JPH0940533A - Hair dye composition of type mixed on employment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hair dye composition of the type mixed on employment, good in the dyeing property on hair, little in fading, excellent in hair touch after dyed, and used by combining a dye with an oxidizing agent on the employment. SOLUTION: This composition comprises (I) a dye, (II) a surfactant arbitrarily selected from amphoteric surfactants and semipolar surfactant, (III) a higher fatty acid, (IV) an anionic surfactant, (V) an oxidizing agent and (VI) water. The first agent comprising the components I, II, III and VI, and, if necessary, a minor amount of the component IV, and the second agent comprising the major amount of the component IV and the component V are prepared, respectively, so that the composition produced by mixing the components on their employment has a pH of 6-12. Therein, 5-50wt.% of the component IV, 5-50wt.% of II, 0.1-5wt.% of III, 0.001-10wt.% of I, and 0.2-20wt.% of V on the basis of the whole weight of the components are compounded. The weight ratio of IV/II is 4/6 to 10/0.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a before-use mixed type hair dye composition. More specifically, the present invention relates to a hair dye composition comprising specific components in a combined state.

[0002]

2. Description of the Related Art Conventionally, a two-pack type hair dye has been generally used as a mixed type hair dye (that is, two or more agents are combined at the time of use), and oxidation such as aromatic amino compounds is used. It is typically formed by mixing a first agent containing a dye as a main agent and a second agent containing an oxidizing agent such as hydrogen peroxide as a main agent at the time of use. Since this mixture is applied to hair before use, the mixture must have a viscosity such that it does not drip from the hair. Therefore, in the conventional technique, a thickening system at the time of mixing is obtained by utilizing the liquid crystal region of the nonionic surfactant aqueous solution. That is, the first agent in which a nonionic surfactant having a liquid crystal formation concentration or higher and a lower alcohol is mixed with a dye is diluted with a second agent containing an oxidizing agent to concentrate the surfactant of the final mixture in the liquid crystal region. A thickening system was obtained by adjusting. However, the conventional systems having a high concentration of nonionic surfactants and lower alcohols have a drawback that the hair after dyeing has a dry feel, and since it becomes a liquid crystal when mixed, the dispersion of the dye is poor and the dyeing property is poor. there were.

On the other hand, at the same time as dyeing or coloring the hair,
For the purpose of providing a hair dye that enables cleaning and conditioning, a hair dye containing a cationic polymer, an anionic surfactant, and an amphoteric or zwitterionic surfactant in specific proportions has been proposed. (See, for example, Japanese Patent Publication No. 4-22884).

However, in the prepared composition in a separated form before mixing, the physical properties are stable and the viscosity is relatively low, but at the time of use, that is, when all the components are mixed, However, it has been difficult to stably provide a hair dye whose mixed composition does not drip from the hair and which is excellent in desired dyeing and feeling of the dyed hair.

For example, the above-mentioned hair dyes using lower alcohols tend to give poor feeling to the hair after dyeing.

[0006]

Therefore, it is an object of the present invention to remove a part or all of a lower alcohol from a composition in which each component is mixed at the time of use, and whether each component is independent. , Or when it is in the form of being separated as a certain group, it has a relatively low viscosity, but when the components are mixed together, it shows an appropriate viscosity. To provide an agent composition.

[0007]

Although not belonging to the technical field of hair dyes, a composition containing an anionic surfactant, an amphoteric surfactant and / or a semipolar surfactant, and a higher fatty acid is It is known that it has an appropriate viscosity as a skin cleanser (see, for example, JP-A-5-17342 and JP-A-6-65596).

[0008] The inventors of the present invention, when the respective components in such a composition are prepared individually or in a specific combination with a dye and a peroxide which are essential components of a mixing type hair dye at the time of use, It has been found that each gives stable and relatively low viscosity preparations, but when all of them are mixed, a mixed composition can be provided which exhibits an excessive viscosity for the purpose of use as a hair dye.

Therefore, the above object is according to the present invention:
A fresh-use type hair dye composition in which a dye and an oxidizing agent are combined at the time of use, wherein the combined composition is (a) a dye (I), an optional amphoteric surfactant and a semi-active agent. One or more kinds of surfactants (II) selected from the group consisting of polar surfactants, and one or more kinds of higher fatty acids (III)
An anionic surfactant (IV), an oxidant (V), and water (VI), and (b)
Prior to use, the components selected from the group consisting of components (I), (II) and (III) are the components (IV) and (V)
It is achieved by providing a hair dye composition which is placed in a form separated from a component selected from the group consisting of:

In a preferred embodiment of the present invention, the mixed composition in which the respective components at the time of use are combined is adjusted to have a pH of 6-12.

