing 1 to 20% by weight of ascorbic acid reduces skin stains without reducing the hair dyeing power.

Patent Document 2 contains an oxidative dye, at least one selected from ascorbic acids and salts thereof, polyethylene glycol, a nonionic surfactant, and an oxidative dye in a hair dye composition, from ascorbic acids and salts thereof. The total content of at least one selected component is 7 to 15% by mass, the content of polyethylene glycol is 4 to 20% by mass, and the content of solid polyethylene glycol at 25 ° C. is 3% by mass or more. Therefore, it is disclosed that the hair dyeing power is good and the skin stain is small, and the emulsion stability is excellent.

Japanese Unexamined Patent Publication No. 2002-29946 Japanese Unexamined Patent Publication No. 2013-151464

An object of the present invention is to provide a hair dye composition containing an oxidative dye, which has less skin stains, excellent hair dyeing power, and excellent emulsification stability.

As a result of diligent studies on the above-mentioned problems, the inventor has made a sulfate of a heterocyclic compound having a specific structure as an oxidation dye in a hair dye composition containing ascorbic acid, erythorbic acid, salts or esters thereof. The present invention was completed by finding that an excellent hair dyeing effect can be obtained while maintaining a high skin stain suppressing effect and that the hair dye composition has high emulsification stability.

（ここで、Ｒは、１～６個の炭素原子を有する直鎖又は分枝したアルキル基、２～６個の炭素原子を有する直鎖又は分枝したモノ－又はポリヒドロキシアルキル基、直鎖又は分枝したモノ－又はポリアミノアルキル基を示す。）
染毛剤組成物を１～１０質量％の（Ａ）アスコルビン酸、エリソルビン酸、これらの塩又はエステル(以下、「Ａ成分」ともいう。)と（Ｂ）上記一般式（１）に示す化合物の硫酸塩からなる酸化染料を含有する油性成分を含む乳化組成物とすることにより、高い地肌汚れ抑制効果を維持したまま、優れた染毛効果を得ることができる。また、当該組成物は、含有する他の組成に影響されずに高い乳化安定性を保持するため、様々な組成の染毛剤組成物とすることができる。 That is, the present invention is an emulsified composition containing an oily component, wherein (A) ascorbic acid, erythorbic acid, salts or esters thereof 1 to 10% by mass, and (B) the compound represented by the following general formula (1). It is a hair dye composition characterized by containing an oxidative dye composed of the sulfate salt of.

(Here, R is a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched mono- or polyhydroxyalkyl group having 2 to 6 carbon atoms, a straight chain. Or a branched mono- or polyaminoalkyl group.)
The hair dye composition comprises 1 to 10% by mass of (A) ascorbic acid, erythorbic acid, salts or esters thereof (hereinafter, also referred to as "A component") and (B) the compound represented by the above general formula (1). By preparing an emulsified composition containing an oily component containing an oxidative dye composed of the sulfate of the above, an excellent hair dyeing effect can be obtained while maintaining a high skin stain suppressing effect. In addition, the composition can be used as a hair dye composition having various compositions because it maintains high emulsion stability without being affected by other compositions contained therein.

Further, the hair dye composition of the present invention is characterized by containing 1-hydroxyethyl-4,5-diaminopyrazole sulfate as the sulfate of the compound represented by the general formula (1) in (B). ..
By containing 1-hydroxyethyl-4,5-diaminopyrazole sulfate, the hair dye composition of the present invention can exhibit a higher effect of the present invention.

Further, the hair dye composition of the present invention has (A) ascorbic acid, erythorbic acid, and (B) the mass ratio (B / A) of the sulfate of the compound represented by the general formula (1) to these salts or esters. The sum of (A) the content of ascorbic acid, erythorbic acid, salts or esters thereof and (B) the content of sulfate of the compound represented by the general formula (1), which is more than 0.1 and less than 1. Is less than 7% by mass.
By preparing a hair dye composition in which the mass ratio of the component (A) and the sulfate of the compound represented by the general formula (1) satisfies the above relationship, both a higher skin stain suppressing effect and a better hair dyeing effect are achieved. Further, by preparing a hair dye composition in which the content of the sulfate of the component (A) and the compound represented by the general formula (1) satisfies the above relationship, higher emulsification stability can be obtained. Can be done.

Furthermore, the hair dye composition of the present invention is further characterized by containing (C) an alkanolamine.
(A) The hair dye composition containing 1 to 10% by mass of the component and the sulfate of the compound represented by the general formula (1) further contains an alkanolamine, thereby further suppressing the skin stain and the hair dyeing effect. Can be improved.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a hair dye composition containing an oxidative dye, which has less background stain, has excellent hair dyeing power, and has excellent emulsification stability.

（ここで、Ｒは、１～６個の炭素原子を有する直鎖又は分枝したアルキル基、２～６個の炭素原子を有する直鎖又は分枝したモノ－又はポリヒドロキシアルキル基、直鎖又は分枝したモノ－又はポリアミノアルキル基を示す。） Next, the best mode for carrying out the present invention will be described.
The hair dye composition of the present invention is an emulsified composition containing an oily component according to the present invention.
Hair dye containing (A) ascorbic acid, erythorbic acid, salts or esters thereof in an amount of 1 to 10% by mass, and (B) an oxidation dye consisting of a sulfate of a compound represented by the following general formula (1). It is an agent composition, which is applied to hair to deposit an oxidation dye on or inside the hair.

