JP5005458B2 - Hair dye composition, oxidative hair dye composition, and method for suppressing hair color change - Google Patents

Description

  The present invention relates to a hair dye composition, an oxidative hair dye composition, and a method for suppressing changes in hair color tone. More specifically, the present invention relates to a hair dye composition, an oxidative hair dye composition that can satisfactorily prevent a change in hair color tone even when stored for a long period of time, and a hair color tone change realized in these compositions. It is related with the suppression method.

  The oxidative hair dye composition is generally a two-component type that is mixed and applied to the hair at the time of use. The first agent (hair dye composition) contains, as main components, an oxidative dye intermediate comprising a main intermediate and a coupler, and an alkaline agent for improving the permeability to the hair. The second agent contains, as a main component, an oxidizing agent for coloring the oxidation dye intermediate. In such an oxidative hair dye composition, the first agent and the second agent are stored in an unmixed state for a period until use.

  Conventionally, due to the oxidation of the oxidative dye intermediate during the storage period of the hair dye composition, a reduction in hair dyeing power before and after storage has been a problem. The “decrease in hair dyeing power” basically means a reduction in the density of the hair color. And in order to prevent the fall of the above hair dyeing power, mixing an antioxidant with the 1st agent (hair dye composition) is known.

JP, 2002-201117, A For example, in above-mentioned patent documents 1, in order to prevent the fall of the hair dyeing power of an oxidative hair dye composition, the art which blends ascorbic acid (and sulfite) as an antioxidant is used. Disclosure. However, it has been found that when taking countermeasures by ascorbic acid, there is a problem that it is not possible to effectively prevent a reduction in hair coloring power during long-term storage.

JP, 2005-41820, A In above-mentioned patent documents 2, ascorbic acid as (A) ingredient and cysteine, cysteamine, and metalin as (B) ingredient about blending of an antioxidant to a hair dye composition. A hair dye composition containing an acid or the like is disclosed. However, the object of the invention is to “prevent discoloration of the hair dye composition itself during storage”, and does not present the problem of “preventing a decrease in hair coloring power”.

  As described above, with respect to the problem of oxidation of the oxidation dye intermediate during storage of the hair dye composition, there is a conventional technique in which an antioxidant is blended by paying attention to the antioxidant power.

  However, an essential problem in preventing changes in the hair dyeing function of the hair dye composition before and after storage is to suppress color changes that can be recognized with the naked eye. In consideration of the fact that the storage period of the agent composition is often long, it is to suppress such a change in hair color tone over a long period of time.

JP, 2007-8892, A In above-mentioned patent documents 3, it is a subject to control change of a dyeing effect over time in a hair dye composition, and here, "change of a dyeing effect" is evaluation of an example. As can be seen from the item, it means “change in color of hair dye”. However, the solution of the problem is to separate the alkali agent and the oxidation dye into a three-agent type.

  Thus, the subject of preventing the change of the hair color tone before and after preservation | save of a hair dye composition over a long term conventionally, and the solution means have not been proposed yet. This problem cannot be solved by the inventions described in Patent Document 1 and Patent Document 2. Although the invention described in Patent Document 3 may eventually become a problem-solving means, it requires an uncommon configuration of three-agent type.

  Then, this invention makes it the technical subject which should be solved to prevent the hair color tone change before and behind the preservation | save of a hair dye composition. The inventor of the present application combines the above-mentioned problem only when a specific type of coupler and a specific type of antioxidant are combined in a hair dye composition and the amount of the coupler is limited to a certain level or less. As a result, the present invention has been completed.

(First invention)
The constitution of the first invention of the present application for solving the above problems is a hair dye composition comprising an oxidation dye intermediate comprising a main intermediate and a coupler, and an alkali agent,
As the component (A), it contains at least one selected from an organic compound having 4 carbon atoms or less and a salt thereof having both a —SH group and a —NH ₂ group and having no —COOH group,
As the component (B) which is the coupler, an aromatic compound in which the same or different substituents arbitrarily selected from the following “Chemical Formula 3” and “Chemical Formula 4” are respectively bonded to the meta position of the mononuclear benzene ring structure (specific A meta coupler, and at least one selected from α-naphthol, and the blending amount of each of the components (B) is in the range of 0.01 to 0.5% by mass. It is a hair composition.