[0011]

Specific Embodiments of the Invention "Mixed-before-use type" referred to in the present specification
Means that when two or more pre-prepared preparations are used,
That is, it means a mode that is mixed in the hair treatment.
Therefore, the present invention is conveniently applied to a hair dye, which is generally called a permanent hair dye.

Therefore, examples of the dye (component (I)) used in the present invention include a dye precursor that develops color by the oxidation of the compound itself and a combination with a coupler that exhibits various color tones by combination with the dye precursor. To be
Specific examples of such dyes include, but are not limited to, 5-aminoorthocresol (also known as paraaminoorthocresol), 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, 1 -Amino-4-methylaminoanthraquinone, 3,3'-iminodiphenol, 2,4-diaminophenol hydrochloride,
Toluene-2,5-diamine hydrochloride, nitroparaphenylenediamine hydrochloride, paraphenylenediamine hydrochloride, hydrochloric acid N
-Phenylparaphenylenediamine, metaphenylenediamine hydrochloride, orthoaminophenol, N-phenylparaphenylenediamine acetate, 1,4-diaminoanthraquinone, 2,6-diaminopyridine, diphenylamine, toluene-2,5-diamine, toluene-3 , 4-diamine, nitroparaphenylenediamine, paraaminophenylsulfamic acid, paraaminophenol, paranitroorthophenylenediamine, paraphenylenediamine, paramethylaminophenol, N, N'-bis (4
-Aminophenyl) -2,5-diamino-1,4-quinonediimine (also known as Bandrovsky base), 2-hydroxy-5-nitro-2 ', 4'-diaminoazobenzene-5-sulfonate sodium (also known as chrome brown) R
H), N-phenylparaphenylenediamine, metaaminophenol, metaphenylenediamine, 5-aminoorthocresol sulfate (also known as paraaminoorthocresol sulfate), 2-amino-5-nitrophenol sulfate, orthoaminophenol sulfate, orthochlor sulfate. Paraphenylenediamine, 4,4'-diaminodiphenylamine sulfate, toluene-2,5-diamine sulfate, nitroparaphenylenediamine sulfate, paraaminophenol sulfate, paranitroorthophenylenediamine sulfate, paranitrometaphenylenediamine sulfate, paraphenylenediamine sulfate , Paramethylaminophenol sulfate, metaaminophenol sulfate, metaphenylenediamine sulfate, and / or fragrance of hematin, tannic acid, catechol, resorcin, etc. called plant dyes Polyhydric alcohol, and the like.

The above dyes are appropriately used depending on the desired hair color, and may be used in combination depending on the case. The compounding amount of the dye is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight.

The oxidant (component (V)) may be any compound or system that acts to bring about color development based on the dye when brought into contact with the oxidative dye, and does not adversely affect the object of the present invention. Both can be used. It is usually preferred to use hydrogen peroxide as such compound. In addition, as the above-mentioned system, a system in which hydrogen peroxide solution and ammonium persulfate or other persulfate are combined, which acts to promote coloring of dye as well as decolorization of hair, or hydrogen peroxide and sodium pyrosulfite A combination of the redox system may be used. In such a system, hydrogen peroxide and other peroxide are separated before use.

The amount of the oxidizing agent used is the type of dye used, the type of each component constituting the mixed composition at the time of use, and p.
Although it cannot be limited because the optimum amount varies depending on H etc., when hydrogen peroxide is used, it is generally 0.2 to 20% by weight, preferably 1 to 5% by weight based on the total weight of the composition.
It is preferable to select

The amphoteric surfactant (component (II)) used in the present invention may be any amphoteric surfactant used in ordinary cosmetic bases and the like. To give a specific example, the general formula (A)

[0017]

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Amidobetaine-type amphoteric surfactant represented by the formula [commercially available products include Levon 2000 (manufactured by Sanyo Kasei), Anon BDF (manufactured by NOF CORPORATION), general formula (B)

[0019]

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Amidosulfobetaine-type amphoteric surfactant represented by the formula [commercially available products include Lonzain-CS (manufactured by Lonza) and Miratain CBS (manufactured by Milanol)]
General formula (C)

[0021]

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A betaine-type amphoteric surfactant represented by the formula [Anon BL (manufactured by NOF CORPORATION), Deheinton A as a commercial product]
B-30 (manufactured by Henkel), etc.], general formula (D)

[0023]

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A sulfobetaine-type amphoteric surfactant represented by the formula [Lonzaine 12CS (manufactured by Lonza) as a commercial product is applicable], a general formula (E)

[0025]

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Examples include imidazolinium-type amphoteric surfactants [commercially available products include Obazoline 662-N (manufactured by Toho Chemical Co., Ltd.) and Anon GLM (manufactured by NOF CORPORATION)].

