JPH09309817A - Acidic hair dye and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an acidic hair dye bearing such characteristics as excellent temperature stability and excellent operability when applied to the hair. SOLUTION: This acidic hair dye, which is a composition comprising an acid dye, dyeing auxiliary and acid, is obtained by the following method: first, a hydrophilic nonionic surfactant of the formula (R is a >=8C alkene, etc.; X is an ether group, etc.; (n) is an integer of 15-120) such as an ethylene oxide 15-80mol adduct of lanolin, etc., is added to an aqueous solvent followed by addition of an oily phase and a dyeing auxiliary to prepare an oil-in-water- soluble solvent type emulsion; next, water, an acid dye and an acid are added to the above emulsion into an oil-in-water type emulsion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acidic hair dye and a method for producing the same, and more specifically, it has good dyeing properties even when the amount of a dyeing aid is small, and the operability when applied to hair ( The present invention relates to an acidic hair dye which is excellent in adhesion to hair and easiness of spreading, has a good feel to the hair, has little decrease in viscosity after application and is less likely to drip, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a hair dye composition for hair, an oxidative hair dye for dyeing hair by utilizing an oxidative polymerization reaction and a legal dye are used. There is an acidic hair dye that dyes hair in the acidic region. Among them, the acidic hair dye is mainly composed of an acidic dye, a dyeing aid (mostly benzyl alcohol is used), a solvent and an acid for pH adjustment (mostly citric acid is used). It contains a thickener to prevent it from dripping from the hair at the time of use.Since it is usually a one-part type, it is easier to use than an oxidative hair dye that requires two or more parts. It has advantages in points. However, the optimum pH range is 1.5-
4.5 (this range is preferable in order to obtain good dyeing property and washing resistance, the average is around 3), which is considerably low in ordinary hair cosmetics, and therefore it is difficult to satisfy the feeling of use. There is a drawback that. In addition, a dyeing aid such as benzyl alcohol is usually used in acidic hair dyes in order to enhance the dyeing property. However, such dyeing aids are irritating to the skin, and blending in a large amount has a problem in safety and is not preferable in terms of stability. Therefore, there has been a demand for the development of an acidic hair dye having good dyeing properties even if the amount of dyeing aid is reduced.

The present invention has been made in view of such conventional circumstances, and it is used by reducing the amount of the dyeing auxiliary agent while satisfying the essential conditions as an acidic hair dye such as dyeing property and washing resistance. It is an object of the present invention to provide an acidic hair dye that can give a good feeling afterwards.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned objects, the present inventors have found that if an oil-in-water emulsion prepared by a specific method is used, a large amount of dyeing aid is added. The inventors have found that good dyeing properties can be obtained without compounding, and have completed the present invention.

That is, the present invention relates to an acidic hair dye containing an acid dye, a dyeing aid and an acid, wherein as a first step, a hydrophilic nonionic surfactant is added to a water-soluble solvent and then added thereto. An oil-in-water emulsion obtained by adding an oil phase and a dyeing aid to prepare an oil-in-water emulsion in a water-soluble solvent, and adding water and an acid dye to the oil-in-water emulsion in a water-soluble solvent as a second step. It is a characteristic acidic hair dye.

In the method for producing the same, as the first step, a hydrophilic nonionic surfactant is added to a water-soluble solvent, and then an oil phase and a dyeing auxiliary agent are added thereto to form an oil-in-water emulsion. It is characterized in that, as a second step, water, an acid dye and an acid are added to the oil-in-water emulsion to prepare an oil-in-water emulsion.

Next, the structure of the present invention will be described. The Applicant has added a hydrophilic nonionic surfactant to a water-soluble solvent as a first step, and then an oil phase to this to prepare an oil-in-water emulsion, and the second step is It has already been found that an oil-in-water emulsion obtained by adding water to an emulsion is very stable (Japanese Patent Publication No. 57-29213).

The present invention uses the above oil-in-water emulsion, and this oil-in-water emulsion is, for example,
A hydrophilic nonionic surfactant obtained by addition-polymerizing 15 mol or more of ethylene oxide is dissolved in a water-soluble solvent, and then an oil phase is added. It is an oil-in-water emulsion obtained by an emulsification method in which an agent is efficiently oriented and then water is gradually added to act as a water phase in a water-soluble solvent.