(Here, R is a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched mono- or polyhydroxyalkyl group having 2 to 6 carbon atoms, a straight chain. Or a branched mono- or polyaminoalkyl group.)

Hair dyes are classified into temporary hair dyes, semi-permanent hair dyes, and permanent hair dyes based on the duration of the hair dyeing effect, that is, the fastness. The hair dye composition of the present invention may be used as any hair dye. For example, it can be used for an oxidative hair dye containing an oxidative dye (permanent hair dye), a color treatment containing a direct dye (semi-permanent hair dye), and the like.

The hair dye composition of the present invention is an emulsified composition containing an oily component and a surfactant. The emulsified composition is not particularly limited in the form of an oil droplet type in water, a water droplet type in oil, or the like, but an oil droplet type emulsified composition in water is preferable.

The form of the hair dye composition of the present invention may be any form as long as it is an emulsified composition. For example, liquid, cream, gel, mist and the like can be mentioned. The emulsified composition may be used at the time of storage, and may be in the form of foam or mist at the time of use. In the case of foaming, an aerosol former container, a non-aerosol former container, or the like may be used.

The hair dye composition of the present invention can be used as the first agent of a multi-agent oxidative hair dye, preferably a two-agent oxidative hair dye. The two-agent oxidative hair dye consists of a first agent, which is a hair dye composition of the present invention containing an oily component and an oxidative dye, and a second agent containing an oxidant, and is used as a first agent and a second agent. Is mixed and used.

Hereinafter, each component contained in the hair dye composition of the present invention will be described in detail.
Unless otherwise specified, the content of each component is the content of the hair dye composition at the time of storage. For example, in the two-agent type oxidative hair dye, it is the content in the first agent containing an oily component and an oxidative dye.

[Ascorbic acid, erythorbic acid, salts or esters thereof]
(A) Ascorbic acid, erythorbic acid, salts or esters thereof are 1 to 10 in the hair dye composition in order to promote the oxidative polymerization reaction of the oxidative dye by the oxidizing agent at the time of preparing the mixture and to suppress the skin stain. It is contained in an amount of% by mass. The content is preferably 2% by mass or more, more preferably 3% by mass or more as a lower limit value, and preferably 8% by mass or less as an upper limit value from the viewpoint of the effect of suppressing skin stains and hair dyeing power. It is preferably 6% by mass or less. When it is 1% by mass or more, a sufficient skin stain preventing effect can be obtained, and when it is 10% by mass or less, the hair dyeing power is improved and the emulsification stability of the dyeing agent composition is also improved, which is preferable.

Ascorbic acid, erythorbic acid, salts or esters thereof are used in the hair dye composition of the present invention. Specific examples include ascorbic acid, sodium ascorbic acid, potassium ascorbic acid, calcium ascorbic acid, ammonium ascorbic acid, monoethanolamine ascorbic acid, diethanolamine ascorbic acid, erythorbic acid, sodium erythorbic acid, ascorbic acid sulfate ester disodium, and ascorbic acid. Magnesium phosphate, ascorbic palmitate, ascorbic stearate, ascorbic dipalmitate, ascorbic tetra2-hexyldecanoate, ascorbic myristate, ascorbic laurate, ascorbic acetate, ascorbic propionate, ascorbic tartrate, ascorbic citrate, ascorbic succinate , Ascorbic benzoate, (ascorbic / tocopheryl) potassium phosphate, ascorbic ethyl, ascorbic acid allantin, ascorbic acid chitosan, ascorbic acid methylsilanol, tetradecylhexyl ascorbic, aminopropyl ascorbic phosphate, ascorbic acid polypeptide, ascorbic acid, ascorbic acid Examples thereof include methylsilanol pectinate.

Among these, ascorbic acid, sodium ascorbic acid, potassium ascorbic acid, calcium ascorbic acid, ammonium ascorbic acid, monoethanolamine ascorbic acid, diethanolamine ascorbic acid, erythorbic acid, sodium erythorbic acid, ascorbic acid sulfate ester disodium, phosphorus ascorbic acid. Magnesium acid ester, ascorbic palmitate, ascorbic stearate, ascorbic dipalmitate, ascorbic tetra2-hexyldecanoate, potassium (ascorbic / tocopheryl) phosphate, ascorbic ethyl, allantoin ascorbic acid, chitosan ascorbic acid, methylsilanol ascorbic acid, tetra Desirhexyl ascorbic, aminopropyl ascorbic phosphate, ascorbic acid polypeptide, ascorbic glucoside, and ascorbic methylsilanol pectinate are preferred. More preferably, it is ascorbic acid or erythorbic acid, and most preferably ascorbic acid.

In the present invention, one or more of these can be used. Further, the component (A) is preferably contained in the first agent from the viewpoint of safety.

[Oxidation dye]
Oxidizing dyes are dyes that develop color by oxidative polymerization with an oxidizing agent. Oxidation dyes include dye intermediates that develop color by their own oxidation and couplers that produce various color tones depending on the combination of the dye intermediates. The hair dye composition of the present invention contains a sulfate of a heterocyclic compound having a specific structure, which is a dye intermediate.

（ここで、Ｒは、１～６個の炭素原子を有する直鎖又は分枝したアルキル基、２～６個の炭素原子を有する直鎖又は分枝したモノ－又はポリヒドロキシアルキル基、直鎖又は分枝したモノ－又はポリアミノアルキル基を示す。） <Sulfate of heterocyclic compound>
The hair dye composition of the present invention contains a sulfate of a heterocyclic compound represented by the following general formula (1).

