TW202245733A - Keratin fiber treatment method - Google Patents

Abstract

This keratin fiber treatment method comprises the following step (i) and step (ii) in the stated order. Step (i): A step for applying a composition (1) including the following components (A) and (B) and having a pH of 8.0-12.0 to a keratin fiber. (A) A compound represented by general formula (1) or a salt thereof [in formula (1), a broken line represents the presence or absence of a [pi] bond; R1 represents a hydroxyl group or an acetoxy group; R2 represents a hydrogen atom or -COOR (where R is a hydrogen atom, a methyl group, or an ethyl group); and R3 represents a hydrogen atom, an acetyl group, a methyl group, or an ethyl group]. (B) An alkali agent. Step (ii): A step for applying a composition (2) including the following components (C) and (D) and having a pH of 3.5 or more and less than 8.0 to the keratin fiber. (C) A cationic surfactant. (D) A higher alcohol.

Description

Keratin fiber treatment method

The present invention relates to a method for treating keratin fibers.

Conventionally, as hair dyes for white hair, air oxidation type hair dyes using 5,6-dihydroxyindole, 5,6-dihydroxyindoline or their derivatives. Since these melanin precursors do not use an oxidizing agent, there is less damage to keratin fibers when used in hair dyes, and the convenience as a dye for hair dyes is high. For example, in Japanese Patent Laid-Open No. 62-238878 (Patent Document 1), Japanese Patent Laid-Open No. 2-218606 (Patent Document 2), Japanese Patent Laid-Open No. 5-058860 (Patent Document 3) and Japanese Patent Japanese Unexamined Patent Publication No. 2018-052833 (Patent Document 4) discloses a composition containing the above-mentioned melanin precursor and a method of dyeing keratin fibers using it. On the other hand, the industry proposes that melanin precursors can be blended into keratin fiber compositions such as shampoos that everyone uses in daily shampooing, which can easily and quickly exert high hair dyeing properties on gray hair (For example, refer to Japanese Patent Laid-Open No. 2019-094326 (Patent Document 5)).

[式(1)中，虛線表示存在或不存在π鍵，R ¹表示羥基或乙醯氧基，R ²表示氫原子或-COOR(R為氫原子、甲基或乙基)，R ³表示氫原子、乙醯基、甲基或乙基] (B)鹼劑 步驟(ii)：將含有如下成分(C)及(D)，且pH值為3.5以上且未達8.0之組合物(2)應用於角蛋白纖維之步驟 (C)陽離子性界面活性劑 (D)高級醇 The present invention relates to a method for treating keratin fibers, comprising the following step (i) and step (ii) in sequence. Step (i): Applying the composition (1) containing the following components (A) and (B) and having a pH value of not less than 8.0 and not more than 12.0 to keratin fibers (A) represented by general formula (1) Compound or its salt [Chemical 1]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl group, methyl group or ethyl group] (B) alkaline agent step (ii): the composition (2 ) Step applied to keratin fibers (C) cationic surfactant (D) higher alcohol

Hair dyes containing melanin precursors have slightly slower dyeability (hair dyeing properties) than ordinary oxidative hair dyes, and have the characteristic that keratin fibers are gradually dyed by repeated use. However, it can be seen that when using a composition containing a melanin precursor such as the shampoo composition shown in the examples of Patent Document 5, the color tone of the dyed keratin fibers is different from the original color tone (natural gray to black) to be dyed. ), sometimes with a yellowish tinge. The inventors of the present invention have studied various compositions used before and after using the composition, and found that if other acidic compositions such as hair conditioner, conditioner or conditioner are used after using the composition, especially For other compositions whose pH value is less than 4.9 at 25°C, the hue of the dyed keratin fibers gradually becomes yellowish, and there is a problem that the keratin fibers are not easily dyed to the original color due to the oxidation of the melanin precursor .

Patent Documents 1, 2, 3, and 4 also describe the case of dyeing hair using a composition containing a melanin precursor and other compositions, but the above-mentioned problem is not described. Also, it does not describe that the above-mentioned problems are solved by making the composition or physical properties of the conditioner or care agent used after applying the melanin precursor to keratin fibers specific. The present invention is concerned with providing a method for treating keratin fibers, which comprises the steps of applying a composition comprising a melanin precursor to keratin fibers in sequence; and imparting a conditioning effect or repair to keratin fibers. The effect composition is applied to the steps of keratin fibers, and even if these steps are repeated, the reduction of dyeability is also suppressed, and the original color that is less yellow due to the oxidation of the melanin precursor can be dyed, and Improves combability.

[式(1)中，虛線表示存在或不存在π鍵，R ¹表示羥基或乙醯氧基，R ²表示氫原子或-COOR(R為氫原子、甲基或乙基)，R ³表示氫原子、乙醯基、甲基或乙基] (B)鹼劑 步驟(ii)：將含有如下成分(C)及(D)，且pH值為3.5以上且未達8.0之組合物(2)應用於角蛋白纖維之步驟 (C)陽離子性界面活性劑 (D)高級醇 [2]一種角蛋白纖維用組合物套組，其具備：組合物(1)，其含有如下成分(A)及(B)，且pH值為8.0以上且12.0以下；及組合物(2)，其含有如下成分(C)及(D)，且pH值為3.5以上且未達8.0。 (A)通式(1)所表示之化合物或其鹽 [化3]

[式(1)中，虛線表示存在或不存在π鍵，R ¹表示羥基或乙醯氧基，R ²表示氫原子或-COOR(R為氫原子、甲基或乙基)，R ³表示氫原子、乙醯基、甲基或乙基] (B)鹼劑 (C)陽離子性界面活性劑 (D)高級醇 The inventors of the present invention have found that the following method for treating keratin fibers can be provided by sequentially combining the first composition (composition (1)) containing a specific melanin precursor and an alkali agent and having a specific pH value; and containing a cationic Surfactant and higher alcohol, and the second composition (composition (2)) with a specific pH value is applied to keratin fibers, and even if the application is repeated, the decrease in dyeability is also suppressed, and less yellow dyeing is possible The original color of the melanin precursor (natural gray to black), and can improve the combability. That is, the present invention relates to the following [1] to [2]. [1] A method for treating keratin fibers comprising the following step (i) and step (ii) in this order. Step (i): Applying the composition (1) containing the following components (A) and (B) and having a pH value of not less than 8.0 and not more than 12.0 to keratin fibers (A) represented by general formula (1) Compound or its salt [Chem. 2]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl group, methyl group or ethyl group] (B) alkaline agent step (ii): the composition (2 ) step of applying to keratin fibers (C) cationic surfactant (D) higher alcohol [2] a composition set for keratin fibers, which comprises: composition (1), which contains the following component (A) and (B) having a pH of 8.0 to 12.0; and a composition (2) containing the following components (C) and (D) and having a pH of 3.5 to less than 8.0. (A) Compound represented by general formula (1) or salt thereof [Chemical 3]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl group, methyl or ethyl] (B) alkaline agent (C) cationic surfactant (D) higher alcohol

According to the present invention, there can be provided a method for treating keratin fibers, which comprises sequentially applying a composition containing a melanin precursor to keratin fibers such as hair; and imparting a conditioning effect or a repairing effect to keratin fibers. When the composition is applied to the steps of keratin fibers, even if these steps are repeated, the decrease in dyeability can be suppressed, and the original color (natural gray to black) of the melanin precursor with less yellow can be dyed, and combing can be achieved. Sexual change is good.

Embodiments of the method for treating keratin fibers and the composition set for keratin fibers according to the present invention will be described in detail below. In addition, in this specification, the term "A to B" related to the description of the numerical value means "more than A and less than B" (in the case of A<B) or "below A and more than B" (in the case of A>B) situation). Moreover, in this invention, the combination of a preferable aspect is a more preferable aspect.

[keratin fiber processing method] In the present invention, keratin fibers refer to body hair of mammals, specifically, hair, eyebrows, eyelashes, beard, and the like. Among these, hair is preferable as keratin fiber. In the present invention, "hair" mainly means hair, and also includes black hair, white hair, or bleached hair. The composition for keratin fibers in this invention is a composition for keratin fibers. In addition, in the following description, the dyeing effect of the keratin fiber using a component (A) may be abbreviated as "dyeability".

[式(1)中，虛線表示存在或不存在π鍵，R ¹表示羥基或乙醯氧基，R ²表示氫原子或-COOR(R為氫原子、甲基或乙基)，R ³表示氫原子、乙醯基、甲基或乙基] (B)鹼劑 步驟(ii)：將含有如下成分(C)及(D)，且pH值為3.5以上且未達8.0之組合物(2)應用於角蛋白纖維之步驟 (C)陽離子性界面活性劑 (D)高級醇 The method for treating keratin fibers of the present invention has the following steps (i) and (ii) in this order. Step (i): Applying the composition (1) containing the following components (A) and (B) and having a pH value of not less than 8.0 and not more than 12.0 to keratin fibers (A) represented by general formula (1) Compound or its salt [Chem. 4]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl group, methyl group or ethyl group] (B) alkaline agent step (ii): the composition (2 ) Step applied to keratin fibers (C) cationic surfactant (D) higher alcohol

The inventors of the present invention have conducted various researches on the following subject: if the operation of repeatedly using a composition containing a melanin precursor on hair and other keratin fibers, and then using other compositions such as hair conditioner or repairing agent, dyeing Decreased, gradually dyed with a yellowish hue. As a result, the inventors of the present invention have found that the above-mentioned problems can be solved by a method for treating keratin fibers comprising the step of treating melanin fibers containing a specific melanin precursor and an alkali agent and having a specific pH value. A step of applying the first composition to keratin fibers; and a step of applying the second composition containing a cationic surfactant and a higher alcohol and having a specific pH to the keratin fibers after the step. According to the method for treating keratin fibers of the present invention, it is possible to provide a method for treating keratin fibers in which the first composition containing a melanin precursor, such as a cleanser, is repeatedly applied to the keratin fibers, followed by the application of a conditioner or conditioner. The operation of the second composition with a specific pH value, such as conditioner, can also suppress the reduction of dyeability, and can dye the original color (natural gray to black) that is less yellow due to the oxidation of the melanin precursor. , and can make the combability become better.