The general characteristics of the surfactant used in the present invention to obtain a stable emulsion are as follows:
15 to 120 mol of ethylene oxide added to a lipophilic group having 8 to 30 carbon atoms, or ethylene oxide (15 mol or more) and propylene oxide (1 to 3 mol)
(0 mol). Since all of these hydrophilic nonionic surfactants are high molecular weight substances, it is impossible to use them suddenly in an oil-water system to obtain a stable emulsion having a strong interface film, but it is impossible. As a first step, a method in which a surfactant is added to a water-soluble solvent and then an oil phase is added can efficiently orient a surfactant at an interface, and then a stable emulsion is produced by adding an aqueous phase. Is what you can do.

Next, the hydrophilic nonionic activators used in the present invention are classified into types I to IX and specifically described. Type (I):

[0011]

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Wherein R represents an alkane, alkene, aryl or steroid group having 8 or more carbon atoms, X represents an ether or ester group, and n represents an integer of 15 to 120. In the type (I) Particularly preferred as the hydrophilic nonionic surfactant in the present invention are lanolin and their fatty acids and ethylene oxides of alcohols 15 to 80.
A molar adduct and a 15-60 molar adduct of ethylene oxide of cholestanol or cholesterol. Type (II):

[0013]

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(Wherein, R represents an alkane, alkene, aryl, or steroid group having 8 or more carbon atoms, X represents an ether or ester group, n represents an integer of 20 or more, X ′ represents an ester group, and R ′ represents a carbon atom. Alkanes and alkene groups of formulas 2 to 18 are shown.) Among the type (II), particularly preferred as the hydrophilic nonionic surfactant in the present invention are lanolin and their fatty acids and ethylene oxides of alcohols 20 to 80.
2-ethylhexanoic acid or isostearic acid ester of a molar adduct and 2-ethylenehexanoic acid and isostearic acid ester of a 15-60 mol adduct of cholesteranol or cholesterol ethylene oxide. Type (III):

[0015]

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Wherein R represents an alkane, alkene, aryl or steroid group having 8 or more carbon atoms, X represents an ether or ester group, n represents an integer of 1 to 30, and n ′ represents 15
The following integers are shown. Among the types (III), particularly preferred as the hydrophilic nonionic surfactant in the present invention are propylene oxide 1 of cetanol, cholestanol and cholesterol.
１２12 mol adduct, and ethylene oxide 20８8
0 mol was added. Type (IV):

[0017]

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(Wherein, R represents an alkane, alkene, aryl, or steroid group having 8 or more carbon atoms, X represents an ether or ester group, R ′ represents an alkane having 2 to 18 carbon atoms,
Shows an alkene group. Among the types (IV), particularly preferred as the hydrophilic nonionic surfactant in the present invention are propylene oxide 1 to cetanol, cholestanol and cholesterol.
It is 2-ethylhexanoic acid or isostearic acid ester of the compound of type (III) obtained by adding 20 to 80 mol of ethylene oxide to a 12 mol adduct. Type (V):

[0019]

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(Wherein, R represents an alkane having 8 or more carbon atoms, an alkene, ethylene glycol of a hydroxycarboxylic acid,
Propylene glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sorbitan, pentaerythritol ester residues, n is an integer of 4 to 50, n 'is an integer of 2 to 6, nx
n ′ is 30 or more in any combination. Among the types (V), particularly preferred as the hydrophilic nonionic surfactant in the present invention are 30-80 mol of ethylene oxide adduct of castor oil and hydrogenated castor oil. Type (VI):

[0021]

[Chemical 6]

Wherein R is an alkane having 8 or more carbon atoms, an alkene, an ethylene glycol of a hydroxycarboxylic acid,
Propylene glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sorbitan, an ester residue of pentaerythritol, n is an integer of 4 to 50, n 'is an integer of 2 to 6, X' is an ester R ′ represents an alkane or alkene group having 2 to 18 carbon atoms. Among the types (VI), particularly preferred as the hydrophilic nonionic surfactant in the present invention are 2- Castane oil and 30-80 mol adduct of ethylene oxide of hydrogenated castor oil.
Ethylhexanoic acid or isostearic acid ester. Type (VII):

[0023]

[Chemical 7]