Further, a semipolar surfactant (component (II))
As the general formula (F)

[0028]

[Chemical 6]

A tertiary amine oxide type semipolar surfactant represented by the formula (commercially available products such as Unisafe A-LM (manufactured by NOF Corporation) and Wandamine OX-100 (manufactured by Shin Nippon Rika)) are exemplified. It

However, in the general formulas (A) to (F), R
₁ is preferably an alkyl group or an alkenyl group having an average carbon number of 9 to 21, and an average carbon number of 11 to 17
Is more preferable, and an alkyl group or alkenyl group having an average carbon number of 11 to 13 is most preferable. When the average number of carbon atoms is less than 9, hydrophilicity is stronger than that in the case of 9 or more, and the viscosity of the composition in which all the components are combined tends to be low. Meanwhile, 2
When it exceeds 1, the solubility in water becomes worse as compared with the case of 21 or less, and the phase separation of these components is caused in the composition and in the preparation containing each of the components before use. It tends to occur, resulting in poor stability of the composition.

R ₂ represents an alkyl group or an alkenyl group having an average of 10 to 18 carbon atoms. x is an integer of 2 to 4, y is an integer of 0 to 3, and z is an integer of 1 or 2.

In the present invention, any one or more of these amphoteric surfactants and semipolar surfactants can be selected and used. Preferred as a combination of two or more kinds is an imidazolinium betaine type amphoteric surfactant represented by the formula (E) and other formulas (A), (B), (C) and (D). , And formula (F)
The combination with at least 1 sort (s) of these can be mentioned.

As will be described later, when a specific type of anionic surfactant used in combination is selected, the component (I
I) may not necessarily be included in the hair dye composition of the present invention.

The higher fatty acid (component (II
As I)), for example, any higher fatty acid represented by the following general formula (G) can be used as long as it is a higher fatty acid used in a general cosmetic base or the like.

General formula (G) R ₃ COOH (G) Here, R ₃ is preferably a straight chain or branched chain having an average carbon number of 7 to 25, or a saturated or unsaturated hydrocarbon having a mercury group, and an average carbon number of 9 To 23 saturated or unsaturated hydrocarbons having a linear or branched chain or a hydroxyl group, and having an average carbon number of 11
Most preferred are saturated and unsaturated hydrocarbons having a straight chain or branched chain or hydroxyl group of -21. If the average carbon number is less than 7,
Compared to the case of more than that, the thickening at the time of mixing is weak. On the other hand, when it exceeds 25, the solubility in one agent is small, phase separation occurs and the viscosity becomes high as compared with the case of less than 25.

Specific examples of the higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid,
Saturated fatty acids such as arachidic acid and behenic acid; 2-palmitoleic acid, petroselinic acid, oleic acid, elaidic acid,
Examples thereof include unsaturated fatty acids such as ricinoleic acid, linoleic acid, linoelaidic acid, linolenic acid, and arachidonic acid, branched fatty acids such as isostearic acid, and hydroxycarboxylic acids such as 12-hydroxystearic acid. Of these, from the viewpoints of stability and skin irritation, saturated fatty acids having 18 carbon atoms are preferable, those having a branched chain are preferable, and more preferable fatty acids that are liquid at room temperature, for example,
A saturated fatty acid having 18 carbon atoms having a methyl branch or oleic acid is preferable. Examples of commercially available products include isostearic acid (Emery # 871, # 875 (manufactured by Emery)),
Examples thereof include oleic acid (extra oil 90, 99 (manufactured by NOF CORPORATION)).

Although not restricted by the mechanism of action, when these higher fatty acids are used in combination with the above component (I), the optional component (II) and the anionic surfactant described below, Not only markedly improves the low temperature stability of the prepared composition (generally the first part) containing but also the viscosity of the composition in which all the components during use are combined (sometimes referred to as "mixed composition") Also works significantly.

In the present invention, any one or more of the above higher fatty acids are selected and used.

The viscosity of the mixed composition at the time of use increases with the amount of the higher fatty acid compounded, and especially 0.1 to 5% by weight.
It is preferable to mix them.