The detailed reason why such an effect is obtained is not clear, but one of the reasons is considered to be as follows. That is, by having step (i) and step (iii) sequentially, first by applying the first composition having a specific pH value, the cuticle of the keratin fiber is opened. Then, by applying a second composition having a specific pH lower than that of the first composition, the keratin fibers shrink, thereby imparting a smooth touch or smear feeling, ensuring good combability. Also, it is considered that the dyeability of the composition (1) applied to keratin fibers in the step (i) is not inhibited by the second composition having an appropriate pH value, and the keratin fibers are removed by repeating the step (i). When the protein fibers are gradually dyed, the yellowing of the keratin fibers can be suppressed.

[式(1)中，虛線表示存在或不存在π鍵，R ¹表示羥基或乙醯氧基，R ²表示氫原子或-COOR(R為氫原子、甲基或乙基)，R ³表示氫原子、乙醯基、甲基或乙基] (B)鹼劑 (Step (i)) Step (i) is a step of applying the composition (1) containing the following components (A) and (B) and having a pH of 8.0 to 12.0 to keratin fibers. (A) Compound represented by general formula (1) or salt thereof [Chem. 5]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl group, methyl group or ethyl group] (B) alkaline agent

By step (i), component (A) which is a melanin precursor is supplied to keratin fiber. After component (A) permeates into keratin fibers, it oxidizes and polymerizes with oxygen in the atmosphere to form melanin (melanin polymer). Then, by repeating the step (i), the keratin fibers are gradually dyed into the original color due to the oxidation of the melanin precursor. In addition, by performing the following step (ii) after the step (i), the composition (2) with a specific pH value is supplied to the keratin fibers, so even if the steps (i) and (ii) are repeated, the dyeability is suppressed The lowering or keratin fibers have a yellowish hue.

In the process (i), after applying composition (1) to keratin fiber, it can be used by making it foam with a hand, a hair brush, etc. It can also be foamed by rubbing the palms or both hands in advance, or sprayed in a foam form from a foaming container, or the composition (1) which has been foamed in advance is applied to the keratin fibers. In addition, it can also be left for a certain period of time after being applied to keratin fibers. From the standpoint of simultaneously achieving simplicity and dyeability, the total of the standing time and foaming time after application to keratin fibers is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 30 seconds to 2 minutes. From the viewpoint of usability, when the mass of keratin fibers is 1, the amount of composition (1) applied to keratin fibers is preferably 0.01-2, more preferably 0.05-1. Furthermore, before the step (i), it is preferable to untangle the keratin fibers with a tool such as a brush in advance from the viewpoint of the ease of spreading the composition (1) to the keratin fibers. Also, from the same viewpoint, it is preferable to wet the keratin fibers with water in advance. The keratin fibers can also be washed with detergents such as shampoo before step (i). It is preferable to include a step of rinsing with water after washing.

It is preferred to have a step of rinsing the keratin fibers with water between step (i) and step (ii). In addition, after the step of rinsing, there may be a step of drying the keratin fibers appropriately (hereinafter also simply referred to as "drying step"). The step of drying the keratin fibers is a step of reducing the moisture content of the keratin fibers. The above-mentioned drying step includes, for example, a method of twisting keratin fibers to remove excess moisture. In addition, in order to actively reduce the water content of keratin fibers, drying with a towel, drying with a blower (cold air or hot air), air drying, and a combination of two or more of these drying treatments are included. From the viewpoint of the ease of wiping off the composition (2) onto keratin fibers, it is preferred to use the composition (2) in the step (ii) while maintaining a wet state after the above-mentioned rinsing step. After the step (i), when the mass of the keratin fiber provided in the step (ii) is set to 1, the water content in the keratin fiber is preferably 0.1 or more, more preferably 0.2 or more, and then Preferably it is 0.5 or more, More preferably, it is 0.8 or more. After the step (i), the upper limit of the water content in the keratin fibers used in the step (ii) is not particularly limited, and it is usually 5 or less, in order to prevent water from dripping from the keratin fibers and improve handling properties. From a viewpoint, it is preferably 3 or less, more preferably 2 or less, and still more preferably 1.2 or less. Furthermore, as a method for measuring the moisture content in keratin fibers, the quality of keratin fibers in each treatment step can be used to dry them with hot air from a hair dryer for 30 minutes, and place them at a temperature of 25°C and a relative humidity of 65%. The difference in mass of keratin fibers that were completely dried over a day and night was measured.

More specifically, it is preferable to have the following steps of step (i-1), step (i-2) and step (i-3) between step (i) and step (ii). ・Step (i-1): a step of standing after applying the composition (1); a step of foaming the composition (1); and a step of foaming the composition (1) and then standing any step ・Step (i-2): A step of rinsing the composition (1) on the keratin fibers with water ・Step (i-3): A step of drying keratin fibers In the step (i-1), when foaming by hand, it can be foamed with fingers or palms, or with a brush or the like. In the step (i-2), from the viewpoint of efficiently rinsing the composition (1), the temperature of the water at the time of rinsing is preferably 0°C or higher, more preferably 5°C or higher, further preferably 10°C or higher , Also, preferably below 45°C, more preferably below 40°C. In the step (i-3), the keratin fibers may be dried completely (that is, specifically, when the mass of the keratin fibers is set to 1, the moisture content in the keratin fibers is made to be 0.01 or less), The keratin fibers can also be twisted to remove excess moisture and keep it moist. Also, between step (i) and step (ii), step (i) can be repeated again arbitrarily, and a composition other than composition (1) and composition (2) can also be applied to keratin fibers the steps.

＜Composition (1)＞ The composition (1) used in the step (i) is not particularly limited as long as it contains component (A) and component (B). The composition (1) of the present invention can make keratin fibers It is gradually dyed, so it is sometimes necessary to use it multiple times. Therefore, as for the composition (1), preferably, combinations for keratin fibers such as shampoos and other cleansers, conditioners, conditioners, and care agents that can be easily dyed by daily hair care activities are exemplified. provided in the form of things. Among them, the composition (1) is more preferably a cleansing agent from the viewpoint of easy dyeing by daily hair care activities and the viewpoint of obtaining good dyeability. The dosage form of the composition (1) is not particularly limited, for example, it can be made into any dosage form such as liquid, foam, ointment, cream, solid or powder. From the viewpoint of spreadability to keratin fibers, it is preferably in the form of liquid, paste or cream.

The composition (1) used in the step (i) contains the following components (A) and (B), and has a pH of 8.0 or more and 12.0 or less. By making the pH value of the composition (1) 8.0 or more, the effect of accelerating the polymerization reaction and improving the dyeability can be obtained, and by making the pH value of the composition (1) 12.0 or less, the dyeability can be improved, And inhibit the damage to keratin fibers. The pH of the composition (1) is preferably at least 8.5, more preferably at least 8.8, and still more preferably at least 9.0, from the viewpoint of further promoting the polymerization reaction and further improving the dyeability. The reason is that component (A), which is the precursor of melanin, easily reacts with oxygen in the air under alkaline conditions, thereby converting into melanin. From the viewpoint of further improving the dyeability and the inhibition of damage to keratin fibers, the pH is preferably at most 11.0, more preferably at most 10.5, and still more preferably at most 10.0. Specifically, the pH value is preferably from 8.5 to 11.0, more preferably from 8.8 to 10.5, and still more preferably from 9.0 to 10.0. The above-mentioned pH value is a measured value at 25° C., and specifically, it can be measured by the method described in the examples.

[式(1)中，虛線表示存在或不存在π鍵，R ¹表示羥基或乙醯氧基，R ²表示氫原子或-COOR(R為氫原子、甲基或乙基)，R ³表示氫原子、乙醯基、甲基或乙基] 成分(A)之黑色素前驅物為作為通式(1)所表示之化合物之吲哚衍生物或吲哚啉衍生物、或該等之鹽，於本發明中，可使用其1種或2種以上之組合。從染色性之觀點出發，成分(A)更佳為吲哚衍生物(即，於通式(1)中之虛線部分存在π鍵)。 從成分(A)之獲取性及染色性之觀點出發，於通式(1)中，R ¹較佳為羥基，R ²較佳為氫原子或-COOR(R為氫原子、甲基或乙基)，更佳為氫原子或-COOH。R ³較佳為氫原子。 <Component (A)> The composition (1) used in a process (i) contains the compound represented by following general formula (1) or the component (A) which is a salt thereof. Component (A) is a melanin precursor converted into melanin by polymerization by air oxidation, and functions as a dyeing agent for keratin fibers. [chemical 6]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents A hydrogen atom, an acetyl group, a methyl group or an ethyl group] The melanin precursor of the component (A) is an indole derivative or an indoline derivative, or a salt thereof, which is a compound represented by the general formula (1), In the present invention, one type or a combination of two or more types thereof can be used. From the viewpoint of dyeability, the component (A) is more preferably an indole derivative (that is, there is a π bond in the dotted line portion in the general formula (1)). From the viewpoint of the availability and dyeability of component (A), in the general formula (1), R ¹ is preferably a hydroxyl group, and R ² is preferably a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), more preferably a hydrogen atom or -COOH. R ³ is preferably a hydrogen atom.

Examples of the compound represented by the above general formula (1) include: 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 5,6-dihydroxyindole-2- Methyl carboxylate, ethyl 5,6-dihydroxyindole-2-carboxylate, N-methyl-5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole-2 -Carboxylic acid, N-ethyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole-2-carboxylic acid, N-acetyl-5,6-dihydroxyindole Indole, N-acetyl-5,6-dihydroxyindole-2-carboxylic acid, 5-acetyloxy-6-oxindole, 5-acetyloxy-6-oxindole-2- Carboxylic acid, 5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 5,6-dihydroxyindoline-2-carboxylic acid methyl ester, 5,6-dihydroxyindoline-2-carboxylic acid Hydroxyindoline-2-carboxylic acid ethyl ester, N-methyl-5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline-2-carboxylic acid, N-ethyl Base-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline-2-carboxylic acid, N-acetyl-5,6-dihydroxyindoline, N- Acetyl-5,6-dihydroxyindoline-2-carboxylic acid, 5-acetyloxy-6-hydroxyindoline, 5-acetyloxy-6-hydroxyindoline-2-carboxy Acid etc.