(Wherein, R represents an alkane having 8 or more carbon atoms, alkene, ethylene glycol of hydroxycarboxylic acid,
The ester residues of propylene glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sorbitan, and pentaerythrit are shown, n is an integer of 1 to 30, n 'is an integer of 4 to 50, and n "is 2
And n ′ × n ″ is 30 or more in any combination.) Among types (VII), particularly preferred as the hydrophilic nonionic surfactant in the present invention are castor oil and castor oil. To 1 to 12 moles of propylene oxide adduct of hydrogenated castor oil,
Further, 30 to 80 mol of ethylene oxide is added. Type (VIII):

[0025]

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(Wherein R represents an alkane or alkene group having 8 or more carbon atoms, X represents an ether or ester group,
Is glycerin having 3 to 6 carbon atoms, trimethylolethane,
Trimethylolpropane, sorbitol, sorbitan,
A pentaerythritol residue, n is an integer of 10 to 50,
n ′ represents an integer of 2 to 5, and n × n ′ is 30 or more in any combination. Of the type (VIII), particularly preferred as the hydrophilic nonionic surfactant in the present invention are 20 to 100 moles of ethylene oxide adduct of oleic acid monoglyceride and stearyl glyceryl ether (batyl alcohol). Type (IX):

[0027]

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(Wherein R represents an alkane or alkene group having 8 or more carbon atoms, X represents an ether or ester group,
Is glycerin having 3 to 6 carbon atoms, trimethylolethane,
Trimethylolpropane, sorbitol, sorbitan,
A pentaerythritol residue, n is an integer of 1 to 10,
n ′ represents an integer of 10 to 50, n ″ represents an integer of 2 to 5, and n ′ × n ″ is 30 or more in any combination. Among the types (IX), particularly preferred as the hydrophilic nonionic surfactant in the present invention are oleic acid monoglyceride or propylene oxide 1 of batyl alcohol.
１２12 mol adduct, and ethylene oxide 20８8
0 mol was added.

It should be noted that only one type may be selected and used from the hydrophilic surfactants mentioned above, and if necessary, 2 types may be used.
You may use it in combination of 2 or more types. The content of the hydrophilic surfactant in the acidic hair dye is 0.1 to 20.0% by weight, preferably 0.5 to 5.0% by weight.

The water-soluble solvent has the effect of dissolving the above-mentioned hydrophilic nonionic surfactant and efficiently orienting it at the interface with the oil phase to be added thereafter. Lower polyhydric alcohols, ketones, aldehydes, ethers, amines, lower fatty acids, and other substances that are hydrophilic and dissolve the above surfactant can be freely selected from a very wide range of substances. it can.

Specific examples of the water-soluble solvent include alcohols such as methanol, ethanol, propanol and isopropanol, glycerin, ethylene glycol,
Diethylene glycol, triethylene glycol, hexane diol 2.5, 2.3 butylene glycol, heptane diol, 2.4 hexylene glycol, 1.5 pentane diol, 1.4 butane diol, propylene glycol, 1.3 butylene glycol, di Polyhydric alcohols such as propylene glycol (molecular weight 60-200
0), ketones such as acetone, acetonylacetone and diacetone alcohol, aldehydes such as formaldehyde and acetaldehyde, ethylene oxide, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono Isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monopropyl ether (monoisopropyl ether), dimethylene glycol monoethyl ether, dimethylene glycol monomethyl ether, dimethylene glycol monobutyl ether, dimethylene Glycol diethyl ether, etoki Ethers such as triglycol, monopropylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol monomethyl ether, acetic acid ethylene glycol monomethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, monoethanolamine, diethanolamine, triethanol Amines such as amine, positive butylamine, ethylenediamine, propylenediamine, ethylamine, pyridine, cyclohexylamine, formic acid, acetic acid, butyric acid,
It is selected from lower fatty acids such as lactic acid, methoxyglycol acetate, methyl lactate, ethyl lactate, acetonitrile, tetrahydrofuran, furfuryl alcohol, and the like, and even one suitable water-soluble solvent may be used in preparing the emulsion. It is good, and in some cases, the solubility of the surfactant can be freely changed by mixing two or more water-soluble solvents, which is very convenient.
The amount of the water-soluble solvent added is 0.1 to 50.
It is 0% by weight, preferably 5.0 to 20.0% by weight.