(Here, R is a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched mono- or polyhydroxyalkyl group having 2 to 6 carbon atoms, a straight chain. Or a branched mono- or polyaminoalkyl group.)

As the sulfate of the compound of the above (B) general formula (1), the 1-hydroxyethyl-4,5-diaminopyrazole sulfate represented by the following formula is preferable.

When used in a hair dye composition containing a large amount (1 to 10%) of the component (A), the oxidation dye composed of the sulfate of the compound of the general formula (1) maintains the effect of suppressing skin stains. As it is, it shows higher hair dyeing power than other oxidative dyes to which sulfate is added. In addition, oxidative dye salts generally have low emulsion stability, which tends to limit the composition allowed as a hair dye composition which is an emulsion. However, oxidative dyes composed of sulfates of the above compounds tend to be used. Since the hair dye composition containing the hair dye composition has high emulsion stability, other compositions are not limited, and hair dye compositions having various compositions can be obtained.

The content of the sulfate of the compound of the above general formula (1) in the hair dye composition is not particularly limited, but is preferably 0.05 to 5% by mass from the viewpoint of hair dyeing power and emulsification stability. The lower limit is more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more. The upper limit is more preferably 4% by mass or less, still more preferably 3% by mass or less. A hair dye composition having higher hair dyeing power can be exhibited by using 5% by mass or less and having higher emulsification stability, and sufficient hair dyeing power can be obtained by setting it to 0.05% by mass or more. be able to.

The mass ratio (B / A) of the sulfate of the compound of the general formula (1) to the component (A) is not particularly limited, but is, for example, 0.05 to 2. The lower limit is preferably more than 0.1, more preferably 0.2 or more. The upper limit is preferably less than 1, more preferably 0.5 or less. When (B / A) is 0.05 or more, the hair dyeing effect can be further exerted, and when it is 2 or less, the skin stain suppressing effect can be further exerted.

The sum of the content of the component (A) and the content of the sulfate of the compound of the general formula (1) is not particularly limited, but is, for example, 11% by mass or less, which is preferable as an upper limit value. Is less than 7% by weight. By setting the sum of the contents to 11% by mass or less, higher emulsification stability can be obtained. The lower limit value is preferably 2% by mass or more, more preferably 4% by mass or more, from the viewpoint of further exerting the effect of the present invention.

<Other oxidation dyes>
The hair dye composition of the present invention may contain other oxidative dyes. Other oxidation dyes include dye intermediates and couplers. The dye intermediate is a dye precursor which is mainly o- or p-phenylenediamines or aminophenols, and is usually a colorless or weakly colored compound itself.
Specifically, p-phenylenediamine, toluene-2,5-diamine (p-toluylenediamine), N-phenyl-p-phenylenediamine, 4,4'-diaminodiphenylamine, p-aminophenol, o-amino. Phenol, p-methylaminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, o-chlor-p-phenylenediamine, 4-amino-m- Examples thereof include cresol, 2-amino-4-hydroxyethylaminoanisole, 2,4-diaminophenol and salts thereof.

Examples of the coupler include mainly m-diamines, aminophenols or diphenols, and specifically, resorcin, catechol, pyrogallol, fluoroglucin, gallic acid, hydroquinone, 5-amino-o-cresol, m-amino. Phenol, 5- (2-hydroxyethylamino) -2-methylphenol, m-phenylenediamine, 2,4-diaminophenoxyethanol, toluene-3,4-diamine, α-naphthol, 2,6-diaminopyridine, diphenylamine, Examples thereof include 3,3'-iminodiphenyl, 1,5-dihydroxynaphthalene and tannic acid and salts thereof.

Oxidation dyes include acid addition salts of each of the above-mentioned compounds. Examples of the acid addition salt include addition salts of inorganic acids such as hydrochlorides and sulfates, and addition salts of organic acids such as acetates. The content of the acid addition salt of the oxidation dye is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less from the viewpoint of emulsion stability.

One or two or more of these oxidation dyes can be selected and used depending on the desired color tone.
The content of the other oxidative dye in the hair dye composition is not particularly limited, but is preferably 0.1 to 10% by mass, and more preferably 1 to 5% by mass.

[Alkaline agent]
The alkaline agent has the effect of swelling the hair and promoting the penetration of dyes and oxidizing agents. Examples of the alkaline agent include alkanolamine, ammonia, silicate, carbonate, hydrogencarbonate, metasilicate, phosphate, sulfate, chloride, organic amine, basic amino acid, alkali metal or alkaline earth. Examples thereof include metal hydroxides. Specific examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol, and isopropylamine, and examples of the silicate include sodium silicate and potassium silicate. Examples of the carbonate include sodium carbonate, ammonium carbonate, magnesium carbonate, guanidine carbonate and the like, examples of the hydrogen carbonate include sodium hydrogen carbonate and ammonium hydrogen carbonate, and examples of the metasilicate include sodium metasilicate and potassium metasilicate. Etc. are exemplified, examples of the phosphate include primary ammonium phosphate, diammonium phosphate, disodium monohydrogen phosphate, trisodium phosphate and the like, and examples of the sulfate salt include ammonium sulfate and the like, chlorides. Examples thereof include ammonium chloride, and examples of organic amines include 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol, and guanidine, which are basic amino acids. Examples thereof include arginine, lysine and salts thereof, and examples of hydroxide of alkali metal or alkaline earth metal include calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide and the like. Among these, it is preferable to contain alkanolamine, and it is more preferable to contain monoethanolamine.