As the salt of the compound represented by the above-mentioned general formula (1), hydrochloride, hydrobromide, sulfate, phosphate, acetate, propionate, lactate, citrate, etc. of the compound can be exemplified. Among these, hydrobromide is preferred from the viewpoint of availability. Also, when R ² is -COOH in the general formula (1), the salt of the compound represented by the general formula (1) may, for example, be a carboxylate (R ² is -COO ^- X ⁺ (X ⁺ is Alkali metal ions such as Na ⁺ , K ⁺ , alkaline earth metal ions such as Ca ⁺ , Mg ⁺ , cations such as ammonium ions)).

From the viewpoint of dyeing keratin fibers in a natural color tone (gray to black), the component (A) is preferably selected from 5,6-dihydroxyindole, 5,6-dihydroxyindole-2- One or more of the group consisting of carboxylic acid, 5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, and their salts, more preferably One or more of the group consisting of 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, and 5,6-dihydroxyindoline hydrobromide , and more preferably one or two selected from the group consisting of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid, and more preferably combined use of 5,6 -Dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid. When 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid are used together, the molar ratio is preferably in the range of 50:50 to 99:1, more preferably It is in the range of 80:20 to 99:1, and more preferably in the range of 85:15 to 95:5. If the molar ratio of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid is in the above-mentioned range, the result of dyed keratin fibers will be close to natural tone. The molar ratio of 5,6-dihydroxyindole to 5,6-dihydroxyindole-2-carboxylic acid can be quantified by reverse phase HPLC (High Pressure Liquid Chromatograph, high performance liquid chromatography).

From the viewpoint of improving dyeability, the content of component (A) in the composition (1) is preferably at least 0.05% by mass, more preferably at least 0.1% by mass. Furthermore, from the viewpoint of economic efficiency, it is preferably at most 5 mass %, more preferably at most 3 mass %, further preferably at most 1.0 mass %, more preferably at most 0.8 mass %, more preferably at most 0.5 mass %, More preferably, it is 0.3 mass % or less. Also, preferably 0.05% by mass to 5% by mass, more preferably 0.05% by mass to 3% by mass, further preferably 0.1% by mass to 1.0% by mass, more preferably 0.1% by mass to 0.8% by mass, more preferably 0.1% by mass to 0.5% by mass, more preferably 0.1% by mass to 0.3% by mass.

＜Ingredient (B)＞ The composition (1) used in the step (i) contains the component (B) as an alkali agent. The alkali agent has the effect of swelling the keratin fibers to open the cuticle, allowing the dye components such as component (A) to penetrate into the inside of the keratin fibers, and has the effect of promoting the polymerization reaction of the component (A) and improving the dyeing property. As the alkali agent, any alkali agent used in general hair dyes can be used without particular limitation. As the alkaline agent, for example, ammonia; alkanolamines such as monomethanolamine, dimethanolamine or trimethanolamine, monoethanolamine, diethanolamine or triethanolamine; methylamine, dimethylamine, ethylamine, Alkylamines such as diethylamine, N-methylethylamine, propylamine, and butylamine; aralkylamines such as benzylamine; inorganic basic compounds such as sodium hydroxide and potassium hydroxide, etc., can be used One or more of these. From the viewpoint of water solubility, the carbon number of alkanolamine, alkylamine, or aralkylamine is preferably 10 or less, more preferably 8 or less. Among them, from the viewpoint of dyeability, the alkali agent is preferably one or two selected from the group consisting of ammonia, alkanolamines, alkylamines, aralkylamines, sodium hydroxide, and potassium hydroxide. The above, more preferably contain one or more kinds selected from the group consisting of ammonia and alkanolamines, further preferably contain monoalkanolamine, still more preferably contain monoethanolamine. More preferably, the component (B) which is an alkali agent is 1 type or 2 or more types selected from the group which consists of ammonia and an alkanolamine.

From the viewpoint of expressing high dyeability, the content of component (B) in the composition (1) is preferably at least 0.01% by mass, more preferably at least 0.1% by mass, further preferably at least 0.5% by mass. Furthermore, from the viewpoint of suppressing irritation, it is preferably at most 10% by mass, more preferably at most 5% by mass, and still more preferably at most 3% by mass. Moreover, it is preferable that it is 0.01 mass % - 10 mass %, it is more preferable that it is 0.1 mass % - 5 mass %, and it is still more preferable that it is 0.5 mass % - 3 mass %. Also, from the viewpoint of developing high dyeability and ensuring good combability of hair, the ratio of the content of component (B) to the content of component (A) in the composition (1) [component ( B)/component (A)] is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more, and is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less. Moreover, it is preferable that it is 2-100, it is more preferable that it is 5-50, and it is still more preferable that it is 8-30.

＜Ingredient (E)＞ It is preferable that the composition (1) used in the process (i) further contains an antioxidant as a component (E) from a viewpoint of improving the stability of a component (A). Examples of antioxidants include sulfurous acid, pyrosulfurous acid, hydrogen sulfite, sulfur dioxide, L-ascorbic acid, thioglycolic acid, L-cysteine, N-acetyl-L-cysteine, and Such salts, and such derivatives. As the salt, alkali metals such as sodium and potassium can be preferably used. Among them, when the composition (2), or the composition (2) and other acidic compositions are used after the application of the composition (1), the effect of suppressing the yellowish color tone from being dyed (hereinafter also referred to as " From the viewpoint of "yellowness suppression effect"), sulfites, pyrosulfites, bisulfites, and sulfur dioxide are preferable as the component (E). More specifically, sodium sulfite, potassium sulfite, sodium hyposulfite, potassium hyposulfite, sulfur dioxide, potassium pyrosulfite, sodium pyrosulfite, etc. are mentioned as a suitable component (E). Among these, from the viewpoint of availability in the market, component (E) is preferably sulfite and pyrosulfite, more specifically, preferably selected from sodium sulfite, potassium sulfite, sodium pyrosulfite and One or more species of the group consisting of potassium metabisulfite. Also, from the viewpoint of improving dyeability, component (E) is preferably L-ascorbic acid and its salts, ascorbic acid glucoside, and more specifically, is preferably selected from the group consisting of L-ascorbic acid, L-sodium ascorbate, and L-ascorbic acid. One or more of the group consisting of glucosides. From the viewpoint of imparting a yellowing suppressing effect and improving dyeability, component (E) preferably contains a salt selected from L-ascorbic acid, sulfurous acid, pyrosulfurous acid, bisulfite or these salts, ascorbyl glucoside and One or more of the group consisting of sulfur dioxide. From the viewpoint of imparting the yellowness suppressing effect and the stabilization of the component (A), the component (E) may contain (combined use): a first antioxidant selected from the group consisting of sulfites, pyrosulfites, bisulfites and one or more of the group consisting of sulfur dioxide; and a second antioxidant that is different from the first antioxidant. In this case, it is preferable to include one or more kinds selected from the group consisting of sulfurous acid, pyrosulfurous acid, bisulfite and their salts, and L-ascorbic acid, L-sodium ascorbate and L-ascorbic acid. - One or more of the group consisting of ascorbyl glucoside.

When the composition (1) contains the component (E), the content of the component (E) in the composition (1) is preferably at least 0.05% by mass, more preferably at least 0.1% by mass. And, it is preferably at most 10 mass %, more preferably at most 5 mass %, and still more preferably at most 2 mass %. Moreover, it is preferable that it is 0.05 mass % - 10 mass %, it is more preferable that it is 0.1 mass % - 5 mass %, and it is still more preferable that it is 0.1 mass % - 2 mass %.

＜Ingredient (F)＞ From the standpoint of improving the foamability of the composition (1) during use and making it easier to evenly apply the component (A) as a dyeing component to the keratin fibers, the composition (1) used in the step (i) is It is preferable to further contain an anionic surfactant as a component (F). When the composition (1) is a cleansing agent, the component (F) imparts a cleansing effect on keratin fibers. Furthermore, when the following cationic polymer is used in combination as an optional component, the combination of the cationic polymer and the component (F) can generate a coacervate in a system in which the composition (1) is diluted with water, so that Ingredient (A) is included in the coacervate at a high concentration, and it is adsorbed on the surface of keratin fibers to achieve cleaning effect and high dyeability at the same time.

As the anionic surfactant, for example, alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, olefin sulfonate, alkane sulfonate, saturated or unsaturated Fatty acid salts, alkyl or vinyl ether carboxylates, α-sulfo fatty acid salts, N-acyl amino acid salts, phosphoric acid monoesters or diesters, sulfosuccinates, etc., one or the other can be used Two or more. As the counter ion of the anionic group of the anionic surfactant, for example: alkali metal ions such as sodium ions and potassium ions; alkaline earth metal ions such as calcium ions and magnesium ions; ammonium ions; Alkanolamines of the alkanol group of 3 (such as monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). Among them, from the standpoint of at least one of good foaming properties, easy cleaning properties, and dyeing properties when the composition (1) is a detergent, it is preferable that the component (F) is selected from the group consisting of alkyl ether sulfuric acid One or more of the group consisting of salt, N-acyl amino acid salt, and alkyl ether carboxylate, more preferably selected from the group consisting of alkyl ether sulfate and alkyl ether carboxylate 1 or more of the group. As said alkyl ether sulfate, a polyoxyethylene alkyl ether sulfate etc. are mentioned, As an alkyl ether carboxylate, a polyoxyethylene alkyl ether acetate etc. are mentioned. Moreover, cocoacyl glutamate etc. are mentioned as said N-acyl amino acid salt.