With respect to the oil content, almost all commonly used oil classifications from non-polar oils to polar oils such as silicone oils, hydrocarbon oils and ester oils can be emulsified. Specific examples include silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, and methylhydrogenpolysiloxane, liquid paraffin, squalane, terpene-based hydrocarbons, other synthetic hydrocarbon oils, and linear oils. Or branched alcohol esters of linear or branched fatty acids such as glycerin esters of branched fatty acids, for example glyceryl-tri-2-ethylhexanoate, glyceryl-tri-isostearate, for example trimethylolpropane-tri-2-ethylhexano Ester, pentaerythritol-tetra-2-ethylhexanoate, and other ester oils such as 2-ethylhexylic acid ester of glycerin-sorbitan condensate and hexadecyl adipate. Only one type of these oil components may be selected and used, or two or more types may be used in combination if necessary. The amount of oil content in the acidic hair dye is 0.1 to 20.0% by weight, and preferably 0.1.
5 to 5.0% by weight.

Examples of the dyeing assistants contained in the acidic hair dye of the present invention include compounds represented by the following formula (1) or (2).

[0034]

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[Wherein R ¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a group

[0036]

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Or a group

[0038]

[Chemical 12]

(In the formula, R ² represents a hydrogen atom, a methyl group or a methoxy group, and R ³ represents --CH _2- , --CH ₂ --CH.
₂ -, - CH ₂ = CH- or -CH ₂ = CH-CH ₂ - shows a. ), P, q and r are integers of 0 to 5, and Y and Z represent a hydrogen atom or a hydroxyl group. ]

[0040]

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(In the formula, R ⁴ represents a linear or branched alkyl group having 1 to 20 carbon atoms.) Of these, benzyl alcohol, phenethyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxy Ethanol, N-methylpyrrolidone, N-octylpyrrolidone, N-laurylpyrrolidone and the like are preferable. Among these, benzyl alcohol is particularly preferable in terms of hair dyeing power.

These dyeing assistants are preferably added to the acidic hair dye of the present invention in an amount of 0.1 to 25.0% by weight.
It is particularly preferable to add 5 to 15.0% by weight. 0.1
If it is less than 5% by weight, sufficient improvement in hair dyeing power cannot be obtained.
When the amount is more than 5.0% by weight, no remarkable improvement in hair dyeing power is observed.

Regarding the quantitative relationship of the oil-in-water emulsion in the present invention, the composition of the oil-in-water emulsion in the first step is such that the oil content is 1 to 90 parts, the dyeing aid is 0.1 to 9 parts.
It is selected in the range of 0 part, 1 to 90 parts of water-soluble solvent, and 0.2 to 10 parts of hydrophilic nonionic surfactant. Next, in the second step, 5 to 95 parts of the emulsion is diluted with 95 to 5 parts of the aqueous phase component to prepare a stable oil-in-water emulsion. The details of the method for producing an oil-in-water emulsion are as described in JP-B-57-29213.

The acidic hair dye of the present invention is prepared by preparing the oil-in-water emulsion and then adding the oil-in-water emulsion to
It is produced by adding an acid dye and an acid.

As the acidic dye contained in the acidic hair dye of the present invention, it is permitted to use for coloring pharmaceuticals, quasi-drugs and cosmetics which have no harmful effect on the human body. The legal dyes listed in "Ministerial Ordinance that defines the tar color that can be used" are listed. The amount of these acidic dyes added is 0.01 to 5.
0% by weight.

Acids for pH adjustment used in the present invention include citric acid, malic acid, acetic acid, lactic acid, oxalic acid, tartaric acid,
There are organic acids such as formic acid and levulinic acid, and inorganic acids such as phosphoric acid and hydrochloric acid. The amount of acid blended is such that the pH of the acidic hair dye is 1.5 to 4.
It may be mixed so that it becomes 5.

The acidic hair dye of the present invention has system stability, pH
In addition to the above components, a preservative, as long as it does not damage
It is possible to appropriately add a chelating agent, a fragrance or the like.

[0048]

Next, the present invention will be described in more detail by way of examples. The present invention is not limited to this. The blending amount is% by weight.