When higher fatty acids which are liquid at room temperature, such as isostearic acid and oleic acid, are used, the effect is further enhanced and the stability is stable even at a low temperature of -5 ° C or lower.

The anionic surfactant (component (IV)) that can be used in the present invention is, for example, a base for soap,
Fatty acid soaps such as sodium laurate and sodium palmitate, higher alkyl sulfate ester salts such as sodium lauryl sulfate and potassium lauryl sulfate, POE lauryl sulfate triethanolamine, alkyl ether sulfates such as POE sodium lauryl sulfate and sodium lauroyl sarcosine Alkyloylalkyl taurine salts such as N-acyl sarcosinic acid, N-myristoyl-N-methyl taurine sodium and N-lauroyl-N-methyl taurine sodium, higher fatty acids such as coconut oil fatty acid methyl tauride sodium and lauryl methyl tauride sodium. Amidosulfonate, sodium phosphate ester of POE oleyl ether phosphate, phosphate ester salt of POE stearyl ether phosphate, sodium di-2-ethylhexyl sulfosuccinate , Monolauroyl monoethanolamide sodium polyoxyethylene sulfosuccinate, lauryl polypropylene glycol sulfosuccinate such as sodium sulfosuccinate, sodium linear dodecylbenzene sulfonate, triethanolamine linear dodecyl benzene sulfonate, alkylbenzene sulfone such as linear dodecyl benzene sulfonate Acid salts, monosodium N-lauroylglutamate, disodium N-stearoylglutamate, N-acylglutamates such as N-myristoyl-L-monosodium glutamate, and higher fatty acid ester sulfates such as hydrogenated coconut oil fatty acid glycerin sodium sulfate; Sulfated oil such as funnel oil, POE alkyl ether carboxylic acid, POE alkyl allyl ether carboxylate, α-o Examples include reffin sulfonate, higher fatty acid ester sulfonate, secondary alcohol sulfate ester salt, higher fatty acid alkylolamide sulfate ester salt, lauroyl monoethanolamide sodium succinate, N-palmitoyl aspartate ditriethanolamine, sodium caseinate and the like. To be

"POE" in the above examples means polyoxyethylene, and usually includes ethylene oxide units having 1 to 20.

Of these, PO is particularly useful for improving the viscosity of the mixed composition at the time of use.
PO such as E sodium lauryl sulfate, POE lauryl sulfate triethanolamine, POE myristyl sulfate triethanolamine, and POE sodium myristyl sulfate
E alkyl ether sulfate, and N-lauroyl-
Alkyloylalkyl taurine salts such as N-methyl taurine salt and N-myristyl-N-methyl taurine salt, wherein the alkyl chain has a carbon number of any of even numbers from 10 to 18, and further α- It is an olefin sulfonate.

These conveniently usable ones can achieve the intended purpose without using the component (II) together.

According to the present invention, one or more of these anionic surfactants can be used in an appropriate combination, but in the preparation before use, in particular, it is separated from the component (II) and the component (III). Used in the form. This uses a small amount of them in combination with component (II) and component (III), and prepares a pre-use preparation in a form in which the main weight is separated from component (II) and component (III). Good.

Due to the nature of the peroxide (component (V)), the pre-use preparations according to the invention avoid the combined use of component (I), component (II) and component (III) with component (V). Is desirable. Therefore, in the hair dye composition mixed at the time of use of the present invention, the first agent is used as the component (I), the optional component (II), the component (III) and water (component VI).
And optionally a small amount of component (IV), the second agent being component (V), a major amount of component (IV) and component V
It is convenient in terms of handling to provide it in a two-pack form prepared from I and I.

Thus, in the mixed composition at the time of use in which the respective components are combined, the component (IV) is calculated on the basis of their total weight.
And (II) in an amount of 5 to 50% by weight, and the component (II
Including 0.1 to 5 parts by weight of I) makes it possible to maintain the viscosity of the preparation (for example, the above-mentioned first agent and second agent) before use relatively low (generally 200 cps or less),
The viscosity of the mixed composition at the time of use is significant (typically 500-1
0000 cps, preferably 500-5000 cps,
More preferably, it can be increased to 1000 to 3000 cps). In addition, the said viscosity means the value measured at 30 degreeC. If the total amount of the components (IV) and (II) is less than 5%, the viscosity of the mixed composition at the time of use cannot be sufficiently increased, and if the total amount exceeds 50%, the system of the mixed composition is a liquid crystal. It is not preferable because it shows the behavior of forming.