When the composition (1) contains the component (F), the content of the component (F) in the composition (1) is preferably 0.1% by mass or more from the viewpoint of good foamability and dyeability, and more preferably Preferably at least 0.5% by mass, more preferably at least 1% by mass, more preferably at most 40% by mass, more preferably at most 30% by mass, further preferably at most 20% by mass, more preferably at most 17% by mass. Moreover, it is preferably 0.1 mass % - 40 mass %, More preferably, it is 0.5 mass % - 30 mass %, More preferably, it is 1 mass % - 20 mass %, More preferably, it is 1 mass % - 17 mass %. Especially when the composition (1) is a cleaning agent, from the standpoint of at least one of good foamability, ease of cleaning and dyeability, the content of the component (F) in the composition (1) is higher than It is preferably at least 3% by mass, more preferably at least 5% by mass, and still more preferably at least 8% by mass. Also, from the viewpoint of improving dyeability and suppressing damage to keratin fibers, the content of component (F) in the composition (1) is preferably at most 40% by mass, more preferably at most 30% by mass, and even more preferably It is 20 mass % or less, More preferably, it is 17 mass % or less. Moreover, it is preferably 3 mass % - 40 mass %, More preferably, it is 5 mass % - 30 mass %, More preferably, it is 8 mass % - 20 mass %, More preferably, it is 8 mass % - 17 mass %.

<Other ingredients in the composition (1)> The composition (1) used in the step (i) may contain, in addition to the above-mentioned components, components generally used in compositions for keratin fibers or hair dyes as appropriate within the range that does not impair the object of the present invention. Examples of such components include buffers, amphoteric surfactants, polysiloxanes, aromatic alcohols, dyes other than component (A), cationic polymers, polymers other than cationic polymers, non- Ionic surfactants, oil agents, anti-dandruff agents, vitamin agents, fungicides, anti-inflammatory agents, preservatives, chelating agents, humectants, pearlescent agents, ceramides, fragrances, ultraviolet absorbers, aqueous media, etc. . Among these, it is preferable to contain one or two or more kinds selected from the group consisting of buffers, amphoteric surfactants, cationic polymers, and aqueous media.

(buffer) The composition (1) used in step (i) preferably contains a buffer. By containing the buffering agent, when the composition (1) is diluted with water at the time of use, it is also easy to maintain the optimum pH range for making component (A) exhibit higher dyeability. The buffer is not particularly limited as long as it has a pH buffering effect, but is preferably a buffer that reacts with oxygen in the air under alkaline conditions due to the component (A) that is a precursor of melanin, It is easy to convert into melanin, so the pH value of the composition (1) can be adjusted to alkaline conditions. From the above point of view, the buffering agent is preferably a buffer containing carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, or glycine, sodium tetraborate, or ammonium chloride as an alkaline component. or a buffer comprising a combination of two or more alkaline components such as sodium carbonate-sodium bicarbonate, more preferably a buffer containing carbonate, more preferably a buffer containing sodium bicarbonate.

From the viewpoint of improving pH buffering ability, the buffering agent may further contain a protonating agent as a component constituting the buffering agent. The protonating agent may be any of monobasic acid and polybasic acid, and may be any of organic acid (with a carbon number of 1 to 8, except ascorbic acid) and inorganic acid. As the protonating agent, for example, one or more selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, and citric acid, more preferably selected from the group consisting of phosphoric acid and citric acid 1 or 2 of them.

From the viewpoint of improving dyeability, the component constituting the buffer is more preferably a combination of sodium bicarbonate and one or two selected from the group consisting of phosphoric acid and citric acid.

When the composition (1) contains a buffer, the content of the buffer in the composition (1) is not particularly limited as long as the pH of the composition (1) can be adjusted to a desired range. From the viewpoint of improving the pH buffering ability of the composition (1) diluted with water, it is preferably at least 0.1% by mass, more preferably at least 1.0% by mass, still more preferably at least 1.5% by mass, especially preferably at least 1.8% by mass %above. Also, from the viewpoint of formulation stability, the content of the buffering agent in the composition (1) is preferably at most 5.0% by mass, more preferably at most 4.0% by mass, further preferably at most 3.5% by mass, more preferably at most 3.0% by mass. % by mass or less, preferably 2.5% by mass or less. Also, preferably 0.1% by mass to 5.0% by mass, more preferably 1.0% by mass to 4.0% by mass, further preferably 1.5% by mass to 3.5% by mass, more preferably 1.8% by mass to 3.0% by mass, especially preferably 1.8% by mass to 2.5% by mass. In addition, the content of a buffer means the total amount of the active ingredient of the component which comprises a buffer.

(amphoteric surfactant) The composition (1) used in step (i) may also contain an amphoteric surfactant. As the amphoteric surfactant, for example: alkyl dimethyl amino acetic acid betaine, fatty amidopropyl betaine, alkyl hydroxy sultaine, N-acylaminoethyl-N-2- Betaine-based surfactants such as hydroxyethylamino carboxylate; sultaine-based surfactants such as lauryl hydroxysultaine. Among these, betaine-based surfactants are preferred, and alimidopropyl betaine is more preferred from the viewpoint of easy affinity for keratin fibers and good foamability. Fatty amidopropyl betaine is preferably an acyl group having a carbon number of 8 to 18, and a carbon number of 10 to 16, preferably selected from lauryl amidopropyl betaine, palm kernel oil fatty acid One or more of the group consisting of aminopropyl betaine and cocoamidopropyl betaine. Also, as N-acylaminoethyl-N-2-hydroxyethylamino carboxylate, for example, N-cocoacyl-N'-carboxymethyl-N'-hydroxyethyl Ethylenediamine [also known as sodium cocoamphoacetate, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine], N-cocoacyl-N'-carboxyethyl Base-N'-Hydroxyethylethylenediamine [Sodium Cocoamphopropionate], N-Lauryl-N'-Carboxymethyl-N'-Hydroxyethylethylenediamine Sodium [Sodium Laurylamphoacetate], etc.

In the case where the composition (1) contains an amphoteric surfactant, the amphoteric interface in the composition (1) can be improved from the viewpoint of easy affinity for keratin fibers, good foaming property, and tactile sensation during rinsing. The content of the active agent is preferably at least 0.05% by mass, more preferably at least 0.10% by mass, further preferably at least 0.15% by mass, more preferably at least 0.50% by mass, more preferably at least 1.0% by mass, and more preferably at least 15% by mass. Mass % or less, More preferably, it is 12 mass % or less, More preferably, it is 10 mass % or less. Also, preferably 0.05% by mass to 15% by mass, more preferably 0.10% by mass to 12% by mass, further preferably 0.15% by mass to 10% by mass, more preferably 0.50% by mass to 10% by mass, more preferably 1.0% by mass to 10% by mass.

(cationic polymer) The composition (1) may also contain a cationic polymer. The combination of cationic polymer and the above-mentioned component (F) produces coagulation, which can make component (A) be included in the coacervate at a high concentration, and make it adsorb on the surface of keratin fibers, showing high dyeability The role. In the present invention, a cationic polymer has a cationic group, and refers to a water-soluble polymer that exhibits cationic properties as a whole. That is, among the cationic polymers, in addition to cationic polymers having only cationic groups and no anionic groups, amphoteric polymers having cationic groups and anionic groups and exhibiting cationic properties as a whole are also Included in the cationic polymer of the present invention. In addition, the above-mentioned anionic group refers to an anionic group, or a group capable of becoming an anionic group by ionization.

As the cationic polymer, for example, cationized guar gum; cationized tara gum; cationized locust bean gum; cationized polyvinyl alcohol; Cationic hydroxyalkyl cellulose such as hydroxypropyl cellulose; cationic starch; vinylpyrrolidone/N,N-dimethylaminoethyl methacrylate diethyl sulfate copolymer, N,N -Dimethylaminoethyl methacrylate diethyl sulfate/N,N-dimethylacrylamide/polyethylene glycol dimethacrylate copolymer and other quaternary dialkylaminoalkyl (Meth)acrylate polymer; Polydiallyldimethylammonium chloride, Diallyldimethylammonium chloride/acrylic acid copolymer, Diallyldimethylammonium chloride/acrylamide Copolymers, diallyldimethylammonium chloride/acrylic acid/acrylamide copolymers and other diallyl quaternary ammonium salt polymers; vinylimidazolium trichloride/vinylpyrrolidone copolymers; Vinylpyrrolidone/Alkylamino(Meth)acrylate Copolymer; Vinylpyrrolidone/Alkylamino(Meth)acrylate/Vinylcaprolactam Copolymer; Vinylpyrrolidone /(Meth)acrylamidopropyltrimethylammonium chloride copolymer; Alkylacrylamide/(meth)acrylate/Alkylaminoalkylacrylamide/polyethylene glycol (meth) Acrylic ester copolymer; adipic acid/dimethylamino hydroxypropyl ethylenetriamine copolymer, and those described in Japanese Patent Laid-Open No. 53-139734 and Japanese Patent Laid-Open No. 60-36407 One kind or two or more kinds of cationic polymers etc. can be used.

From the viewpoint of easy aggregation and high dyeability, the cationic polymer is preferably selected from cationized guar gum, cationized tara gum, cationized locust bean gum, cationized polyvinyl alcohol, cationic Hydroxyethyl cellulose, cationized hydroxypropyl cellulose, vinylpyrrolidone/N,N-dimethylaminoethyl methacrylate diethyl sulfate copolymer, N,N-dimethyl Diethyl Aminoethyl Methacrylate Sulfate/N,N-Dimethacrylamide/Polyethylene Glycol Dimethacrylate Copolymer, Polydiallyldimethylammonium Chloride, Chloride Diallyldimethylammonium/acrylic acid copolymer, diallyldimethylammonium chloride/acrylamide copolymer and diallyldimethylammonium chloride/acrylic acid/acrylamide polymer One or more of the group, more preferably selected from the group consisting of cationized guar gum, cationized tara gum, cationized polyvinyl alcohol, cationized hydroxyethyl cellulose, cationized hydroxypropyl cellulose, N,N-Dimethylaminoethyl Diethyl Methacrylate Sulfate/N,N-Dimethacrylamide/Polyethylene Glycol Dimethacrylate Copolymer, Chlorinated Polydiallyl Dimethylammonium, diallyldimethylammonium chloride/acrylic acid copolymer, diallyldimethylammonium chloride/acrylamide copolymer and diallyldimethylammonium chloride/acrylic acid/ One or more of the group consisting of acrylamide polymers, more preferably selected from cationized guar gum, cationized tara gum, cationized polyvinyl alcohol, cationized hydroxyethyl cellulose, Cationic Hydroxypropyl Cellulose, N,N-Dimethylaminoethyl Diethyl Methacrylate Sulfate/N,N-Dimethacrylamide/Polyethylene Glycol Dimethacrylate Copolymer , diallyldimethylammonium chloride/acrylic acid copolymer, and diallyldimethylammonium chloride/acrylamide copolymer, one or more of them.