The content of the alkaline agent in the hair dye composition is not particularly limited, but is preferably 0.5 to 10% by mass. The lower limit is more preferably 1% by mass or more, still more preferably 2% by mass or more. The upper limit is more preferably 7% by mass or less, still more preferably 5% by mass or less.

The hair dye composition of the present invention preferably contains (C) alkanolamine. The hair dye composition containing 1 to 10% by mass of the component (A) and the sulfate of the compound of the general formula (1) further contains an alkanolamine to further suppress the skin stain and the hair dyeing effect. Can be improved.

(C) The mass ratio (A / C) of the component (A) to the alkanolamine is not particularly limited, but is preferably 0.7 to 6. The lower limit value is more preferably 0.9 or more, and the upper limit value is more preferably less than 5. When (A / C) is 0.7 or more, the skin stain suppressing effect and the hair dyeing effect can be further exerted, and when it is 6 or less, the skin stain suppressing effect can be further exerted, and the residual alkali can be further exerted. It is possible to suppress the deterioration of the feel due to.

(C) The mass ratio (B / C) of the sulfate of the compound of the general formula (1) to the alkanolamine is not particularly limited, but is preferably 0.10 to 10.0. The lower limit is more preferably 0.20 or more, further preferably 0.25 or more, and particularly preferably 0.30 or more. The upper limit is more preferably 5.0 or less, further preferably 2.0 or less, and particularly preferably 1.0 or less. When the mass ratio (B / C) is in the above range, the skin stain suppressing effect and the hair dyeing effect can be further exhibited.

[Oil component]
The hair dye composition of the present invention contains an oily component. Examples of the oily component include higher alcohols, fats and oils, waxes, hydrocarbons, higher fatty acids, esters, silicone oils, fluorine oils and the like. From these oily components, one kind or two or more kinds can be selected and used. By containing an oily component, the hair dyeing power can be improved.

Examples of higher alcohols include cetyl alcohol (cetanol), stearyl alcohol, cetostearyl alcohol, oleyl alcohol, linoleil alcohol, linolenyl alcohol, araquil alcohol, behenyl alcohol, lauryl alcohol, myristyl alcohol, 2-hexyldecanol and isostearyl. Examples thereof include alcohol, 2-octyldodecanol, decyltetradecanol, phytosterol, phytostanol, cholesterol, cholestanol, lanosterol, ergosterol and the like.

Fats and oils are triglycerides, that is, triesters of fatty acids and glycerin. For example, olive oil, rose hip oil, camellia oil, shea butter, macadamia nut oil, almond oil, brown seed oil, southern ka oil, saflower oil, sunflower oil, soybean oil, cotton seed oil, sesame oil, beef fat, cacao fat, corn oil, peanuts. Examples thereof include oil, rapeseed oil, rice bran oil, rice germ oil, wheat germ oil, honeybee oil, grape seed oil, avocado oil, carrot oil, castor oil, flaxseed oil, palm oil, mink oil, egg yolk oil and the like.

Waxes are esters of higher fatty acids and higher alcohols. Examples thereof include beeswax, candelilla wax, carnauba wax, jojoba oil, lanolin, whale wax, rice bran wax, sugarcane wax, palm wax, montan wax, cotton wax, baby wax, ibota wax, capoc wax, celac wax and the like.

Hydrocarbons are compounds consisting of carbon and hydrogen. Examples thereof include liquid paraffin, paraffin, microcrystalline wax, petrolatum, isoparaffins, zokerite, selecin, polyethylene, α-olefin oligomer, polybutene, synthetic squalane, squalane, hydrogenated squalane, limonene, turpentine and the like.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, hydroxystearic acid, 12-hydroxystearic acid, oleic acid, undecylenic acid, linoleic acid, ricinoleic acid, lanolin fatty acid and the like. Can be mentioned.

Esters are compounds obtained by the dehydration reaction between fatty acids and alcohols. For example, diisopropyl adipate, -2-hexyldecyl adipate, isopropyl myristate, myristyl myristate, cetyl octanoate, cetyl isooctanoate, isononyl isononanoate, diisopropyl sebacate, isopropyl palmitate, 2-ethylhexyl palmitate, for example, Cetyl ethylhexanate, butyl stearate, isocetyl isostearate, hexyl laurate, decyl oleate, fatty acid (C10-30) (cholesteryl / lanosteryl), lauryl lactate, octyldodecyl lactate, lanolin acetate, dipentaerythritol fatty acid ester, mono Examples thereof include N-alkyl glycol isostearate and lanolin derivatives.

Silicone oil is a synthetic polymer in which silicon with an organic group and oxygen are alternately linked by chemical bonds. For example, dimethylpolysiloxane (INCI name: dimethicone), dimethylpolysiloxane with hydroxy end group (INCI name: dimethiconol), methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, polyether-modified silicone, average. Examples thereof include highly polymerized silicone having a degree of polymerization of 650 to 10,000, amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, and fluorine-modified silicone.

Among the above, examples of the amino-modified silicone include aminopropylmethylsiloxane / dimethylsiloxane copolymer (INCI name: aminopropyldimethicone), aminoethylaminopropylsiloxane / dimethylsiloxane copolymer (INCI name: amodimethicone), and the like. Examples thereof include an aminoethylaminopropylmethylsiloxane / dimethylsiloxane copolymer (INCI name: trimethylsilyl amodimethicone).

The content of the oily component in the hair dye composition is not particularly limited, but is preferably 0.1 to 30% by mass. The lower limit is more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more. The upper limit is more preferably 20% by mass or less, still more preferably 10% by mass or less.