Furthermore, an anionic surfactant (component I
V) and the amphoteric surfactant and / or the semipolar surfactant (component II) are mixed in a weight ratio of 4/6 to 10/0.
You can choose to be Within this weight ratio range, a high thickening effect can be obtained within a wider pH range (specifically, pH 6 to 12) when mixing the first agent and the second agent as described above, and dyeing of gray hair and It becomes a hair dye with high uniformity. It is also possible to dye a bright color, which is so-called fashionable dyeing. In particular, a pH of 6 or more and less than 8 is preferably selected for dyeing gray hair, while a pH of 8 to 12 is preferably selected for fashionable dyeing involving decolorization of hair. Furthermore, the weight ratio of the component (IV) and the component (II) is from 4/6 to
A more excellent composition can be provided by adjusting the pH to 6/4 and selecting the pH of the final mixed composition from 8 to 12. First and second agents,
And their mixtures each exhibit desirable viscosities and stability.

According to the present invention, in addition to the above combination of the respective components, it is important that the pH of the mixed composition at the time of use is adjusted to have 6 to 12. By adjusting the pH in this manner, the viscosity of the mixed composition (that is, the hair dye composition at the time of use) can be appropriately maintained, and the dyeing property can be improved.

As mentioned above, according to the invention, before use, at least component (I), optionally included component (II), component (III) and component (VI), optionally component (IV). The preparation consisting of the small amount combination of)) is placed in separate form from the preparation consisting of the combination of the major amounts of component (V), component (VI) and component (IV). Therefore, assuming that the former preparation is the first agent and the latter preparation is the second agent, when the first agent is made alkaline and the second agent is combined (mixed) with the first agent, the pH is Can be adjusted to fall within the above range.

To make the first agent alkaline, an alkaline pH adjuster is blended. Specific examples of the pH adjusting agent are usually ammonia water, alkanolamines such as monoethanolamine, alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkali carbonates such as sodium carbonate, and silicic acid such as sodium silicate. Examples include alkali. Also, inorganic ammonium salts such as ammonium sulfate, ammonium nitrate, ammonium chloride, ammonium carbonate, primary ammonium phosphate and secondary ammonium phosphate can be used.

The pH of the hair dye composition at the time of use can be adjusted by adding the pH adjusting agent before mixing the first agent and the second agent as described above, or by adding it at the time of mixing. It is also possible to adjust. In this case, the time of mixing means during or after mixing, but it is preferable to mix during mixing.

In the present invention, lower alcohols may be blended in a range that does not affect the effects of the present invention (that is, 3% by weight or less is preferable in the first hair dye agent). Specific examples of the lower alcohol are usually ethyl alcohol,
Examples include monohydric alcohols having 2 to 5 carbon atoms such as n-propanol, isopropanol, butanol and the like. Incorporation of a lower alcohol promotes the penetration of the dye into the hair, but the feel of the hair is reduced accordingly, and therefore it is often preferable not to mix. On the other hand, in the conventional hair dye, a large amount of lower alcohol is added to the first agent, but since the present invention can reduce the content thereof to zero or less, hair dye excellent in usability even during rinsing. Become an agent.

Other than the above, the mixed hair dye of the present invention may contain other hair protecting agents at the stage of its preparation or at the stage of mixing the preparations, as long as the object of the present invention is not impaired.
Stabilizers, perfumes, humectants and the like can be incorporated.

As described above, the hair dye composition obtained by combining the preparations before use and the preparations at the time of use substantially causes the dripping from the hair when the final product is applied to the hair. And shows excellent hair dyeing properties. Furthermore, each preparation has excellent storage stability, is easy to handle, and can be provided as a composition having a relatively low viscosity.

[0056]

The present invention will be further described below with reference to specific examples. The parts or percentages (%) used in the examples mean (weight / weight) parts or (weight / weight)% unless otherwise specified.

First, a method of evaluating the effect of the present invention will be described.

1) Dyeing test with hair strands: 10 g of hair dye was applied to 2 g of hair strands that had been bleached (decolorized) in advance, and the hair dye was evaluated from the relationship between the standing time and the L value. The L value is the value of L in the Hunter color difference formula.

2) Dyeability and dryness comparison test by panelists The dyeability of dry hair and the dryness after drying when a series of hair dyeing operations were carried out by 10 professional panelists according to the following criteria. evaluated.