When the composition (1) contains a cationic polymer, the content of the cationic polymer in the composition (1) is preferably at least 0.05% by mass, more preferably 0.1% by mass, from the viewpoint of improving dyeability or more, more preferably at least 0.2% by mass, more preferably at least 0.3% by mass. Also, from the viewpoint of improving stability and dyeability, it is preferably at most 5% by mass, more preferably at most 3% by mass, further preferably at most 1.5% by mass, more preferably at most 1.0% by mass. Moreover, it is preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass, further preferably 0.2% by mass to 1.5% by mass, and more preferably 0.3% by mass to 1.0% by mass.

(aqueous medium) Composition (1) generally contains an aqueous medium. Examples of aqueous media include: water; lower alcohols such as ethanol and isopropanol; 1,3-butanediol, glycerin, ethylene glycol, propylene glycol and other low-molecular-weight diols and triols with carbon numbers below 6, preferably for water. When the composition (1) contains an aqueous medium, the content of the aqueous medium in the composition (1) can be appropriately selected according to the dosage form of the composition (1), and is usually in the range of 1 to 95% by mass. In the case of using water as the aqueous medium, the composition (1) aggregates when it is diluted with water during use, so that the component (A) is adsorbed on the surface of the keratin fiber, and from the viewpoint of showing higher dyeability, the combination The content of water in the substance (1) is preferably at least 40% by mass, more preferably at least 50% by mass, further preferably at least 60% by mass, more preferably at least 70% by mass, and more preferably at least 95% by mass Below, more preferably below 90% by mass. Moreover, it is preferably 40 mass % - 95 mass %, More preferably, it is 50 mass % - 95 mass %, More preferably, it is 60 mass % - 90 mass %, More preferably, it is 70 mass % - 90 mass %.

The production method of composition (1) is not specifically limited. For example, it can manufacture by the method of preparing components (A), (B) and other components used as needed by the method described in an Example, and mixing using a well-known stirring apparatus etc..

(step (ii)) The step (ii) is performed after the step (i), and the composition (2) containing the following components (C) and (D) and having a pH value of 3.5 or more and less than 8.0 is applied to keratin fibers. (C) Cationic surfactant (D) higher alcohol In the step (ii), the component (C) which is a cationic surfactant and the component (D) which are higher alcohols are supplied to keratin fiber. By supplying the component (C) and the component (D), it is possible to impart a smooth touch or easy spreadability after drying, and to ensure good combability. Also, the composition (2) containing the above-mentioned component (C) and component (D) and having a specific pH value does not affect the dyeability of the composition (1) applied to the keratin fiber in the above-mentioned step (i). To have greater influence, and suppress the keratin fibers from being yellowish when repeating step (i) to gradually dye the keratin fibers.

In step (ii), from the viewpoint of usability, when the mass of keratin fibers is set as 1, the amount of composition (2) applied to keratin fibers is preferably 0.01 to 2, more preferably 0.05-1.

After step (ii), it is preferred to have the following steps. [1] When the composition (2) is used in a rinse-off form ・Step (ii-1): A step of rinsing the composition (2) on the keratin fibers with water After step (ii), step (ii-1) can be carried out immediately, or step (ii-1) can be carried out after standing. In the case of placing, the standing time is preferably more than 5 seconds, more preferably more than 30 seconds, more preferably more than 1 minute, and preferably less than 20 minutes, more preferably less than 15 minutes, and more preferably less than 1 minute. It is preferably less than 10 minutes. In the step (ii-1), from the viewpoint of efficiently rinsing the composition (2), the temperature of the water for rinsing is preferably 0°C or higher, more preferably 5°C or higher, further preferably 10°C or higher, Moreover, it is preferably 45°C or lower, more preferably 40°C or lower. Moreover, it is preferably 0°C to 45°C, more preferably 5°C to 40°C, and still more preferably 10°C to 40°C. ・Step (ii-2): A step of drying keratin fibers After performing step (ii-1), it is preferable to perform a step of drying keratin fibers (step (ii-2)). The keratin fibers can be completely dried (that is, specifically, when the quality of the keratin fibers is set to 1, the moisture content in the keratin fibers is reduced to 0.01 or less), or the keratin fibers can be twisted to remove the remaining Moisture is supplied to step (i) again under the condition of keeping the wet state. Moreover, after process (ii-2), compositions other than composition (1) and composition (2) can also be arbitrarily applied to keratin fiber.

[2] When the composition (2) is used in a leave-on form ・Step (ii-2): A step of drying keratin fibers It is preferable to perform a step of drying the keratin fibers (step (ii-2)) after applying the composition (2) to the keratin fibers in the step (ii). In this case, it is more preferable to completely dry the keratin fibers from the viewpoint of fixing the composition (2) to the keratin fibers. Moreover, after process (ii-2), compositions other than composition (1) and composition (2) can also be arbitrarily applied to keratin fiber.

＜Composition (2)＞ The composition (2) used in step (ii) is not particularly limited as long as it contains component (C) and component (D) and has a specific pH value, and is preferably a composition for keratin fibers, such as Examples include detergents such as shampoos, conditioners, conditioners, conditioners (including non-rinsing types), styling agents, and hair restorers used in daily hair care. Among them, the composition (2) is preferably a conditioner, a conditioner, and a care agent from the viewpoint of maintaining the dyeability of keratin fibers treated with the composition (1) and ensuring good combability. , a styling agent or a hair growth agent, more preferably a conditioner, conditioner or care agent. The dosage form of the composition (2) is not particularly limited, for example, it can be made into any dosage form such as liquid, foam, ointment, cream, solid or powder. From the viewpoint of spreadability to keratin fibers, it is preferably in the form of liquid, paste or cream.

The composition (2) used in the step (ii) contains the following components (C) and (D), and has a pH of 3.5 or more and less than 8.0. When the pH of the composition (2) is within the above-mentioned range, the reduction of dyeability is suppressed, the yellowness in the color tone after dyeing is suppressed, and the effect of ensuring good combability can be obtained. From the viewpoint of suppressing the reduction of dyeability and imparting the yellowness suppressing effect, the pH of the composition (2) is preferably at least 4.0, more preferably at least 4.2, still more preferably at least 4.3, more preferably at least 4.8, and even more preferably at least 4.8. Better than 5.0. Moreover, from the viewpoint of suppressing damage to keratin fibers and ensuring good combability, it is preferably at most 7.5, more preferably at most 7.3, and still more preferably at most 7.1. Moreover, it is preferably 4.0-7.5, more preferably 4.2-7.5, still more preferably 4.3-7.3, more preferably 4.8-7.3, still more preferably 5.0-7.3, still more preferably 5.0-7.1. The said pH value is the measured value at 25 degreeC, Specifically, it can measure by the method described in an Example.

＜Ingredient (C)＞ The composition (2) used in the process (ii) contains the component (C) which is a cationic surfactant. As the cationic surfactant of component (C), for example, (i) alkyltrimethylammonium salt, (ii) alkoxyalkyltrimethylammonium salt, (iii) dialkyldimethylammonium salt (iv) alkyl dimethyl amine and its salt, (v) alkoxy alkyl dimethyl amine and its salt, (vi) alkyl amido amine and its salt, etc.

(i) Alkyltrimethylammonium salt As an alkyltrimethylammonium salt, what is represented by following General formula (2) is mentioned, for example. R ¹³ -N ⁺ (CH ₃ ) ₃ An ^- (2) [In the formula, R ¹³ represents an alkyl group with 12 to 22 carbons, An ^- represents halide ions such as chloride ion and bromide ion; methylsulfate ion, ethylsulfate ion, methylphosphate ion, ethylphosphate ion, methylcarbonate ion, etc.]

Specifically, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyltrimethylammonium methylsulfate, etc. .

(ii) Alkoxyalkyltrimethylammonium salt As an alkoxyalkyltrimethylammonium salt, what is represented by following General formula (3), for example is mentioned. R ¹⁴ -OR ¹⁵ -N ⁺ (CH ₃ ) ₃ An ^- (3) [In the formula, R ¹⁴ represents an alkyl group with 12 to 22 carbons, R ¹⁵ represents an ethyl or propyl group that may be substituted by a hydroxyl group, An ^- represents halide ions such as chloride ion, bromide ion; methylsulfate ion, ethylsulfate ion, methylphosphate ion, ethylphosphate ion, methylcarbonate ion, etc.]

Specifically, stearoxypropyltrimethylammonium chloride, stearyloxyethyltrimethylammonium chloride, stearoxyhydroxypropyltrimethylammonium chloride, and the like may, for example, be mentioned.

(iii) Dialkyldimethylammonium salt As a dialkyldimethylammonium salt, what is represented by following General formula (4) is mentioned, for example. (R ¹⁶ ) ₂ N ⁺ (CH ₃ ) ₂ An ^- (4) [wherein, R ¹⁶ independently represents an alkyl group with 12 to 22 carbon atoms, and An ^- represents halide ions such as chloride ion and bromide ion. ; Methyl sulfate ion, ethyl sulfate ion, methyl phosphate ion, ethyl phosphate ion, methyl carbonate ion, etc.]

Specifically, distearyldimethylammonium chloride and the like may, for example, be mentioned.