Examples 1 to 5 and Comparative Examples 1 to 5 Acidic hair dyes were prepared according to the combination formulations shown in Table 1 and Table 2. The manufacturing methods of Examples 1 to 5 and Comparative Examples 1 to 4 at this time are as follows.

(1) Manufacturing method of Examples 1 to 5 (1) to (4) are added to (6), (7) and (16) and dissolved by heating at 50 to 55 ° C. (5), (8), (11), (17) to (21) are also temperature-controlled at 50 to 55 ° C and added to the water-soluble solvent while gradually stirring,
Emulsification is performed to obtain a gel or an oil-in-water emulsion. When this is cooled to 25 to 30 ° C. by stirring, a stable gel or oil-in-water emulsion is obtained. Next, (10), (13) to (15) were dissolved in (9) and added to the emulsion to adjust the pH to 2.5 to obtain an acidic hair dye.

(2) Production method of Comparative Examples 1 to 5 Comparative Examples 1 to 3 Acid hair dyes were produced in the same manner as in Examples 1 to 5. Comparative Examples 4 and 5 (1) to (4) and (7) were added to a part of (9) and heated and dissolved at 50 to 55 ° C. (5), (8), (11), (17), (18) also 50 ~ 55 ℃
The temperature is adjusted to, and the mixture is gradually stirred and added to emulsify.
This is cooled to 25 to 30 ° C. by stirring to obtain an oil-in-water emulsion in a water-soluble solvent. Then, in the rest of (9), (10),
(12) to (15) are dissolved and added to the emulsion to obtain a pH of 2.
It was adjusted to 5, and an acidic hair dye was obtained.

Using the obtained acidic hair dye, the following methods and criteria were used to evaluate the temperature stability and the dry feel of the hair when applied to hair, operability, sag after application and dyeability. did. Table 3 shows the results.

(1) Evaluation of temperature stability <Evaluation method> Each sample was stored in a constant temperature bath at 50 ° C. for 1 month, and then
It was visually observed and evaluated according to the following criteria.

<Evaluation Criteria> A: No change. ◯: The viscosity was slightly lowered. Δ: Slightly separated. X: Separated.

(2) Evaluation of dryness of hair after drying hair <Evaluation method> Evaluation of the dryness of hair after drying a hair when a series of hair dyeing operations was performed using each sample by an evaluation panel. Was evaluated according to the standard.

<Evaluation Criteria> ⊚: It is not dry and is smooth. ○: Not dry. Δ: Somewhat dry. X: Remarkably dry.

(3) Evaluation of operability <Evaluation method> Evaluation panel was used to evaluate the operability at the time of application when a series of hair dyeing operations were performed using each sample according to the following criteria.

<Evaluation Criteria> ⊚: Good adhesion to hair and easy spreading. ○: Easy to extend. Δ: The spread is poor. X: Adhesion to hair and spread are poor, and application is difficult.

(4) Evaluation of Sagging <Evaluation Method> Each sample was applied to the hair for 20 minutes by a special evaluation panel, allowed to stand for 20 minutes, visually observed, and evaluated according to the following criteria.

<Evaluation Criteria> A: No decrease in viscosity and no dripping is observed. ◯: Some decrease in viscosity is observed. Δ: Some dripping is recognized. X: Dripping is recognized. (5) Evaluation of dyeability <Evaluation method> The dyeability to hair when a series of hair dyeing operations was performed using each sample was evaluated by the evaluation specialist panel according to the following criteria.

<Evaluation Criteria> ⊚: Dyeability is good and the hair is shiny. ◯: Dyeability is slightly good. Δ: Poor dyeability. X: Remarkably poor dyeing property.

[0062]