<Dyeing property> ++ ... Remarkably good dyeing property and uniform dyeing + ... Good dyeing property and uniform dyeing +/- Somewhat poor dyeing property -... unevenness Stainless and non-staining <Smoothness> ++ ・ ・ ・ Gives a smooth feel without touching ＋ ・ ・ ・ No touching ± ・ ・ ・ Slightly touching- ・ ・ ・ Remarkably touching 3) Mixing liquid Viscosity The viscosity of the mixed solution was measured at 30 ° C. using a B-type viscometer after mixing the first agent and the second agent.

4) Low Temperature Stability One agent (100 g) was stored in a thermostat at -5 ° C. for 1 month, and the condition was visually observed and evaluated according to the following criteria.

++ ... no change at all from the beginning + ... no change at all from the beginning, but slightly thickened ± ... slightly turbid --- causing separation Example 1, Comparative Example 1 ( (Conventional system) The first agent and the second agent of the present invention and the conventional system shown below are 1: 1.
Was mixed to prepare a hair dye, and a hair strand was used to evaluate the difference in dyeing property between the present invention and the conventional system from the relationship between the standing time and the L value.

Further, the viscosities of the first agent, the second agent, and the mixture of both agents were measured.

Example 1 (First agent) (% by weight) Undecyl-N-hydroxyethyl-N-carboxymethyl rumidazolinium betaine 3.0 Coconut oil fatty acid amidopropyl dimethylamine acetate betaine 7.0 Oleic acid 3. 0 Monoethanolamine 2.0 Ammonia water (28%) 10.0 L-Ascorbic acid 0.5 Paraphenylenediamine 1.0 Resorcinol 1.0 Perfume Suitable amount Purified water Balance total 100.0 (Second agent) Polyoxyethylene (1.5) Alkyl (12,14) Sodium ether sulfate 10.0 Hydrogen peroxide water 20.0 Methyl paraben Suitable amount Sodium stannate Suitable amount Phosphate buffer solution Adjusted to pH 3 Purified water Balance total 100.0 Comparative example 1 (1st Agent) Polyoxyethylene (2) oleyl ether 15.0 Polyoxyethylene (5) octylfe Nyl ether 5.0 Oleic acid 10.0 Monoethanolamine 2.0 Ammonia water (28%) 10.0 Paraphenylenediamine 1.0 Resorcinol 1.0 L-Ascorbic acid 0.5 Sodium hydrosulfite 0.1 Perfume Suitable amount Purified water Balance total 100.0 (2nd agent) Hydrogen peroxide water (30%) 20.0 Methylparaben Suitable amount Sodium stannate Suitable amount Phosphate buffer pH 3 Adjusted purified water Balance total 100.0 Hair dye of Example 1 The L value of 20 minutes after the treatment by 14.
6 and 16.9 in the comparative example, and also by visual observation,
The product of the present invention was superior in dyeing property as compared with the conventional system. Next, the dyed hair was irradiated with carbon arc for 20 hours or with a xenon lamp for 30 hours to examine the change in L value (ΔL). In Comparative Example 1, ΔL = 12.2 (xenon), whereas in this Example, ΔL = 3.6 (xenon), and the hair dyed in this Example is less likely to fade. I understood.

The first agent of Example 1 had a pH of 10.
65, viscosity = 150 cps, second agent pH = 3.0,
Viscosity = 12 cps, and after mixing both, pH =
9.3, viscosity = 4200 cps, and a remarkable thickening effect was recognized.

Next, using the first agent and the second agent of Example 1, a pH adjusting agent (ammonia water or phosphoric acid) was added during mixing.
Was added to prepare a hair dye having a pH of 5, 6, or 12, and the viscosity was measured. The results were 460 cps and 2510 c, respectively.
It was found that the hair dye having a ps of 890 cps and a pH of 6 to 12 has an excellent thickening effect. The L values after 20 minutes of hair dyeing treatment are 52, 23 and 3, respectively.
It was 8 and it was found that the dyeing property was high in the pH range of 6 to 12.

Examples 2 to 25 and Comparative Examples 2 to 9 Hair dyes obtained by mixing the first agent and the second agent of various compositions were evaluated by the above-mentioned evaluation methods. The results are shown in Tables 1 to 4
Summarized in

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

As is clear from Tables 1 to 4 above, the hair dye of the present invention has excellent dyeing properties and does not have a feeling of dryness.
It can be seen that when prepared as the first agent and the second agent, the viscosity is low, the viscosity after mixing is appropriate, and the stability at low temperature is also excellent. Further, it was found that the hair dyes of the present invention all had a good thickening effect, and all had a viscosity of 500 cps or higher, and had a high thickening effect.