(iv) Alkyldimethylamine and its salt Alkyldimethylamine reacts with acid to form a quaternary ammonium salt, which becomes a surfactant. Therefore, here, alkyldimethylamine and its salt are defined as a cationic surfactant. In addition, the content is converted by the mass of an alkyldimethylamine. As an alkyldimethylamine and its salt, what is represented by following General formula (5), and its salt are mentioned, for example. R ¹⁷ -N(CH ₃ ) ₂ (5) [wherein, R ¹⁷ represents an alkyl group having 12 to 22 carbon atoms]

The salt may, for example, be a salt of an organic acid or an inorganic acid. Examples of organic acids include: monocarboxylic acids such as acetic acid and propionic acid; malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, etc. Dicarboxylic acids; Polycarboxylic acids such as polyglutamic acid; Hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, citric acid, etc.; Acidic amino acids such as glutamic acid, aspartic acid, etc. . As an inorganic acid, hydrochloric acid, sulfuric acid, phosphoric acid etc. are mentioned, for example. Among these, organic acids are preferable, dicarboxylic acids, hydroxycarboxylic acids, and acidic amino acids are preferable, and maleic acid and succinic acid are more preferable as dicarboxylic acids. As the hydroxycarboxylic acid, glycolic acid, lactic acid, and malic acid are more preferable. As the acidic amino acid, glutamic acid is more preferable.

Specific examples of alkyldimethylamine and its salts include: N,N-dimethylbehenylamine, N,N-dimethylstearylamine and their organic acid salts, preferably It is the lactate of N,N-dimethylbehenylamine, the lactate of N,N-dimethylstearylamine, etc.

(v) Alkoxyalkyldimethylamine and its salt Alkoxyalkyldimethylamine reacts with an acid to form a quaternary ammonium salt, which becomes a surfactant. Therefore, here, alkoxyalkyldimethylamine and its salt are defined as a cationic surfactant. In addition, the content is converted by the mass of alkoxyalkyl dimethylamine. As alkoxyalkyldimethylamine and its salt, what is represented by following General formula (6), and its salt are mentioned, for example. R ¹⁸ -OR ¹⁹ -N(CH ₃ ) ₂ (6) [In the formula, R ¹⁸ represents an alkyl group with 12 to 22 carbons, and R ¹⁹ represents an ethyl or propyl group that may be substituted by a hydroxyl group]

As the salt, a salt formed from an organic acid or an inorganic acid may, for example, be mentioned. As an organic acid or an inorganic acid, the organic acid or inorganic acid used for neutralization of the alkyldimethylamine represented by the said general formula (5) is mentioned.

Specific examples of alkoxyalkyldimethylamine and its salts include: N,N-dimethyl-3-hexadecyloxypropylamine, N,N-dimethyl-3-deca Octalkoxypropylamine and their organic acid salts, preferably N,N-dimethyl-3-hexadecyloxypropylamine lactate, N,N-dimethyl-3- Glycolate of octadecyloxypropylamine.

(vi) Alkylamide amines and their salts Alkylamide amines react with acids to form quaternary ammonium salts and become surfactants. Therefore, here, alkylamide amines and salts thereof are defined as cationic surfactants. In addition, the content is converted by the mass of alkyl amido amine. Examples of the alkylamide amine and its salt include those represented by the following general formula (7) and their salts. R ²⁰ -CONH-(CH ₂ ) _t -N(CH ₃ ) ₂ (7) [In the formula, R ²⁰ represents an alkyl group with 12-22 carbons, and t represents the number of 2-4]

Among these, R ²⁰ is preferably an alkyl group having 14 to 22 carbon atoms. As the salt, a salt formed from an organic acid or an inorganic acid may, for example, be mentioned. As an organic acid or an inorganic acid, the organic acid or inorganic acid used for neutralization of the alkyldimethylamine represented by the said general formula (5) is mentioned.

As specific alkylamide amines and salts thereof, N-(3-(dimethylamino)propyl)behenylamine and its salts, N-(3-(dimethylamine) base) propyl) stearamide and salts thereof.

Among these, from the viewpoint of improving combability, (i) alkyltrimethylammonium salt, (ii) alkoxyalkyltrimethylammonium salt, (v) alkoxyalkyldimethylammonium salt, (v) alkoxyalkyldimethylammonium salt, Methylamine and its salts, (vi) alkyl amidoamines and their salts, (i) alkyltrimethylammonium salts, (v) alkoxyalkyldimethylamines and their salts, (vi) alkane Amino amines and their salts. Further preferred are cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, N,N-dimethyl-3-hexadecyloxypropylamine and its salts, N,N- Dimethyl-3-octadecyloxypropylamine and its salts, N-(3-(dimethylamino)propyl)behenylamine and its salts, N-(3-(dimethyl (amino)propyl)stearylamide and salts thereof.

The cationic surfactant of a component (C) can be used individually by 1 type or in combination of 2 or more types. From the viewpoint of ensuring good combability, the content of component (C) in the composition (2) is preferably at least 0.01% by mass, more preferably at least 0.1% by mass, still more preferably at least 0.5% by mass, even more preferably It is 1.0 mass % or more, and, Preferably it is 20 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 5 mass % or less, More preferably, it is 4 mass % or less. Moreover, it is preferably 0.01 mass % - 20 mass %, more preferably 0.1 mass % - 10 mass %, further preferably 0.5 mass % - 5 mass %, more preferably 1.0 mass % - 4 mass %.

＜Ingredient (D)＞ The composition (2) used in the step (ii) contains the component (D) as a higher alcohol. The higher alcohol as component (D) can be any aliphatic alcohol of straight chain or branched chain, saturated or unsaturated, and its carbon number is preferably 10 or more, more preferably 14 or more, and still more preferably 16 or more , and, preferably 22 or less, more preferably 20 or less, further preferably 18 or less. Specifically, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, hexyldecanol, isostearyl alcohol, oleyl alcohol, 2-octyldodecanol, etc. are mentioned. Among these, stearyl alcohol, cetyl alcohol, and myristyl alcohol are preferable. These higher alcohols may be used alone or in combination of two or more.

From the viewpoint of ensuring good combability, the content of component (D) in (2) in the composition is preferably at least 0.1% by mass, more preferably at least 1% by mass, still more preferably at least 1.5% by mass, even more preferably It is at least 2% by mass, and is preferably at most 20% by mass, more preferably at most 10% by mass, further preferably at most 8% by mass. Also, it is preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass, further preferably 1.5% by mass to 8% by mass, and more preferably 2% by mass to 8% by mass. From the viewpoint of ensuring the stability and good combability of the composition (2), the ratio of the content of the component (D) in the composition (2) to the content of the component (C) [component (D)/component ( C)] is preferably 0.2 or more, more preferably 0.3 or more, still more preferably 0.4 or more, and is preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.0 or less. Moreover, it is preferable that it is 0.2-2.0, it is more preferable that it is 0.3-1.5, and it is still more preferable that it is 0.4-1.0.

<Other ingredients in composition (2)> The composition (2) used in the process (ii) may suitably contain the component normally used in the composition for keratin fibers other than the said component in the range which does not impair the object of this invention. As this component, for example, anionic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxanes, polyhydric alcohols, acids, alkali agents, aromatic alcohols, components other than (A) Coloring agent, polymer, oil agent, anti-dandruff agent, vitamin agent, fungicide, anti-inflammatory agent, preservative, chelating agent, humectant, pearlescent agent, ceramides, fragrance, ultraviolet absorber, antioxidant, aqueous media, etc. Among them, it is preferable to contain one or two or more kinds selected from the group consisting of polysiloxanes, polyols, acids, alkali agents, preservatives, and aqueous media.

(polysiloxane) From the viewpoint of smoothness during drying, it is preferable that the composition (2) used in the step (ii) contains polysiloxanes. Examples of such polysiloxanes include those shown below.

(1) Dimethicone represented by following general formula (8), for example. (CH ₃ ) ₃ SiO-[(CH ₃ ) ₂ SiO] _b -Si(CH ₃ ) ₃ (8) [in formula (8), b represents a number from 3 to 20000]

(2) Amino-modified polysiloxane Amino-modified polysiloxane can also be in any form such as oil, emulsion, low-viscosity polysiloxane, or a solution diluted with liquid paraffin. As the amino-modified polysiloxane, preferably Amodimethicone, Aminoethylaminopropyl Dimethicone, or Aminopropyl Dimethicone The name of Aminopropyl Dimethicone is recorded in the 10th edition of INCI (International Nomenclature Cosmetic Ingredient, International Cosmetic Raw Material Nomenclature) Dictionary (USA, International Cosmetic Raw Material Nomenclature Dictionary and Handbook). The amine-modified polysiloxane is preferably used as an aqueous emulsion. Commercially available products of amodimethicone include: "DOWSIL SM8904", "DOWSIL CB-1002" (above Manufactured by Dow Toray Co., Ltd.), "KT-0032", "XF42-B8922" (manufactured by Momentive Advanced Materials Co., Ltd.), etc.

(3) Other silicones In addition to the above, polyether-modified polysiloxane, methylphenyl polysiloxane, fatty acid-modified polysiloxane, alcohol-modified polysiloxane, alkoxy-modified polysiloxane, epoxy Oxygen-modified polysiloxane, fluorine-modified polysiloxane, cyclic polysiloxane, alkyl-modified polysiloxane, etc.

Polysiloxanes can be used alone or in combination of two or more. When the composition (2) contains polysiloxanes, the content of the polysiloxanes in the composition (2) is preferably at least 0.01% by mass, more preferably 0.015% from the viewpoint of ensuring good combability. Mass % or more, More preferably, it is 0.02 mass % or more, Moreover, Preferably it is 10 mass % or less, More preferably, it is 6 mass % or less, More preferably, it is 3 mass % or less. Moreover, it is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 6% by mass, further preferably 0.015% by mass to 6% by mass, and more preferably 0.02% by mass to 3% by mass.

(Polyol) Examples of polyols include those having 2 to 20 carbon atoms, specifically, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and 1,2-butanediol , 1,3-butanediol, hexanediol and other alkylene glycols; glycerin such as glycerin, diglycerin and polyglycerin; sugar alcohols such as xylitol, mannitol, galactitol and sorbitol ; In addition to pentaerythritol, pentylene glycol, etc., especially preferably one or two or more selected from the group consisting of propylene glycol, dipropylene glycol, 1,3-butanediol, glycerin, and dipropylene glycol. The polyhydric alcohol can be used individually or in combination of 2 or more types. When polyhydric alcohol is used, the content of polyhydric alcohol in the composition (2) is preferably 0.1% by mass or more, more preferably 0.5% by mass, from the aspects of touch, spreadability, or usability during and after use. % or more, and preferably at most 20% by mass, more preferably at most 8% by mass. Moreover, it is preferable that it is 0.1 mass % - 20 mass %, and it is more preferable that it is 0.5 mass % - 8 mass %.