(R1 and R2 in the above "Chemical Formula 3" are each independently selected from hydrogen, a hydrocarbon group having 2 or less carbon atoms, an aliphatic alcohol group having 2 or less carbon atoms or a salt thereof, and R1 and R2 Are the same or different groups)

(R in the above "Chemical Formula 4" formula is arbitrarily selected from hydrogen, a hydrocarbon group having 2 or less carbon atoms, and an alcohol group having 2 or less carbon atoms or a salt thereof)
When the hair dye composition of the first invention is used, the color tone of the hair dye does not change even after long-term storage as compared to use in the initial stage of storage.

  When the (A) component and the (B) component are not blended in the hair dye composition, it is not possible to effectively prevent a change in the color of the hair dye over time during the storage period.

  When the blending amount of each type of component (B) is less than 0.01% by mass, a sufficient hair dyeing effect cannot be obtained due to a lack of absolute amount. When the blending amount of each component (B) exceeds 0.5% by mass, it is an area that is difficult to feel visually even if there is a change in the color of the hair, and thus the effects of the present invention are produced. However, the effect cannot be felt visually.

  In addition, in the invention described in Patent Document 2, the same compounding of the meta coupler as in the first invention and the compounding of cysteamine belonging to the component (A) are disclosed. However, the invention described in Patent Document 2 presents a problem different from that of the present invention, and requires the incorporation of ascorbic acids. Furthermore, although the blending of 0.5% by mass or less of the meta coupler is not excluded, only examples and comparative examples relating to the hair dye composition in which the blending amount of the meta coupler is 1% by mass are verified. Therefore, the invention described in Patent Document 2 does not disclose or suggest the problem and configuration of the first invention.

(Second invention)
The configuration of the second invention of the present application for solving the above problem is a hair dye composition in which the component (A) according to the first invention is at least one selected from cysteamine and a salt thereof.

  Although it does not limit as (A) component of a hair dye composition, At least 1 sort (s) chosen from the cysteamine prescribed | regulated to 2nd invention and its salt can be illustrated preferably.

(Third invention)
The structure of the third invention of the present application for solving the above-mentioned problems is that the specific meta coupler according to the first invention or the second invention is resorcin, metaaminophenol, 5-aminoorcresol, 5- (2-hydroxyethyl). A hair dye composition which is at least one selected from amino) -2-methylphenol and salts thereof.

  Specific meta couplers among the component (B) of the hair dye composition (that is, the same or different substitutions arbitrarily selected from the above “Chemical Formula 3” and “Chemical Formula 4” at the meta position of the mononuclear benzene ring structure) The aromatic compound to which each group is bonded is not limited, but at least one of the compounds listed in the third invention can be preferably exemplified.

(Fourth invention)
The constitution of the fourth invention of the present application for solving the above-mentioned problems is that the alkalinity defined by the consumption of the 0.1N acid standard solution of the hair dye composition according to any one of the first invention to the third invention. Is a hair dye composition having a pH of 6.0 ml / g or more.

  As in the fourth invention, the alkalinity of the hair dye composition is preferably 6.0 ml / g or more. If the alkalinity is less than 6.0 ml / g, sufficient hair dyeing power may not be obtained.

(Fifth invention)
The structure of the fifth invention of the present application for solving the above-described problem is at least a first agent which is a hair dye composition according to any one of the first to fourth inventions, and the hair dye containing an oxidizing agent. It is an oxidative hair dye composition comprised including the 2nd agent which is an oxidant composition mixed at the time of use with respect to a composition.

  The oxidative hair dye composition according to the fifth invention includes at least the first agent and the second agent, but is not necessarily a two-agent type, and has a suitable composition as described later. An agent may be added to form a three-agent system.