[Other ingredients]
The hair dye composition of the present invention may contain the following components in addition to the above components, if necessary.
Other components include, for example, direct dyes, surfactants, antioxidants such as anhydrous sodium sulfite, preservatives such as phenoxyethanol and sodium benzoate, organic solvents such as ethanol, saccharides such as sorbitol and maltose, hydroxyethyl cellulose, and the like. Water-soluble polymers such as carboxyvinyl polymers, cationized water-soluble polymers such as polydimethyldimethylene piperidinium solution (polydimethyldimethylenepyrrolidinium solution), diallyldimethylammonium chloride and hydroxyethyl cellulose, polyethylene glycol, Polyhydric alcohols such as dipropylene glycol, chelating agents such as ethylenediamine hydroxyethyl trisodium trisodium dihydrate, tetrasodium hydroxyethanediphosphonate, inorganic salts such as sodium chloride, ammonium sulfate, ammonium nitrate, ammonium acetate, citric acid, Excluding tartrate acid, lactic acid, malic acid, succinic acid, fumaric acid, maleic acid, pyrophosphate, gluconic acid, glucuronic acid, pH adjuster, hair growth ingredient, plant extract, crude drug extract, amino acid / peptide, urea, ascorbic acid. Examples include vitamins (excluding vitamin A), fragrances, and UV absorbers.

<Direct dye>
The direct dye is a compound having a color, and is not particularly limited as long as it is a dye that adheres to or penetrates into the hair to dye the hair. For example, acid dyes, basic dyes, natural dyes, nitro dyes, HC dyes, disperse dyes and the like can be mentioned.
Further, these direct dyes may be blended alone or in combination of two or more depending on the desired color tone of the hair.

Specific examples of the acidic dye include, for example, Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 227, and Red No. 230. (1), Yellow 4, Yellow 5, Yellow 202 (1), Yellow 202 (2), Yellow 203, Orange 205, Orange 207, Orange 402, Green 3 , Green No. 204, Green No. 401, Purple No. 401, Blue No. 1, Blue No. 2, Blue No. 202, Bracket No. 201, Black No. 401 and the like.

Specific examples of basic dyes include Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 47, Basic Blue 75, Basic Blue 99, and Basic Blue 124. , Basic Brown 4, Basic Brown 16, Basic Brown 17, Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange 2, Basic Orange 31, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 51, Basic Red 76, Basic Red 118, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 11: 1, Basic Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28, Basic Yellow 57, Basic Yellow 87, etc.

Specific examples of natural dyes include kuchinashi dye, turmeric dye, annatto dye, sodium copper chlorophyllin, paprika dye, lac dye, henna and the like.

Specific examples of the nitro dye include, for example, 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picric acid, picric acid. Acids and salts thereof may be mentioned.

Specific examples of HC dyes include, for example, HC Blue No.2, HC Blue No.5, HC Blue No.6, HC Blue No.9, HC Blue No.10, HC Blue No.11, and HC Blue No. 12, HC Blue No.13, HC Blue No.16, HC Orange No.1, HC Orange No.2, HC Orange No.3, HC Red No.1, HC Red No.3, HC Red No.7, HC Red No.10, HC Red No.11, HC Red No.13, HC Red No.14, HC Violet No.1, HC Violet No.2, HC Yellow No.2, HC Yellow No.4, HC Yellow No.5, HC Yellow No.6, HC Yellow No.9, HC Yellow No.10, HC Yellow No.11, HC Yellow No.12, HC Yellow No.13, HC Yellow No.14, HC Yellow No. 15 and so on.

Specific examples of disperse dyes include, for example, Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Blue 7, Disperse Brown 4, Disperse Orange 3, Disperse Red 11, Disperse Red 15, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Violet 15 and so on.

The content of the direct dye in the hair dye composition is not particularly limited, but is preferably 0.001% by mass or more and 20.0% by mass or less. The lower limit value is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more. On the other hand, the upper limit value is more preferably 15.0% by mass or less, further preferably 10.0% by mass or less, and particularly preferably 5.0% by mass or less.

<Surfactant>
Examples of the surfactant include a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.
In the following description, POE indicates a polyoxyethylene chain, POP indicates a polyoxypropylene chain, and the numbers in parentheses following the POE indicate the number of added moles thereof. The number in parentheses following the alkyl indicates the number of carbon atoms in the fatty acid chain.

Examples of the nonionic surfactant include POE alkyl ethers, POE alkyl phenyl ethers, POE / POP alkyl ethers, POE sorbitan fatty acid esters, POE mono fatty acid esters, POE glycerin fatty acid esters, and polyglycerin fatty acid esters. , Monoglycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, alkylpolyglucosides and the like. Specific examples of POE alkyl ethers include POE lauryl ether, POE cetyl ether, POE stearyl ether, POE behenyl ether, POE lanolin, POE phytosterol and the like.
Examples of the number of repeating units of POE and POP include 2 to 100, and any one that exhibits a surface-active action can be used.

The content of the nonionic surfactant in the hair dye composition is not particularly limited, but is preferably 0.001 to 40% by mass. The lower limit is more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more. The upper limit is more preferably 30% by mass or less, still more preferably 20% by mass or less.