(acid) Composition (2) may contain an acid from the viewpoint of repairing damaged keratin fibers. As the acid, it is preferable to use a weak acid from the viewpoint of easiness of pH adjustment. Specific examples of weak acids include citric acid, glycolic acid, succinic acid, tartaric acid, lactic acid, acetic acid, fumaric acid, malic acid, levulinic acid, butyric acid, valeric acid, oxalic acid, and maleic acid. Diacids, carboxylic acids such as mandelic acid, phosphoric acid, etc. These acids are further preferably combined with these potassium salts and sodium salts to make the system have a buffering capacity. Among these, carboxylic acid is preferred, and lactic acid is more preferred from the viewpoint of odor or irritation. When the composition (2) further contains an acid, the content of the acid in the composition (2) is preferably 3.0% by mass or less, more preferably It is 2.5 mass % or less, More preferably, it is 1.5 mass % or less, More preferably, it is 1.0 mass % or less, More preferably, it is 0.6 mass % or less. However, it is preferable that composition (2) does not contain an acid substantially, and it is more preferable that the content of the acid in composition (2) is 0 mass % from a viewpoint of providing a yellowishness suppressing effect.

Also, when the composition (2) further contains an acid, the content of the acid in the composition (2) is higher than that in the composition (1) from the viewpoint of ensuring good combability and the viewpoint of imparting a yellowishness suppressing effect. The ratio [(acid)/component (A)] of the content of the component (A) is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less, still more preferably 5 or less.

(alkaline agent) From the viewpoint of adjusting the pH of the preparation, the composition (2) may contain an alkali agent. Examples of the alkaline agent include ammonia; alkanolamines such as monomethanolamine, dimethanolamine, or trimethanolamine, monoethanolamine, diethanolamine, or triethanolamine; methylamine, dimethylamine, ethylamine, and diethylamine. , N-methylethylamine, propylamine, butylamine and other alkylamines; benzylamine and other aralkylamines; sodium hydroxide, potassium hydroxide and other inorganic basic compounds, etc., one or more of these can be used . From the viewpoint of water solubility, the carbon number of alkanolamine, alkylamine, or aralkylamine is preferably 10 or less, more preferably 8 or less. Among them, from the viewpoint of ease of pH adjustment, the alkali agent is preferably one selected from the group consisting of ammonia, alkanolamines, alkylamines, aralkylamines, sodium hydroxide, and potassium hydroxide. One or more kinds, more preferably one or more kinds selected from the group consisting of ammonia and alkanolamines, more preferably monoalkanolamines, still more preferably monoethanolamines.

When the composition (2) contains an alkali agent, from the viewpoint of formula stability, the content of the alkali agent in the composition (2) is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably Preferably, it is 0.5% by mass or less.

(preservative) Composition (2) may contain a preservative. As this preservative, for example, methyl p-hydroxybenzoate (methyl p-hydroxybenzoate), isopropylmethylphenol, phenoxyethanol, dehydroacetic acid, salts thereof, and the like may be mentioned. When the composition (2) contains a preservative, the content of the preservative in the composition (2) is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, and preferably at most 5% by mass, More preferably, it is 2 mass % or less, More preferably, it is 1 mass % or less. Moreover, it is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 2% by mass, more preferably 0.05% by mass to 1% by mass.

(aqueous medium) Composition (2) generally contains an aqueous medium. As an aqueous medium, what was exemplified in composition (1) is mentioned, Preferably it is water. When the composition (2) contains an aqueous medium, the content of the aqueous medium in the composition (2) can be appropriately selected according to the dosage form of the composition (2), and is usually in the range of 1 to 95% by mass. In the case of using water as the aqueous medium, from the standpoint of smearability to keratin fibers, stability of the composition (2), and good combability, the content of water in the composition (2) is preferably 50 mass % or more, more preferably 60 mass % or more, further preferably 70 mass % or more, more preferably 80 mass % or more, and preferably 95 mass % or less, more preferably 90 mass % or less. Moreover, it is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 95% by mass, still more preferably 70% by mass to 90% by mass, more preferably 80% by mass to 90% by mass.

The production method of composition (2) is not specifically limited. For example, it can manufacture by the method of preparing components (C), (D) and other components used as needed by the method described in an Example, and mixing using a well-known stirring apparatus etc..

[keratin fiber dyeing method] The present invention further provides a method for dyeing keratin fibers, which sequentially comprises: a step of applying the above-mentioned composition (1) to keratin fibers; and a step of applying the above-mentioned composition (2) to keratin fibers. The step of applying the above-mentioned composition (1) to keratin fibers may be the same as the above-mentioned step (i). The step of applying the above-mentioned composition (2) to keratin fibers may be the same as the above-mentioned step (ii). Also, in the above-mentioned keratin fiber dyeing method, as in the above-mentioned keratin fiber treatment method, in the step of applying the above-mentioned composition (1) to the keratin fiber and the step of applying the above-mentioned composition (2) to the keratin fiber Between the steps, the above steps (i-1) to (i-3) may be included. In addition, in the above-mentioned keratin fiber dyeing method, in the same manner as the above-mentioned keratin fiber treatment method, after the step of applying the above-mentioned composition (2) to the keratin fiber, in the case of using the composition (2) in a rinsed form In this case, the above-mentioned steps (ii-1) to (ii-2) may be included, and when the composition (2) is used in a leave-on form, the step (ii-2) may be included.

As one embodiment of the present invention, the present invention also provides a method for dyeing keratin fibers, which has: the step of applying composition (1) to keratin fibers as a cleaning agent; and using composition (2) as an optional A step of applying one or more of the group consisting of conditioner, conditioner and care agent to keratin fibers. That is, the composition (1) as a cleansing agent is applied to keratin fibers, foamed to wash keratin fibers, and then rinsed with water. Then, apply the above-mentioned composition (2) as one or more than two kinds selected from the group consisting of conditioner, conditioner and care agent to the keratin fiber, and leave it for a short time (1 to 5 minutes) if necessary. left and right), then rinse with water. By routinely repeating the above steps, keratin fibers can be dyed easily and in a short time, and the dyed hue can be suppressed from being yellowish.

[Composition Set for Keratin Fiber] The present invention also provides a composition set for keratin fibers comprising the following constitutions. Specifically, it is a composition set for keratin fibers comprising: a composition (1) containing the above-mentioned components (A) and (B), and having a pH value of 8.0 or more and 12.0 or less; and the composition ( 2) It contains the above-mentioned components (C) and (D), and its pH value is 3.5 or more and less than 8.0. The above-mentioned composition set for keratin fibers can be, for example, an aspect in which the composition (1) and the composition (2) are respectively accommodated in separate containers, and these containers are set as a set. As another aspect, the above-mentioned composition set for keratin fiber may be set as the following, which has one container divided into at least two sections, and is accommodated in the first section of the above-mentioned sections. There is a composition (1), and the composition (2) is accommodated in the 2nd block different from the 1st block among the said blocks.

[式(1)中，虛線表示存在或不存在π鍵，R ¹表示羥基或乙醯氧基，R ²表示氫原子或-COOR(R為氫原子、甲基或乙基)，R ³表示氫原子、乙醯基、甲基或乙基] (B)鹼劑 步驟(ii)：將含有如下成分(C)及(D)，且pH值為3.5以上且未達8.0之組合物(2)應用於角蛋白纖維之步驟 (C)陽離子性界面活性劑 (D)高級醇 ＜2＞ 如＜1＞之角蛋白纖維處理方法，其中組合物(1)之pH值為8.5～11.0，較佳為8.8～10.5，更佳為9.0～10.0。 ＜3＞ 如＜1＞或＜2＞之角蛋白纖維處理方法，其中組合物(2)之pH值為4.0～7.5，較佳為4.2～7.5，更佳為4.3～7.3，進而較佳為4.8～7.3，更佳為5.0～7.3，進而較佳為5.0～7.1。 ＜4＞ 一種角蛋白纖維處理方法，其依序具有下述步驟(i)及步驟(ii)。 步驟(i)：將含有如下成分(A)及(B)，且pH值為8.5以上且11.0以下之組合物(1)應用於角蛋白纖維之步驟 (A)通式(1)所表示之化合物或其鹽 0.05～3質量% [化8]

[式(1)中，虛線表示存在或不存在π鍵，R ¹表示羥基或乙醯氧基，R ²表示氫原子或-COOR(R為氫原子、甲基或乙基)，R ³表示氫原子、乙醯基、甲基或乙基] (B)鹼劑 0.1～5質量% 步驟(ii)：將含有如下成分(C)及(D)，且pH值為4.2以上且7.5以下之組合物(2)應用於角蛋白纖維之步驟 (C)陽離子性界面活性劑 0.1～10質量% (D)高級醇 1～10質量% ＜5＞ 一種角蛋白纖維處理方法，其依序具有下述步驟(i)及步驟(ii)。 步驟(i)：將含有如下成分(A)及(B)，且pH值為8.8以上且10.5以下之組合物(1)應用於角蛋白纖維之步驟 (A)通式(1)所表示之化合物或其鹽 0.1～1.0質量% [化9]