Examples 26 to 29 When hair dyes were prepared using the first and second agents of the compositions of Examples 18 to 24 shown below, all had a viscosity of 50.
It was 0 cps or more, and it was confirmed that the dyeing property, the feeling of dryness, the discoloration property, the stability at low temperature, and the usability were all excellent.

Example 26 (First agent) (% by weight) Undecyl-N-hydroxyethyl-N-carboxymethytyl 2.0 Rumidazolinium betaine Palm oil fatty acid amide propyldimethylaminoacetate betaine 8.0 Oleic acid 3. 0 Keratin protein hydrolyzate 1.0 Pyrrolidone carboxylate 1.0 Monoethanolamine 2.0 Ammonia water (28%) 10.0 L-Ascorbic acid 0.5 Paraphenylenediamine 1.0 Resorcin 1.0 Metaamino Phenol 0.5 Perfume Appropriate amount Purified water Balance total 100.0 (Second agent) Polyoxyethylene (1.5) Alkyl (12, 14) Sodium ether sulfate 10 Hydrogen peroxide solution (30%) 20 Methylparaben Appropriate amount Sodium stannate qs phosphate buffer pH3 adjustment purified water balance total 100 example 27 (first ) (% By weight) Undecyl-N-hydroxyethyl-N-carboxymethylethylimidazolinium betaine 8.0 Coconut oil fatty acid amide propyldimethylaminoacetic acid betaine 7.0 Myristic acid 4.0 Dimethylpolysiloxane 20cs 1.0 Keratin hydrolyzate Degradation product 1.0 Monoethanolamine 2.0 Ammonia water (28%) 10.0 L-Ascorbic acid 0.5 Sodium hydrosulfite 0.2 Paraphenylenediamine 1.0 Resorcinol 0.5 Metaaminophenol 0.1 Fragrance Suitable amount Purified water Balance total 100.0 (2nd agent) α-alkenyl (12, 13) sodium sulfonate 8 Polyoxyethylene (1.5) alkyl (12, 14) Sodium ether sulfate 2 Hydrogen peroxide solution (30 %) 20 Methylparaben Suitable amount Sodium stannate Suitable amount Phosphorus Buffer pH3 adjustment Purified water balance Total 100 Example 28 (first agent) (wt%) Polyoxyethylene (1.5) lauryl ether sulfate triethanolamine 1.0 undecyl -N- hydroxyethyl -N- carboxy methyl Imidazolinium betaine 5.0 Lauryl dimethylamino acetic acid betaine 5.0 Isostearic acid 3.0 Keratin protein hydrolyzate 1.0 Dimethyl polysiloxane (polymerization degree 3000 to 6000) 1.5 Monoethanolamine 2.0 Ammonia water ( 28%) 15.0 L-ascorbic acid 0.5 Thioglycolate 1.0 Paraphenylenediamine 1.0 Resorcinol 0.5 Orthoaminophenol 1.0 Fragrance Suitable amount Purified water Balance total 100.0 (2nd agent) α-Alkenyl (12,13) Sodium Sulfonate 10 Carboxy Vinyl polymers ( "Hiviswako 105", manufactured by Wako Pure Chemical Industries, Ltd.) 0.5 hydrogen peroxide (30%) 20 Methylparaben qs sodium stannate qs phosphate buffer pH3 adjustment Purified water balance Total 100 Example 29 (a (1 agent) (% by weight) Undecyl-N-hydroxyethyl-N-carboxymethyl rumidazolinium betaine 2.0 Coconut oil fatty acid amidopropylmethylaminoacetic acid betaine 8.0 Oleic acid 3.0 1,3-butylene glycol 3 0.0 Collagen protein hydrolyzate 1.0 Monoethanolamine 2.0 Ammonia water (28%) 10.0 L-Ascorbic acid 0.5 Paraphenylenediamine 1.0 Resorcinol 1.0 Metaaminophenol 0.5 Perfume Suitable amount purified water balance total 100.0 (second agent) polyoxyethylene (1.5) alkyl (1 , 14) Sodium ether sulfate 8 Sodium lauroylmethyltaurine 2 O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethyl cellulose chloride 0.5 Hydrogen peroxide solution (30%) 20 Methylparaben Suitable amount Sodium stannate Suitable amount Phosphorus Acid buffer pH adjusted to pH 3 Purified water Balance total 100

[0075]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a hair dye which has good dyeability on hair, is resistant to fading, and is excellent in the feel of the hair after dyeing. In particular, when two or more preparations are combined in use to form a hair dye composition, the composition exhibits a viscosity that does not drip from the applied hair, but prior to combining, each preparation Since it has a viscosity suitable for putting things in and out of containers and the like, it is convenient to handle, and the hair dye of the present invention exhibits excellent effects as a hair dye for gray hair and fashionable dyeing.