[Table 1] ─────────────────────────────────── Example 1 2 3 4 5 5 ──── ────────────────────────────────────── (1) Polyoxyethylene (40 mol) Cetyl ether 2.0 − − 1.0 1.0 (2 ) Polyoxyethylene (20 mol) cetyl ether − 2.0 2.0 2.0 2.0 (3) Polyoxypropylene (12 mol) cetyl ether 2.0 1.0 2.0 1.0 1.0 (4) Polyoxyethylene (10 mol) cetyl ether 2.0 1.0 1.0 1.0 1.0 ( 5) Polyoxilanoline alcohol derivative − 2.0 3.0 1.0 1.0 (6) Ethylene glycol 5.0 − − − − (7) Dipropylene glycol 5.0 − 5.0 3.0 3.0 (8) Dimethyl polysiloxane (20cs) 5.0 − − 5.0 5.0 (9) Ion-exchanged water balance balance balance balance balance (10) Citric acid 0.5 0.5 0.5 0.5 0 .5 (11) Benzyl alcohol 10.0 10.0 10.0 5.0 3.0 (12) EDTA salt 0.1 0.1 0.1 0.1 0.1 (13) Daidai 205 No. 0.1 0.1 0.1 0.1 0.1 (14) Purple 401 0.1 0.1 0.1 0.1 0.1 (15) Black 401 No. 0.1 0.1 0.1 0.1 0.1 (16) Propylene glycol − 10.0 − − − (17) Squalane − 20.0 10.0 2.0 2.0 (18) Deodorized lanolin − 40.0 − 5.0 5.0 (19) Purified petrolatum − 1.0 − − − (20) Beeswax − 2.0 5.0 − − (21) Hexadecyl adipate − 24.0 − − − ─────────────────────────────────── ─

[0063]

[Table 2] ─────────────────────────────────── Comparative Example 1 2 3 4 5 ──── ─────────────────────────────── (1) Polyoxyethylene (40 mol) Cetyl ether − 2.0 2.0 1.0 1.0 (2 ) Polyoxyethylene (20 mol) cetyl ether − − − 2.0 2.0 (3) Polyoxypropylene (12 mol) cetyl ether − 2.0 2.0 1.0 1.0 (4) Polyoxyethylene (10 mol) cetyl ether − 2.0 2.0 1.0 1.0 ( 5) Polyoxilanoline alcohol derivative − − − 1.0 1.0 (6) Ethylene glycol − − − − − (7) Dipropylene glycol 5.0 − 5.0 3.0 3.0 (8) Dimethyl polysiloxane (20cs) 5.0 5.0 − 5.0 5.0 (9) Ion-exchanged water balance balance balance balance balance (10) Citric acid 0.5 0.5 0.5 0.5 0 .5 (11) Benzyl alcohol 10.0 10.0 10.0 5.0 3.0 (12) EDTA salt 0.1 0.1 0.1 0.1 0.1 (13) Daidai color No. 205 0.1 0.1 0.1 0.1 0.1 (14) Purple No. 401 0.1 0.1 0.1 0.1 0.1 (15) Black 401 No. 0.1 0.1 0.1 0.1 0.1 (16) Propylene glycol − − − − − (17) Squalane − − − 2.0 2.0 (18) Deodorized lanolin − − − 5.0 5.0 (19) Purified petrolatum − − − − − (20) Beeswax − − − − − (21) Hexadecyl adipate − − − − − ─────────────────────────────────── ─

[0064]

[Table 3] ────────────────────────────────── Examples Comparative Examples Evaluation ─────── ──── ─────────── 1 2 3 4 5 1 2 3 4 5 ───────────────────────── ───────── Temperature stability ◎ ◎ ◎ ◎ ◎ ◎ × × × × × Dryness after dry hair ◎ ◎ ◎ ◎ ◎ △ × × × × × Operability ◎ ◎ ◎ ◎ ◎ ◎ × △ × △ △ Dripping after application ◎ ◎ ◎ ◎ ◎ ◎ × × × × × Dyeability ◎ ◎ ◎ ○ △ × × × △ × ─────────────────────── ─────────────

As is clear from the results in Table 3, the product of the present invention was an excellent acidic hair dye as compared with the comparative product. next,
Formulation examples of the acidic hair dye according to the present invention will be given.

Example 6 (1) Polyoxyethylene (40) cetyl ether 2.0% by weight (2) Polyoxypropylene (12) cetyl ether 2.0 (3) Polyoxyethylene (10) cetyl ether 2.0 (4) Ethylene glycol 5.0 (5) Dipropylene glycol 5.0 (6) Dimethylpolysiloxane (20cs) 50.0 (7) Ion-exchanged water balance (8) Citric acid pH adjusted to 2 (9) Benzyl alcohol 10 .0 (10) EDTA salt 0.1 (11) Daidai color No. 205 0.1 (12) Purple No. 401 0.1 (13) Black No. 401 0.1 (14) Ethanol 2.0 (Production method) First hydrophilic The nonionic surfactants (1) to (3) are added to the water-soluble solvents (4), (5) and (15) and dissolved by heating at 50 to 55 ° C. The oil phases (6) and (9) are also temperature-controlled at 50 to 55 ° C., and the oil phase is gradually stirred and added to the water-soluble solvent phase for emulsification to obtain a gel or an oil-in-water emulsion.
After cooling to room temperature by stirring, EDTA and citric acid are dissolved in water, and then added to obtain a stable acidic hair dye comprising an oil-in-water emulsion.