Examples of the cationic surfactant include monoalkyl type quaternary ammonium salt, dialkyl type quaternary ammonium salt, trialkyl type quaternary ammonium salt, benzalconium type quaternary ammonium salt, and monoalkyl ether type quaternary ammonium salt. Quaternary ammonium salts such as alkyl quaternary ammonium salts, alkylamine salts, fatty acid amidoamine salts, ester-containing tertiary amine salts, amine salts such as arcobel type tertiary amine salts, alkylpyridinium salts, and cyclic quaternary ammonium salts such as alkylisoquinolium salts. Examples include salts and benzethonium chloride.

Alkyl quaternary ammonium salts are preferable, monoalkyl type quaternary ammonium salts and dialkyl type quaternary ammonium salts are more preferable, and monoalkyl type quaternary ammonium salts are particularly preferable.

Examples of the monoalkyl type quaternary ammonium salt include lauryltrimethylammonium chloride, lauryltrimethylammonium bromide, alkyl (16,18) trimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium saccharin, and chloride. Stearyltrimethylammonium, stearyltrimethylammonium bromide, behenyltrimethylammonium chloride, stearyltrimethylammonium saccharin, alkyl chloride (28) trimethylammonium, diPOE chloride (2) oleylmethylammonium, diPOE stearylmethylammonium chloride, POE chloride (1) POP (25) diethylmethylammonium, POPmethyldiethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, behenyltrimethylammonium methylsulfate and the like can be mentioned. Particularly preferred are stearyltrimethylammonium chloride, alkyl (16,18) trimethylammonium chloride, and cetyltrimethylammonium chloride.

Examples of the dialkyl type quaternary ammonium salt include dialkyl chloride (12 to 15) dimethylammonium, dialkyl chloride (12 to 18) dimethylammonium, dialkyl chloride (14 to 18) dimethylammonium, dicocoyl dimethylammonium chloride, and disetyl chloride. Examples thereof include dimethylammonium, disstearyldimethylammonium chloride, isostearyllauryldimethylammonium chloride and the like.

The content of the cationic surfactant in the hair dye composition is not particularly limited, but is preferably 0.001 to 10% by mass. The lower limit is more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more. The upper limit is more preferably 5% by mass or less, still more preferably 3% by mass or less.

Examples of the anionic surfactant include alkyl ether sulfate, POE alkyl ether sulfate, alkyl sulfate, alkenyl ether sulfate, alkenyl sulfate, olefin sulfonate, alkane sulfonate, saturated or unsaturated fatty acid salt. , Alkyl or alkenyl ether carboxylate, α-sulfon fatty acid salt, N-acylamino acid type surfactant, phosphoric acid mono or diester type surfactant, and sulfosuccinic acid ester are exemplified. The counterion of the anion group of these surfactants may be, for example, sodium ion, potassium ion, or triethanolamine.

More specifically, sodium lauryl sulfate, sodium myristyl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, sodium POE lauryl ether sulfate, POE triethanolamine lauryl ether sulfate, POE. Sodium lauryl ether sulfate, POE stearyl ether sulfate sodium, stearoyl methyl taurine sodium, dodecylbenzene sulfonate triethanolamine, sodium tetradecene sulfonate, sodium lauryl phosphate, POE lauryl ether phosphate and its salts, N-lauroyl glutamates (lauroyl). (Sodium glutamate, etc.), N-lauroylmethyl-β-alanine salt, N-acylglycine salt, N-acylglutamate salt, higher fatty acids lauric acid, myristic acid, and salts of these higher fatty acids are exemplified. More than seeds can be used.

The content of the anionic surfactant in the hair dye composition is not particularly limited, but is preferably 0.01 to 5% by mass. The lower limit is more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more. The upper limit is more preferably 3% by mass or less, still more preferably 1.5% by mass or less.

Examples of the amphoteric tenside include an amino acid type amphoteric tenside agent and a betaine type amphoteric tenside agent.
Specific examples of the amino acid-type amphoteric surfactant include N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium (Na lauroamphoacetate) and 2-alkyl-N-carboxymethyl-N-hydroxyethyl. Imidazolinium betaine, undecyl hydroxyethyl imidazolinium betaine sodium, alkyldiaminoethylglycine hydrochloride, N-coconut oil fatty acid acyl-N'-carboxyethyl-N'-hydroxyethylethylenediamine sodium, N-coconut oil fatty acid acyl-N '-Carboxyethoxyethyl-N'-carboxyethylethylenediamine disodium, N-coconut oil fatty acid acyl-N'-carboxymethoxyethyl-N'-carboxymethylethylenediamine disodium, lauryldiaminoethylglycine sodium, palm oil fatty acid acyl-N Glycin-type amphoteric surfactants such as -carboxyethyl-N-hydroxyethylethylenediamine sodium; aminopropionic acid-type amphoteric surfactants such as sodium laurylaminopropionate, sodium laurylaminodipropionate, triethanolamine laurylaminopropionate; And so on.
Specific examples of the betaine-type amphoteric surfactant include coconut oil alkyl betaine, lauryldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, stearyldimethylbetaine sodium, coconut oil fatty acid amide propyl betaine, and palm. Examples thereof include aminoacetate betaine-type amphoteric surfactants such as oil fatty acid amide propyl betaine, lauric acid amide propyl betaine, ricinoleic acid amide propyl betaine, and stearyldihydroxyethyl betaine; and sulfobetaine-type amphoteric surfactants such as lauryl hydroxysulfobetaine. ..

The content of the amphoteric tenside agent in the hair dye composition is not particularly limited, but is preferably 0.001 to 5% by mass. The lower limit is more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more. The upper limit is more preferably 3% by mass or less, still more preferably 2.5% by mass or less.