[0076]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Michihiro Yamaguchi 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Inside Shiseido Daiichi Research Center (72) Inventor Masaaki Yasuda 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Kanagawa Shiseido Daiichi Research Center Co., Ltd.

Claims (16)

[Claims] 1. An in-use mixed hair dye composition in which a dye and an oxidizing agent are combined at the time of use, wherein the combined composition (a) is an amphoteric amphoteric dye (I) and an optional component. One or more kinds of surfactants (II) selected from the group consisting of surfactants and semipolar surfactants, one or more kinds of higher fatty acids (III), and one or more kinds of anionic surfactants (IV); An oxidant (V) and water (VI), and (b) components (I), (II) before use
And a component selected from the group consisting of (III), a component selected from the group consisting of components (IV) and (V),
The hair dye composition, which is placed in a separated form. 2. A hair dye composition according to claim 1, wherein the combined composition is adjusted to have a pH of 6-12. 3. The combined composition, based on its total weight, comprises 5 to 50% by weight of components (IV) and (II).
And 0.1 to 5% by weight of component (III),
The hair dye composition according to claim 1 or 2. 4. The combined composition, wherein the weight ratio of component (IV) to component (II) is 4/6 to 10 /.
It is 0, The hair dye composition in any one of Claims 1-3. 5. The combined composition has a content of monohydric alcohol having 2 to 5 carbon atoms of 3 based on the total weight thereof.
The hair dye composition according to any one of claims 1 to 3, which is contained in an amount of not more than 5% by weight. 6. Components (I), (II) and (III)
And (VI) and optionally a minor amount of (IV) as the first agent, and a major amount of component (IV), (V) and (VI) as the first agent. The hair dye composition according to any one of claims 1 to 3, which is used as two agents. 7. The component (II) comprises an imidazolinium betaine-type amphoteric surfactant, an amidobetaine-type amphoteric surfactant, an amide sulfobetaine-type amphoteric surfactant, a betaine-type amphoteric surfactant, and a sulfobetaine-type surfactant. The hair dye composition according to any one of claims 1 to 3, which comprises at least one surfactant selected from the group of amphoteric surfactants and tertiary amine oxide type semipolar surfactants. 8. The component (II) comprises at least one imidazolinium betaine-type amphoteric surfactant, an amidobetaine-type amphoteric surfactant, an amide-sulfobetaine-type amphoteric surfactant, a betaine-type amphoteric surfactant, The hair dye composition according to any one of claims 1 to 3, which is a mixture with at least one selected from the group consisting of a sulfobetaine type amphoteric surfactant and a tertiary amine oxide type semipolar surfactant. . 9. The component (III) has 7 to 25 carbon atoms,
The hair dye according to any one of claims 1 to 3, comprising at least one higher fatty acid composed of a straight chain or branched chain saturated or unsaturated hydrocarbon optionally having a hydroxyl group. Composition. 10. Component (IV) is a polyoxyalkylene alkyl ether sulfate, an alkyl ether sulfate,
The hair dye composition according to any one of claims 1 to 3, which comprises one or more surfactants selected from the group consisting of alkyloylalkyl taurine salts and α-olefin sulfonates. 11. A surfactant selected from the group consisting of polyoxyethylene alkyl ether sulfates and alkyl ether sulfates, wherein component (IV) has an even numbered alkyl chain of 10 to 18 carbon atoms. The hair dye composition according to any one of claims 1 to 3, containing one or more kinds. 12. The combined composition, wherein the weight ratio of component (IV) to component (II) is 4/6 to 6/4 and the pH is 6 or more and less than 8. The hair dye composition according to any one of 1. 13. The combined composition, wherein the weight ratio of component (IV) to component (II) is 4/6 to 6/4 and the pH is 8 to 12. The hair dye composition according to any one of 1. 14. The combined composition, wherein the weight ratio of component (IV) to component (II) is 4/6 to 10/0.
And pH is 6-12, The hair dye composition in any one of Claims 1-3 and 11. 15. The hair dye composition according to claim 14, which does not contain the component (II). 16. The viscosity of the combined composition is 30.
The hair dye composition according to any one of claims 1 to 15, which has a temperature of 500 cps or more at a temperature of 0 ° C.