  In the oxidative hair dye composition according to the fifth invention, when the first agent and the second agent are mixed and used, the effects according to the first to fourth inventions described above can be ensured.

(Sixth invention)
The structure of the sixth invention of the present application for solving the above-mentioned problem contains an oxidation dye intermediate consisting of a main intermediate and a coupler and an alkali agent, and the coupler contains the component (B) defined in the first invention. Inhibiting the change in hair color tone by suppressing the change over time in the hair color tone of the hair dye composition by containing the component (A) specified in the first invention to the hair dye composition Is the method.

  According to the sixth invention, for the reason described above with respect to the first invention, it is possible to satisfactorily suppress the temporal change in the hair color tone of the hair dye composition during the storage period.

  According to the present invention, in the hair dye composition and the oxidative hair dye composition, it is possible to effectively prevent changes in the color of the hair dye over time during a long storage period.

  Next, modes for carrying out the present invention will be described including the best mode.

[Oxidative hair dye composition]
The oxidative hair dye composition according to the present invention comprises at least a hair dye composition (first agent), which will be described later, and an oxidant composition that contains an oxidant and is mixed with the hair dye composition at the time of use. (Second agent).

  This oxidative hair dye composition may be configured as a two-part formulation comprising the above-described hair dye composition (first agent) and oxidant composition (second agent). On the other hand, you may comprise as a 3 agent type of the structure which added the 3rd agent further. Examples of the third agent include hair treatment and conditioning having an arbitrary composition. These two-component and three-component oxidative hair dye compositions are used by mixing at the time of use.

  The hair dye composition (first agent), the oxidant composition (second agent) or the third agent dosage form constituting the oxidative hair dye composition can be selected from various known dosage forms. It can be arbitrarily selected according to its use and purpose of use. Examples thereof include liquid, emulsion, cream, gel, paste, mist (spray type), and aerosol foam.

[Oxidizing agent composition]
The composition of the oxidizing agent composition as the second agent is not limited as long as it contains an oxidizing agent. In addition to the oxidizing agent, the oxidizing agent composition may contain any necessary or beneficial component.

  The kind of oxidizing agent contained in the oxidizing agent composition is not particularly limited, and can be arbitrarily selected from various known oxidizing agents used for such purposes. Hydrogen peroxide is usually used, but other examples include potassium bromate, sodium bromate, sodium perborate, peroxide and the like. The blending amount of the oxidizing agent in the oxidizing agent composition is not particularly limited, and may be appropriately determined according to the purpose of use, dosage form, and the like of the oxidizing agent composition.

[Hair dye composition and its main components]
The hair dye composition according to the present invention is mixed with the above-mentioned oxidizing agent composition (second agent) or further with the third agent at the time of use. The hair dye composition comprises at least an oxidation dye intermediate comprising at least a main intermediate and a component (B) coupler (at least one selected from a specific meta coupler and α-naphthol), an alkali agent, (A) component mentioned above regarding invention is contained. The compounding quantity of a coupler exists in the range of 0.01-0.5 mass% about each 1 type.

  In addition, the ratio of the blending amount of the component (A) and the component (B) is within the range of (B) / (A) = 0.01 to 2 for each type of the component (B). More preferred. If the (B) / (A) value is below the above range, the hair dyeing power tends to be insufficient, and if the (B) / (A) value exceeds the above range, the effect of the present invention is insufficient. There is a risk of becoming.

  Moreover, it is more preferable that the hair dye composition further contains a hydrosulfite salt as the component (C). When the hair dye composition further contains a hydrosulfite salt, the effect of the present invention is further improved.

  The pH of the hair dye composition is not particularly limited, but is generally preferably about pH 7-12. An appropriate pH buffer component can be blended for such pH adjustment.