The total content of all the surfactants in the hair dye composition is not particularly limited, but is preferably 0.01 to 50% by mass. The lower limit is more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more. The upper limit is more preferably 40% by mass or less, still more preferably 30% by mass or less.

<Multivalent alcohol>
Examples of the polyhydric alcohol include polyethylene glycol and dipropylene glycol. Among these, polyethylene glycol is preferable, and (D) polyethylene glycol 400 is more preferable, from the viewpoint of improving the effect of suppressing skin stains. The content of the polyhydric alcohol in the hair dye composition is not particularly limited, but is preferably 0.1 to 20% by mass. The lower limit value is more preferably 1% by mass or more, and the upper limit value is more preferably 10% by mass or less.

The pH of the hair dye composition of the present invention is not particularly limited, but is, for example, pH 7 to 11 immediately after mixing.
The sulfate of the compound of the general formula (1), particularly 1-hydroxyethyl-4,5-diaminopyrazole sulfate, has a characteristic of exhibiting a red color in a low pH region, which is not found in other oxidation dyes. From the viewpoint of improving the hair dyeing power, the upper limit of the pH immediately after mixing is preferably pH 9.5 or less, more preferably pH 9.2 or less, still more preferably pH 9 or less. From the viewpoint of producing a bright red color, the lower limit of pH immediately after mixing is preferably pH 7.5 or higher, more preferably pH 7.8 or higher, and even more preferably pH 8.0 or higher.

The pH of the hair dye composition can be adjusted by using an acid such as phosphoric acid or an alkali such as sodium hydroxide. The pH of the hair dye composition of the present invention is a measured value measured immediately after mixing in a 10% solution of a 1: 1 mixture of the first agent and the second agent. As a measuring method, it can be measured using a pH meter such as pH-METERF-22 manufactured by HORIBA.

[Composition of the second agent]
When the hair dye composition of the present invention is used as the first agent of a two-agent hair dye, the second agent used is a general second agent used in the field of oxidative hair dye. be able to. The composition of the second agent is not particularly limited, but preferably contains an oxidizing agent, and hydrogen peroxide is preferable as the oxidizing agent. The content of hydrogen peroxide in the second agent is 0.1 to 9% by mass from the viewpoint of the effect of suppressing skin stains, and the lower limit is preferably 0.5% by mass or more, more preferably. Is 1% by mass or more. The upper limit is preferably 6% by mass or less, and more preferably 3% by mass or less. When it is 9% by mass or less, the effect of suppressing skin stains is further improved. Further, by setting the concentration to 0.1% by mass or more, a sufficient effect as an oxidizing agent can be obtained.

Hereinafter, the present invention will be specifically described with reference to Examples, but the technical scope of the present invention is not limited by these Examples.

1. 1. Evaluation of hair dye composition [Preparation of hair dye composition]
(Hair dye composition containing oxidative dye)
As a hair dye composition containing an oxidative dye, the first agent of a two-agent oxidative hair dye was prepared. The formulation of the first agent is shown in Tables 1 to 3 below. The first agent was prepared according to a conventional method. The unit of the blending amount in the table is mass%.

[Preparation of second agent]
A second agent (hydrogen peroxide concentration 2% by mass) having the following composition was prepared by a conventional method.
(Second agent)
Cetanol 1.2% by mass
POE (30) cetyl ether 0.3% by mass
POE (10) cetyl ether 0.3% by mass
Stearyl Trimethylammonium Chloride 1.0% by mass
Hydrogen peroxide solution (35% by mass) 5.7% by mass
Hydroxyethanediphosphonic acid 0.1% by mass
Hydroxyethanediphosphonic acid 4Na 0.2% by mass
Phenoxyethanol 0.1% by mass
Total balance of purified water 100% by mass

[Evaluation methods]
<Emulsification stability>
Weigh 30 grams of the hair dye composition (first agent) prepared above in a No. 4 standard bottle, cover it with an inner lid, and let it stand at 50 ° C and 60 ° C. Evaluation was performed.
(Criteria for emulsification stability)
No separation was observed even after standing at 5:50 ° C for 1 month and at 60 ° C for 2 weeks.
No separation was observed even after standing at 4: 50 ° C for 1 month and at 60 ° C for 1 week.
No separation was observed even after standing at 3: 50 ° C for 1 month and at 60 ° C for 3 days.
No separation was observed even after standing at 2:50 ° C for 1 month and at 60 ° C for 1 day.
Separation is not observed at 1:50 ° C. for 1 month, but separation is observed at 60 ° C. after 1 day.

<Skin stains>
The hair dye composition (first agent) according to each example is mixed 1: 1 with the second agent to prepare an oxidative hair dye, and 1 g of the oxidative hair dye is circular with a diameter of 1 cm in the inner part of the arm. It was applied to the area, left for 10 minutes, and then rinsed with warm water. Next, it was lightly rubbed with a finger for 1 minute using soap and rinsed with warm water.

After the treatment as described above, 10 panelists visually observed the skin stain (degree of staining on the skin). In the visual evaluation, the skin stains were evaluated according to the following evaluation criteria, and the value obtained by rounding off the average value of the evaluation points of the 10 panelists was used as the evaluation point of each hair dye composition.
(Criteria for judging skin stains)
5: Very little skin stains.
4: There is little skin stain.
3: There is little background stain.
2: There is a lot of dirt on the skin.
1: There is a lot of skin stains.