Example 7 (1) Polyoxylanolin alcohol derivative (30) 2.0% by weight (2) Polyoxyethylene (20) cetyl ether 2.0 (3) Polyoxypropylene (12) cetyl ether 1.0 (4) Polyoxyethylene (10) cetyl ether 1.0 (5) Propylene glycol 7.0 (6) Squalane 15.0 (7) Deodorized lanolin 30.0 (8) Purified petrolatum 1.0 (9) Beeswax 2 0.0 (10) Hexadecyl adipate 20.0 (11) Ion-exchanged water balance (12) Citric acid pH adjusted to 3 (13) Benzyl alcohol 10.0 (14) EDTA salt 0.1 (15) Daidai color No. 205 0.2 (16) Purple No. 401 0.1 (17) Black No. 401 0.1 (18) Polyoxyethylene-modified dimethylsiloxane 0.1 (Shin-Etsu Silicone SC9450) (Production method) Acidic as in Example 6 Make hair dye I made it.

Example 8 (1) Polyoxyethylene (60) hydrogenated castor oil ester 1.0% by weight (2) glycerin 10.0 (3) propylene glycol 3.0 (4) liquid paraffin 15.0 (5) Ion-exchanged water balance (6) Citric acid adjusted to pH 3 (7) Benzyl alcohol 10.0 (8) EDTA salt 0.1 (9) Daidai color 205 0.1 (10) Purple 401 0.1 (11) Black No. 401 0.1 (12) Polyoxyethylene-modified dimethyl siloxane 0.1 (Shin-Etsu Silicone SC1014M) (13) Xanthan gum Appropriate amount (14) N-methylpyrrolidone 5.0 (Production method) Xanthan gum in the aqueous phase in Example 6. Was dissolved and then added to an oil-in-water emulsion, to prepare an acidic hair dye in the same manner as in Example 6.

Example 9 (1) Polyoxyethylene (60) hydrogenated castor oil ester 1.0% by weight (2) glycerin 7.0 (3) polyglycerin 8.0 (4) liquid paraffin 18.0 (5) Ion-exchanged water balance (6) Citric acid adjusted to pH 4 (7) Benzyloxyethanol 10.0 (8) EDTA salt 0.1 (9) Daidai color 205 0.1 (10) Purple 401 0.1 (11) ) Black No. 401 0.1 (12) Dimethylpolysiloxane 0.1 (Molecular weight 300,000 to 1,500,000) (13) Carboxyvinyl polymer Suitable amount (14) N-methylpyrrolidone 3.0 (15) Ethanol 3.0 (Production method ) An acidic hair dye was produced in the same manner as in Example 6, except that the carboxyvinyl polymer was dissolved in the aqueous phase and then added to the oil-in-water emulsion.

Example 10 (1) Polyoxypropylene (70) Decaglyceryl ether 5.0% by weight (2) Polyoxypropylene (60) Hardened castor oil ester 1.0 (3) Polyglycerin 10.0 (4) Diglycerin 2.0 (5) Squalane 10.0 (6) Ion-exchanged water balance (7) Citric acid pH adjusted to 2 (8) Benzyl alcohol 10.0 (9) EDTA salt 0.1 (10) Daidai color No. 205 0.1 (11) Purple No. 401 0.1 (12) Black No. 401 0.1 (13) Amino-modified silicone 0.1 (Toray Dow Corning's SM-8702C) (14) Hydroxyethyl cellulose Appropriate amount (production method) An acidic hair dye was produced in the same manner as in Example 6 except that hydroxyethyl cellulose was dissolved in the aqueous phase and then added to the oil-in-water emulsion.