(Alkaline agent)
The type of the alkaline agent to be contained in the hair dye composition is not limited, but, for example, ammonia, alkanolamine (monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, etc.), ammonium salt Organic amines (2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, guanidine, etc.), inorganic alkalis (sodium hydroxide, potassium hydroxide, sodium carbonate, Potassium carbonate etc.), basic amino acids (arginine, lysine etc.) and their salts etc. can be selected suitably and used. In particular, when an organic alkali is contained, the effect of the present invention is easily obtained.

  The content of the alkaline agent in the hair dye composition is not necessarily limited, but for the reasons described above with respect to the fifth invention, the alkalinity is preferably 6.0 ml / g or more, and in particular, the alkalinity is 8.0 ml / g. The above is preferable.

(Major intermediate)
The main intermediate in the oxidation dye intermediate is not particularly limited, but one or more of salts such as phenylenediamines, aminophenols, diaminopyridines and their hydrochlorides, sulfates, acetates, etc. Can be illustrated. Specifically, p-phenylenediamine, toluene-2,5-diamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 2-β-hydroxyethyl-p-phenylenediamine, N-β -Hydroxyethyl-N-ethyl-p-phenylenediamine, N-phenyl-p-phenylenediamine, 4,4'-diaminodiphenylamine, 2-chloro-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, Examples include p-aminophenol, o-aminophenol, p-methylaminophenol, 2,6-dichloro-p-phenylenediamine, p-aminophenylsulfamic acid, 2,5-diaminopyridine and salts thereof. it can. The blending amount of the main intermediate may be appropriately determined according to the target hair color shade, and is not particularly limited.

(coupler)
In the hair dye composition according to the present invention, at least one selected from a specific meta coupler and α-naphthol is used as the coupler in the oxidation dye intermediate, that is, the component (B). The “specific meta coupler” refers to an aromatic compound in which the same or different substituents arbitrarily selected from the above “Chemical Formula 3” and “Chemical Formula 4” are bonded to the meta position of the mononuclear benzene ring structure.

  The type of the specific meta coupler is not limited as long as it meets the above definition, but preferred specific examples include resorcin, metaaminophenol, 5-aminoorthocresol, 5- (2-hydroxyethylamino) -2-methyl. Mention may be made of at least one selected from phenol and salts thereof.

  The blending amount of the component (B) in the hair dye composition is in the range of 0.01 to 0.5% by mass as described above for each one of the components (B) in which one or more are blended. Is within. Particularly preferably, it is in the range of 0.01 to 0.3% by mass in that an effect of preventing a change in hair color tone of the hair dye composition after short-term to long-term storage can be easily obtained.

((A) component)
The component (A) has both a -SH group and -NH ₂ group, and having 4 or less of the organic compound carbon no -COOH group, and refers to at least one selected from the salts thereof. As such component (A), at least one selected from cysteamine and a salt thereof can be particularly preferably exemplified.

((C) component)
The hydrosulfite salt as component (C) is preferably contained in the hair dye composition for the reason described above. Preferred examples of the hydrosulfite salt include Na salt and K salt. Although content of a hydrosulfite salt is not limited, For example, it can be set as about 0.01-1.0 mass%.

[Other components in hair dye composition]
In addition to the above-mentioned various components, the hair dye composition includes vitamins, oily components, surfactants, polymer substances, polypeptides, protein hydrolysates, amino acids, sequestering agents, as necessary. Antioxidants, fragrances, bactericides / preservatives, anti-inflammatory agents, ultraviolet absorbers, propellants, thickeners, colorants, and the like can be optionally blended. Various known or publicly known ingredients can be arbitrarily used as these compounding ingredients. Moreover, water is mix | blended as a solvent or dispersion medium of each component of a hair dye composition, and the density | concentration (mass percentage) of each component is adjusted. Some of these ingredients are described in detail below.

(Vitamins)
In the hair dye composition, one or more of various vitamins can be blended in an arbitrary blending amount range. The type of vitamins is not limited. For example, fat-soluble or water-soluble vitamins such as ascorbic acids and tocopherols can be arbitrarily selected and used.