<Hair dyeing power>
(Hair dyeing treatment method for hair dye composition)
An oxidative hair dye was prepared by mixing the hair dye composition (first agent) and the second agent according to each example at a ratio of 1: 1. 1 g of this oxidative hair dye was applied to 1 g of hair bundles and left at 30 ° C. for 30 minutes. Then, the hair bundle was washed with shampoo to wash off the oxidative hair dye. Next, a conditioner was applied to the hair bundle. After rinsing the hair tresses and rinsing the conditioner, the moisture in the hair tresses was wiped off with a towel and finally dried with a dryer.

Ten panelists visually observed the dyed state of the hair bundles that had been dyed as described above. In the visual evaluation, the hair dyeing ability was evaluated according to the following evaluation criteria, and the value obtained by rounding off the average value of the evaluation points of the 10 panelists was used as the evaluation point of each hair dye composition.
(Criteria for judging hair dyeing power)
5: Hair dyeing power is very high.
4: High hair dyeing power.
3: Hair dyeing power is slightly high.
2: Hair dyeing power is low.
1: Hair dyeing power is very low.

Referring to Table 1, in Examples 1 to 3 containing 1 to 10% by mass of (A) ascorbic acid and 1-hydroxyethyl-4,5-diaminopyrazole sulfate as (B), the content of ascorbic acid is Compared with Comparative Examples 1 to 3 which are out of the specified range, a high effect of suppressing skin stains, hair dyeing power, and emulsification stability were confirmed at the same time. Further, in Comparative Examples 4 and 5 containing 1-hydroxyethyl-4,5-diaminopyrazole sulfate, it was difficult to achieve both the skin stain suppressing effect, the hair dyeing power, and the emulsification stability.

In Table 2, the total mass ratio and content of (A) ascorbic acid and (B) 1-hydroxyethyl-4,5-diaminopyrazole sulfate were examined. In the examples in which the mass ratio (B / A) of (B) 1-hydroxyethyl-4,5-diaminopyrazole sulfate to (A) ascorbic acid exceeded 0.1, excellent hair dyeing power was confirmed. Further, in the examples in which (B / A) was less than 1, an excellent skin stain suppressing effect was confirmed.

Further, excellent emulsion stability was confirmed in Examples in which the sum of the content of (A) ascorbic acid and the content of (B) 1-hydroxyethyl-4,5-diaminopyrazole sulfate was less than 7% by mass. Was done.

In Table 3, the presence / absence and content of (C) alkanolamine were examined.
(C) Compared with Example 10 which does not contain monoethanolamine, which is an alkanolamine, in Examples 1 and 7 to 9 containing monoethanolamine, a high skin stain suppressing effect and an excellent hair dyeing effect were observed. Further, in the examples in which the mass ratio (A / C) of (A) ascorbic acid to (C) alkanolamine was 0.7 or more, a higher skin stain suppressing effect was confirmed, and in particular, it was 0.9 or more and less than 5. In Example 1, it was confirmed that both the skin stain suppressing effect and the hair dyeing effect were particularly excellent.
In addition, the improvement of the skin stain suppressing effect and the hair dyeing effect by alkanolamine was not observed in the comparative example containing (B) 1-hydroxyethyl-4,5-diaminopyrazole sulfate.

2. 2. About the influence of the composition of the second agent In order to confirm the influence of the composition of the second agent on the skin stain suppressing effect and the hair dyeing effect, it is excessive with the second agent (second agent-A) used in the above experiment shown in Table 4. Oxidative hair dyes A and B were prepared using the second agent-B in which the hydrogen peroxide concentration was increased to 5.8%, and the same experiments as in the previous experiment were conducted for skin stains and hair dyeing power. As the first agent, the hair dye composition of Example 1 used in the above experiment was used. The results of the experiment are shown in Table 5. The unit of the blending amount in the table is mass%.

As shown in Table 5, the oxidative hair dye B having a high hydrogen peroxide concentration of 6% by mass in the second agent has a lower effect of suppressing skin stains than the oxidative hair dye A having 2% by mass. Was observed. No difference in hair dyeing ability was observed.

The oxidative hair dye composition of the present invention can be used as a hair dye for dyeing body hair such as human head hair, beard, eyebrows, and shin hair. In addition, it may be used to dye the body hair of animals such as pets.
The oxidative hair dye composition of the present invention can be used as a hair dye for coloring in a beauty salon, a barber shop, etc., and a hair dye for self-coloring.

Claims (4)

An emulsified composition containing an oily component,
Hair dyeing characterized by containing (A) ascorbic acid, erythorbic acid, salts or esters thereof in an amount of 1 to 10% by mass, and (B) an oxidation dye consisting of a sulfate of a compound represented by the following general formula (1). Agent composition.

(Here, R is a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched mono- or polyhydroxyalkyl group having 2 to 6 carbon atoms, a straight chain. Or a branched mono- or polyaminoalkyl group.) The hair dye composition according to claim 1, wherein the sulfate of the compound represented by (B) the general formula (1) is 1-hydroxyethyl-4,5-diaminopyrazole sulfate. (A) The mass ratio (B / A) of the sulfate of the compound represented by the general formula (1) to ascorbic acid, erythorbic acid, salts or esters thereof is more than 0.1 and less than 1, and is less than 1. The sum of the content of (A) ascorbic acid, erythorbic acid, salts or esters thereof and the content of (B) sulfate of the compound represented by the general formula (1) is less than 7% by mass. The hair dye composition according to claim 1 or 2. The hair dye composition according to any one of claims 1 to 3, further comprising (C) an alkanolamine.