Example 11 (1) Polyoxypropylene (60) hydrogenated castor oil ester 0.7% by weight (2) glycerin 4.0 (3) diglycerin 4.0 (4) liquid paraffin 20.0 (5) Ion-exchanged water balance (6) Citric acid adjusted to pH 3 (7) Benzyloxyethanol 10.0 (8) EDTA salt 0.1 (9) Daidai color 205 0.1 (10) Purple 401 0.1 (11 ) Black No. 401 0.1 (12) Carboxymethylcellulose proper amount (13) Dimethylpolysiloxane 0.1 (14) N-methylpyrrolidone 5.0 (Production method) After dissolving carboxymethylcellulose in the aqueous phase in Example 6, An acidic hair dye was produced in the same manner as in Example 6 except that it was added to the oil-in-water emulsion.

Example 12 (1) Polyoxyethylene (60) hydrogenated castor oil ester 1.0% by weight (2) polyglycerin 5.0 (3) glycerin 5.0 (4) liquid paraffin 13.0 (5) Ion-exchanged water balance (6) Citric acid pH adjusted to 4 (7) Benzyl alcohol 10.0 (8) EDTA salt 0.1 (9) Daidai color 205 0.2 (10) Purple 405 0.2 (11) Black No. 405 0.2 (12) Polyoxyethylene-modified dimethylsiloxane 0.1 (Shin-Etsu Silicone SC9450) (13) Keratin hydrolyzate 0.1 (Production method) In Example 6, the keratin hydrolyzate was dissolved in the aqueous phase. After that, an acidic hair dye was manufactured in the same manner as in Example 6 except that the oil-in-water emulsion was added.

Example 13 (1) 5.0% by weight of sodium lauryl sulfate (2) Triethanolamine lauryl sulfate 5.0 (3) Betaine lauryl dimethylaminoacetate 6.0 (4) Ethylene glycol distearate 2.0 ( 5) Glycerin 20.0 (6) Squalene 11.0 (7) Ion-exchanged water balance (8) Citric acid pH adjusted to 2 (9) Benzyloxyethanol 5.0 (10) EDTA salt 0.1 (11) White color 205 0.1 (12) Purple 405 0.1 (13) Black 405 0.1 (14) Polyoxyethylene-modified dimethylsiloxane 0.1 (Shin-Etsu Silicone SC-1014M) (15) Collagen hydrolyzate 0.1 (16) N-methylpyrrolidone 10.1 (Production method) Example 6 except that the collagen hydrolyzate was dissolved in the aqueous phase and then added to the oil-in-water emulsion in Example 6. It was prepared an acidic hair dye in the same manner.

Example 14 (1) Polyoxyethylene (40) 2.0% by weight (2) Polyoxypropylene (12) 2.0 (3) Cetyl alcohol ether 2.0 (4) Ethylene glycol 3.0 ( 5) Dipropylene glycol 4.0 (6) Dimethylpolysiloxane 50.0 (7) Ion-exchanged water balance (8) Citric acid pH adjusted to 3 (9) Benzyl alcohol 5.0 (10) EDTA salt 0.1 (11) ) Daidai color No. 205 0.1 (12) Purple No. 401 0.1 (13) Black No. 401 0.1 (14) Ethanol 2.0 (Production method) An acidic hair dye was produced in the same manner as in Example 6.

[0075]

As described above, the acidic hair dye of the present invention is excellent in temperature stability, has good adhesion to hair, is easy to spread, and can be dyed with a small amount of dyeing aid. It has good wearability, does not drip due to a decrease in viscosity after application, has a smooth feel on the hair, and has no dryness.

Claims (2)

[Claims] 1. An acidic hair dye containing an acid dye, a dyeing aid and an acid, wherein a hydrophilic nonionic surfactant is added to a water-soluble solvent as a first step, and then an oil phase and a dyeing are added thereto. An acidic, characterized in that it comprises an oil-in-water emulsion obtained by adding an auxiliary agent, and as a second step, water and an acid dye are added to the oil-in-water emulsion Hair dye. 2. As a first step, a hydrophilic nonionic surfactant is added to a water-soluble solvent, and then an oil phase and a dyeing auxiliary agent are added thereto to prepare an oil-in-water emulsion. A method for producing an acidic hair dye, comprising adding water, an acidic dye and an acid to the oil-in-water emulsion in two steps to form an oil-in-water emulsion.