(Oil component)
Examples of the oil component include hydrocarbons, polyhydric alcohols, waxes, fats and oils, higher alcohols, higher fatty acids, alkyl glyceryl ethers, esters, silicones, and the like. One of these can be blended alone, or two or more can be blended together.

  Examples of the hydrocarbon include paraffin, polyethylene powder, microcrystalline wax, petrolatum and the like. Examples of hydrocarbons that are liquid at room temperature include α-olefin oligomers, light isoparaffins, light liquid isoparaffins, synthetic squalane, vegetable squalane, squalane, polybutene, liquid isoparaffin, and liquid paraffin.

  Examples of the polyhydric alcohol include glycols and glycerins. Examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, isoprene glycol, and 1,3-butylene glycol. Examples of glycerins include glycerin, diglycerin, and polyglycerin.

  Examples of waxes include beeswax, candelilla wax, carnauba wax, jojoba oil, lanolin, whale wax, rice bran wax, sugar cane wax, palm wax, montan wax, cotton wax, bayberry wax, ibota wax, kapok wax, shellac wax, and the like. it can.

  Examples of the fats and oils include various vegetable oils and animal oils other than fats and oils that are polyhydric alcohol fatty acid esters.

  Higher alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol (cetanol), stearyl alcohol, cetostearyl alcohol, aralkyl alcohol, behenyl alcohol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol, decyltetradecanol, oleyl Alcohol, linoleyl alcohol, linolenyl alcohol, lanolin alcohol, etc. are mentioned.

  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, and lanolin fatty acid. It is done.

  Examples of the alkyl glyceryl ether include batyl alcohol (monostearyl glyceryl ether), chimyl alcohol (monocetyl glyceryl ether), selachyl alcohol (monooleyl glyceryl ether), and isostearyl glyceryl ether.

  Esters include various glycerin-based vegetable oils such as soybean oil, olive oil, hydrogenated castor oil, polyhydric alcohol fatty acid esters such as pentaerythritol-based fatty acid esters, diisopropyl adipate, diisobutyl adipate, dioctyl adipate, and adipic acid 2-hexyldecyl, diisostearyl adipate, isopropyl myristate, cetyl octanoate, cetyl isooctanoate, isononyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, diisopropyl sebacate, octyldodecyl myristate, isopropyl palmitate, stearin Butyl acid, stearyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, and myristic acid Isodecyl, isostearyl myristate, 2-ethylhexyl palmitate, octyldodecyl ricinoleate, fatty acid (C10-30) (cholesteryl / lanosteryl), lauryl lactate, cetyl lactate, myristyl lactate, octyldodecyl lactate, lanolin acetate, stearic acid Isocetyl, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, cetyl caprate, glyceryl tricaprylate, neopentyl glycol dicaprate , Diisostearyl malate, lanolin derivatives and the like.

  Examples of silicones include methylpolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, highly polymerized silicone having an average polymerization degree of 650 to 10,000, amino-modified silicone, and polyether-modified silicone. , Betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, trimethylsiloxysilicic acid, methylhydrogenpolysiloxane and the like. Examples of amino-modified silicones include aminopropylmethylsiloxane / dimethylsiloxane copolymer (aminopropyldimethicone), aminoethylaminopropylsiloxane / dimethylsiloxane copolymer (amodimethicone), aminoethylaminopropylmethylsiloxane / dimethylsiloxane copolymer. (Trimethylsilylamodimethicone) and the like.

(Surfactant)
Examples of the surfactant include cationic surfactants, nonionic surfactants, anionic surfactants and amphoteric surfactants other than the above-described cured castor oil fatty acid ester derivatives. One of these can be blended alone, or two or more can be blended together.

  Cationic surfactants include lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, behenyl trimethyl ammonium methyl sulfate, tri (polyoxyethylene) stearyl ammonium chloride, quaternium-91 (INCI). Name), behenyltrimethylammonium chloride, distearyldimethylammonium chloride, ethyl lanolin sulfate fatty acid amidopropylethyldimethylammonium bromide, cetyltrimethylammonium bromide, stearyltrimethylammonium bromide, stearyltrimethylammonium saccharin, cetyltrimethylammonium saccharin, N, N- Di (acyloxy), N- (hydroxyethyl), N-methyl Nmo methosulfate, and the like.

  Nonionic surfactants include polyoxyethylene (hereinafter referred to as POE) alkyl ethers, POE alkylphenyl ethers, POE / polyoxypropylene alkyl ethers, POE sorbitan fatty acid esters, POE propylene glycol fatty acid esters, fats Group alkanolamides and the like.

  Examples of anionic surfactants include alkyl sulfates such as sodium lauryl sulfate, POE alkyl sulfates such as POE lauryl ether sodium sulfate, alkyl sulfate esters such as lauryl sulfate triethanolamine, stearoylmethyl taurine sodium, dodecylbenzenesulfonic acid Examples include triethanolamine, sodium tetradecenesulfonate, POE lauryl ether phosphate and salts thereof, N-lauroyl glutamates, and N-lauroylmethyl-β-alanine salts.

  Examples of amphoteric surfactants include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine sodium, cocoamidopropyl betaine, lauryldimethylaminoacetic acid betaine.

(Polymer substance)
Examples of the polymer substance include anionic polymers such as cationic polymers and carboxyvinyl polymers, amphoteric polymers such as diallyl quaternary ammonium salts / acrylic acid copolymers, and various water-soluble polymers. One of these can be blended alone, or two or more can be blended together.

  Specific examples of water-soluble polymers include vegetable polymers such as gum arabic, xanthan gum, carrageenan, pectin, agar, starch, microbial polymers such as dextran and pullulan, animal polymers such as collagen, casein and gelatin, methylcellulose, hydroxy Cellulose polymers such as ethyl cellulose are exemplified, and other examples include sodium alginate, carboxyvinyl polymer, polyoxyethylene polymer, sodium polyacrylate, polyacrylamide polydimethylmethylenepiperidinium chloride and the like.

(Polypeptides, protein hydrolysates, amino acids)
Polypeptides include proteins such as collagen, keratin, elastin, fibroin, egg, silk, conchiolin, casein, gelatin, rice, wheat, barley, oats, soybeans, peas, almonds, Brazil nuts, potatoes and corn. Examples include the resulting protein. Examples of the protein hydrolyzate include protein hydrolysates obtained by hydrolyzing the above-mentioned various proteins with acid, alkali, enzyme, or the like. Amino acids include various acidic, neutral or basic amino acids.

[Method of suppressing changes in hair color tone]
The method for suppressing a change in hair color tone according to the present invention comprises an oxidation dye intermediate comprising a main intermediate and a coupler and an alkali agent, and the coupler includes a hair dye composition containing the component (B). It is a method for suppressing a change in hair color tone over time, and is characterized by containing the component (A) in such a hair dye composition.

  Examples of the application target of the method for suppressing a change in hair color tone include the above-described hair dye composition, or a two-part or three-part oxidative hair dye composition containing the same as the first agent.

  In the hair dye composition, the contents of the main intermediate and the alkali agent are the same as described above. The more preferable compounding quantity of (B) component and (A) component is as having mentioned above. When the (C) component is added to the hair dye composition in addition to the (B) component and the (A) component, the effect is further improved. In the hair dye composition, various components described in the above-mentioned section “Other components in the hair dye composition” can be blended as necessary.

Examples of the present invention will be described below together with comparative examples. The technical scope of the present invention is not limited by these examples and comparative examples.
[Examples and Comparative Examples According to First Example Group]
Cream-like hair dye compositions having compositions according to Examples 1 to 15 shown in Table 1 at the end and Comparative Examples 1 to 13 shown in Table 2 at the end were prepared according to a conventional method. In addition, Example 15, the comparative example 12, and the comparative example 13 are the compounding examples used as dark hair dyeing so that a composition may show. These hair dye compositions are all used as the first agent of the oxidative hair dye, and are mixed with the cream-like oxidant composition having the following composition as the second agent of the oxidative hair dye when used. Thus, an oxidative hair dye is prepared.
(Second agent)
35% hydrogen peroxide solution 17.0% by mass
Sodium stannate 0.1% by mass
EDTA 0.5% by mass
Cetanol 2.0% by mass
Sodium lauryl sulfate 1.0 mass%
Phosphoric acid 0.5% by mass
Purified water balance Regarding the components shown in Tables 1 and 2, the (A) component, (B) component, and (C) component are indicated in the margin. In addition, the numerical values of the component amounts shown in Tables 1 and 2 are all expressed in mass%. Moreover, the alkalinity (ml / g) prescribed | regulated by the consumption of the 0.1N acid standard solution of each hair dye composition is also shown together in the table | surface.
[Evaluation of Examples and Comparative Examples]
(Evaluation 1: Dyeing test)
The hair dye compositions according to the examples and comparative examples shown in Table 1 and Table 2 were mixed with the above oxidizer composition in a mass ratio of 1: 1 to prepare an oxidative hair dye. (1) These oxidative hair dyes immediately after preparation, and (2) these oxidative hair dyes after storage for 2 weeks at 60 ° C. are attached to a test white cloth (JIS L0803 dyeing fastness test attachment) White fabric), left for 20 minutes, washed with water, and dried to give a dyed fabric. In addition, “storage at 60 ° C. for 2 weeks” of the oxidative hair dye corresponds to storage for 3 years at room temperature.

L ^* a ^* b ^* table using a spectrocolorimeter (manufactured by Konica Minolta: CM508d) for the dyed fabrics of the above-mentioned (1) and (2) according to each example and comparative example using the oxidative hair dye. Values in the color system (CIE 1976) were measured. For each example, a ^* b ^* value (a ₀ , b ₀ ) in a dyed fabric using an oxidized hair dye immediately after preparation, and a dyed fabric using an oxidized hair dye after storage at 60 ° C. for 2 weeks. The a ^* b ^* values (a ₁ , b ₁ ) were measured, and the color difference ΔE (a, b) was calculated according to the following formula 1. The values are shown in the column “ΔE (a, b) 60 ° C. 2 W” in Tables 1 and 2.

ΔE (a, b) = {(a ₁ −a ₀ ) ² + (b ₁ −b ₀ ) ² } ^1/2 Equation 1
The case where the calculated ΔE (a, b) is 0 or more and less than 0.5 is “◎”, the case where 0.5 or more and less than 1 is “◯”, and the case where it is 1 or more and less than 2 is “ The case of 2 or more was designated as “x”, and the results were shown in the “Evaluation of ΔE (a, b)” column of Tables 1 and 2.
(Evaluation 2: Visual color difference evaluation)
The hair dye compositions according to the examples and comparative examples shown in Table 1 and Table 2 were mixed with the above oxidizer composition in a mass ratio of 1: 1 to prepare an oxidative hair dye. (1) These oxidative hair dyes immediately after preparation, and (2) these oxidative hair dyes after storage at 60 ° C. for 2 weeks, respectively, (a) untreated human black hair bundles, (B) Dye to which a black hair bundle is applied to a commercially available bleaching agent (trade name “Beauty Lab Bleach S” manufactured by Hoyu Co., Ltd.) and subjected to plain rinsing after being left for 30 minutes. Hair treatment was performed.

And about the hair | bristle bundle which concerns on the hair dyeing | staining by the oxidation hair dye of said (1) and (2), the color difference between each other was evaluated visually. This color difference was evaluated for each of the cases using (a) and (b). The evaluation is “◯” when no color difference is felt, “△” when a slight color difference is felt, and “X” when a clear color difference is felt, and the results are shown in the “Visual color difference” column in Tables 1 and 2. Indicated. In addition, about the same Example or comparative example, about the case where the evaluation result with the case where (a) was used and the case where (b) was used, we decided to employ | adopt a bad evaluation result. . However, in practice, in most examples and comparative examples, the evaluation results obtained when (a) was used were the same as when (b) was used.
[Examples and Comparative Examples According to Second Example Group]
Liquid hair dye compositions having compositions according to Example 16 and Comparative Example 14 shown in Table 3 at the end were prepared according to a conventional method. These hair dye compositions are all used as the first agent of the oxidative hair dye, and are the same composition as that described above in the first embodiment group as the second agent of the oxidative hair dye, and are emulsion-like. It mixes with an oxidizing agent composition at the time of use, and prepares an oxidation hair dye.

  Regarding each component shown in Table 3, about the (A) component, the (B) component, and the (C) component, the fact was described in the margin. The numerical values of the component amounts shown in Table 3 are all expressed in mass%. Moreover, the alkalinity (ml / g) prescribed | regulated by the consumption of the 0.1N acid standard solution of each hair dye composition is also shown together in the table | surface.

For the hair dye composition according to Example 16 and Comparative Example 14 shown in Table 3, the dyeing cloth test was performed in exactly the same manner as in the first example group, including the mass mixing ratio with the oxidant composition, A value in the L ^* a ^* b ^* color system (CIE 1976) is measured to calculate a color difference ΔE (a, b) according to the above-mentioned formula 1, and for the calculated ΔE (a, b), “◎” to “×” Was evaluated. The results are shown in the column “Evaluation of ΔE (a, b)” in Table 3.

  Further, for the hair dye composition according to Example 16 and Comparative Example 14, visual color difference evaluation was performed in exactly the same manner as in the first example group including the mass mixing ratio with the oxidant composition. . The results are shown in the “Visual color difference” column of Table 3.

  The present invention provides a hair dye composition and an oxidative hair dye composition that can effectively prevent changes in hair color tone even during long-term storage.

Claims (5)

A hair dye composition containing an oxidation dye intermediate comprising a main intermediate and a coupler and an alkali agent (excluding those containing more than 0.5% by mass of ascorbic acid) ,
(A) As a component, it contains at least one selected from cysteamine and a salt thereof ,
As the component (B) which is the coupler, an aromatic compound in which the same or different substituents arbitrarily selected from the following “Chemical Formula 1” and “Chemical Formula 2” are respectively bonded to the meta position of the mononuclear benzene ring structure (specific (Meta coupler) and at least one selected from α-naphthol, and the amount of the component (A) is in the range of 0.2 to 0.5% by mass, and the component (B) The hair dye composition characterized by the compounding quantity about each 1 type being in the range of 0.01-0.5 mass%.
(R1 and R2 in the above "Chemical Formula 1" are each arbitrarily selected from hydrogen, a hydrocarbon group having 2 or less carbon atoms, an aliphatic alcohol group having 2 or less carbon atoms or a salt thereof, and R1 and R2 Are the same or different groups)
(R in the above “Chemical Formula 2” formula is arbitrarily selected from hydrogen, a hydrocarbon group having 2 or less carbon atoms, and an alcohol group having 2 or less carbon atoms or a salt thereof) The specific meta coupler is at least one selected from resorcin, metaaminophenol, 5-aminoorthocresol, 5- (2-hydroxyethylamino) -2-methylphenol, and salts thereof. The hair dye composition according to claim 1 . The hair dyeing composition according to claim 1 or 2 , wherein the alkalinity defined by the consumption amount of the 0.1N acid standard solution of the hair dye composition is 6.0 ml / g or more. Agent composition. The oxidizing agent composition which contains at least the 1st agent which is the hair dye composition in any one of Claims 1-3, and an oxidizing agent, and is mixed with respect to the said hair dye composition at the time of use. And a second agent, wherein the composition comprises an oxidative hair dye composition. A hair dye composition containing a component (B) defined in claim 1 as the coupler contains an oxidation dye intermediate consisting of a main intermediate and a coupler, and an alkali agent. (A) The suppression method of the hair color tone change characterized by suppressing the temporal change of the hair color tone of the said hair dye composition by containing (A) component to do.