[式(1)中，虛線表示存在或不存在π鍵，R ¹表示羥基或乙醯氧基，R ²表示氫原子或-COOR(R為氫原子、甲基或乙基)，R ³表示氫原子、乙醯基、甲基或乙基] (B)鹼劑 0.5～3質量% 步驟(ii)：將含有如下成分(C)及(D)，且pH值為5.0以上且7.3以下之組合物(2)應用於角蛋白纖維之步驟 (C)陽離子性界面活性劑 0.5～5質量% (D)高級醇 2～8質量% ＜6＞ 如＜1＞至＜5＞中任一項所記載之角蛋白纖維處理方法，其中組合物(2)進而含有酸，且組合物(2)中之酸之含量為3.0質量%以下，較佳為2.5質量%以下，更佳為1.5質量%以下，進而較佳為1.0質量%以下，更佳為0.6質量%以下。 ＜7＞ 如＜6＞中所記載之角蛋白纖維處理方法，其中組合物(2)中之酸之含量相對於組合物(1)中之成分(A)之含量的比[(酸)/成分(A)]為30以下，較佳為20以下，更佳為15以下，進而較佳為10以下，更進而較佳為5以下。 ＜8＞ 如＜1＞至＜5＞中任一項所記載之角蛋白纖維處理方法，其中組合物(2)實質上不含酸。 ＜9＞ 如＜1＞至＜8＞中任一項所記載之角蛋白纖維處理方法，其中成分(B)係選自由氨及烷醇胺所組成之群中之1種或2種以上。 ＜10＞ 如＜1＞至＜9＞中任一項所記載之角蛋白纖維處理方法，其中組合物(1)進而含有抗氧化劑作為成分(E)。 ＜11＞ 如＜10＞中所記載之角蛋白纖維處理方法，其中成分(E)含有選自由L-抗壞血酸、亞硫酸、焦亞硫酸、亞硫酸氫或該等之鹽、抗壞血酸葡糖苷及二氧化硫所組成之群中之1種或2種以上。 ＜12＞ 如＜1＞至＜11＞中任一項所記載之角蛋白纖維處理方法，其中組合物(1)進而含有陰離子性界面活性劑作為成分(F)。 ＜13＞ 如＜1＞至＜12＞中任一項所記載之角蛋白纖維處理方法，其中組合物(1)為洗淨劑。 ＜14＞ 如＜1＞至＜13＞中任一項所記載之角蛋白纖維處理方法，其中組合物(2)為潤絲劑、調理劑或護理劑。 ＜15＞ 如＜1＞至＜14＞中任一項所記載之角蛋白纖維處理方法，其於步驟(i)與步驟(ii)之間，具有使用水沖洗角蛋白纖維之步驟。 ＜16＞ 如＜15＞中所記載之角蛋白纖維處理方法，其中於上述沖洗之步驟後於保持濕潤狀態之情況下供於步驟(ii)。 ＜17＞ 如＜1＞至＜14＞中任一項所記載之角蛋白纖維處理方法，其於步驟(i)與步驟(ii)之間，具有下述步驟(i-1)、步驟(i-2)及步驟(i-3)之步驟。 步驟(i-1)：於應用組合物(1)後放置之步驟；使組合物(1)起泡之步驟；及使組合物(1)起泡，其後放置之步驟中之任一步驟 步驟(i-2)：使用水沖洗角蛋白纖維上之組合物(1)之步驟 步驟(i-3)：使角蛋白纖維乾燥之步驟 ＜18＞ 如＜17＞中所記載之角蛋白纖維處理方法，其中於保持濕潤狀態之情況下供於步驟(ii)。 ＜19＞ 如＜1＞至＜17＞中任一項所記載之角蛋白纖維處理方法，其於步驟(ii)後，具有使用水沖洗角蛋白纖維上之組合物(2)之步驟(ii-1)。 ＜20＞ 如＜19＞中所記載之角蛋白纖維處理方法，其於進行步驟(ii-1)後，具有使角蛋白纖維乾燥之步驟(步驟(ii-2))。 ＜21＞ 如＜1＞至＜18＞中任一項所記載之角蛋白纖維處理方法，其於步驟(ii)後，具有使角蛋白纖維乾燥之步驟(ii-2)。 ＜22＞ 如＜1＞至＜21＞中任一項所記載之角蛋白纖維處理方法，其為角蛋白纖維染色方法。 ＜23＞ 一種角蛋白纖維用組合物套組，其具備：組合物(1)，其含有如下成分(A)及(B)，且pH值為8.0以上且12.0以下；及組合物(2)，其含有如下成分(C)及(D)，且pH值為3.5以上且未達8.0。 (A)通式(1)所表示之化合物或其鹽 [化10]

[式(1)中，虛線表示存在或不存在π鍵，R ¹表示羥基或乙醯氧基，R ²表示氫原子或-COOR(R為氫原子、甲基或乙基)，R ³表示氫原子、乙醯基、甲基或乙基] (B)鹼劑 (C)陽離子性界面活性劑 (D)高級醇 ＜24＞ 如＜23＞之角蛋白纖維用組合物套組，其中組合物(1)之pH值為8.5～11.0，較佳為8.8～10.5，更佳為9.0～10.0。 ＜25＞ 如＜23＞或＜24＞之角蛋白纖維用組合物套組，其中組合物(2)之pH值為4.0～7.5，較佳為4.2～7.5，更佳為4.3～7.3，進而較佳為4.8～7.3，更佳為5.0～7.3，進而較佳為5.0～7.1。 ＜26＞ 一種角蛋白纖維用組合物套組，其具備：組合物(1)，其含有如下成分(A)及(B)，且pH值為8.5以上且11.0以下；及組合物(2)，其含有如下成分(C)及(D)，且pH值為4.2以上且7.5以下。 (A)通式(1)所表示之化合物或其鹽 0.05～3質量% [化11]

[式(1)中，虛線表示存在或不存在π鍵，R ¹表示羥基或乙醯氧基，R ²表示氫原子或-COOR(R為氫原子、甲基或乙基)，R ³表示氫原子、乙醯基、甲基或乙基] (B)鹼劑 0.1～5質量% (C)陽離子性界面活性劑 0.1～10質量% (D)高級醇 1～10質量% ＜27＞ 一種角蛋白纖維用組合物套組，其具備：組合物(1)，其含有如下成分(A)及(B)，且pH值為8.8以上且10.5以下；及組合物(2)，其含有如下成分(C)及(D)，且pH值為5.0以上且7.3以下。 (A)通式(1)所表示之化合物或其鹽 0.1～1.0質量 [化12]

[式(1)中，虛線表示存在或不存在π鍵，R ¹表示羥基或乙醯氧基，R ²表示氫原子或-COOR(R為氫原子、甲基或乙基)，R ³表示氫原子、乙醯基、甲基或乙基] (B)鹼劑 0.5～3質量% (C)陽離子性界面活性劑 0.5～5質量% (D)高級醇 2～8質量% ＜28＞ 如＜23＞至＜27＞中任一項所記載之角蛋白纖維處理方法，其中組合物(2)進而含有酸，酸於組合物(2)中為3.0質量%以下，較佳為2.5質量%以下，更佳為1.5質量%以下，進而較佳為1.0質量%以下，更佳為0.6質量%以下。 ＜29＞ 如＜28＞中所記載之角蛋白纖維處理方法，其中組合物(2)中之酸之含量相對於組合物(1)中之成分(A)之含量的比[(酸)/成分(A)]為30以下，較佳為20以下，更佳為15以下，進而較佳為10以下，更進而較佳為5以下。 ＜30＞ 如＜23＞至＜27＞中任一項所記載之角蛋白纖維處理方法，其中組合物(2)實質上不含酸。 [實施例] Regarding the above-mentioned embodiment, the present invention discloses a method for treating keratin fibers, a composition set for keratin fibers, and a method for dyeing keratin fibers. <1> A method for treating keratin fibers comprising the following step (i) and step (ii) in this order. Step (i): Applying the composition (1) containing the following components (A) and (B) and having a pH value of not less than 8.0 and not more than 12.0 to keratin fibers (A) represented by general formula (1) Compound or its salt [Chem. 7]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl group, methyl group or ethyl group] (B) alkaline agent step (ii): the composition (2 ) Step of applying keratin fiber (C) cationic surfactant (D) higher alcohol <2> such as <1> to the keratin fiber treatment method, wherein the pH value of the composition (1) is 8.5-11.0, which is higher than Preferably it is 8.8-10.5, more preferably 9.0-10.0. <3> The method for treating keratin fibers as described in <1> or <2>, wherein the pH value of the composition (2) is 4.0-7.5, preferably 4.2-7.5, more preferably 4.3-7.3, and still more preferably 4.8 to 7.3, more preferably 5.0 to 7.3, still more preferably 5.0 to 7.1. <4> A method for treating keratin fibers comprising the following step (i) and step (ii) in this order. Step (i): Applying the composition (1) containing the following components (A) and (B) and having a pH value of not less than 8.5 and not more than 11.0 to keratin fibers (A) represented by general formula (1) Compound or its salt 0.05 to 3% by mass [Chem. 8]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl group, methyl group or ethyl group] (B) Alkaline agent 0.1-5% by mass Step (ii): Prepare the following components (C) and (D) and have a pH value of 4.2 or more and 7.5 or less The step of applying the composition (2) to keratin fibers (C) 0.1-10% by mass of cationic surfactant (D) 1-10% by mass of higher alcohol <5> A method for treating keratin fibers comprising the following steps in order Describe step (i) and step (ii). Step (i): Applying the composition (1) containing the following ingredients (A) and (B) and having a pH value of not less than 8.8 and not more than 10.5 to keratin fibers (A) represented by general formula (1) Compound or its salt 0.1 to 1.0% by mass [Chemical 9]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl group, methyl group or ethyl group] (B) Alkaline agent 0.5-3% by mass Step (ii): Prepare the following components (C) and (D), and the pH value is not less than 5.0 and not more than 7.3 Composition (2) Step of applying the composition to keratin fibers (C) Cationic surfactant 0.5-5% by mass (D) Higher alcohol 2-8% by mass <6> Such as any one of <1> to <5> The described method for treating keratin fibers, wherein the composition (2) further contains an acid, and the content of the acid in the composition (2) is 3.0% by mass or less, preferably 2.5% by mass or less, more preferably 1.5% by mass or less, more preferably 1.0 mass % or less, more preferably 0.6 mass % or less. <7> The method for treating keratin fibers as described in <6>, wherein the ratio of the content of the acid in the composition (2) to the content of the component (A) in the composition (1) [(acid)/ Component (A)] is 30 or less, preferably 20 or less, more preferably 15 or less, further preferably 10 or less, still more preferably 5 or less. <8> The method for treating keratin fibers according to any one of <1> to <5>, wherein the composition (2) does not substantially contain an acid. <9> The method for treating keratin fibers according to any one of <1> to <8>, wherein the component (B) is one or two or more selected from the group consisting of ammonia and alkanolamines. <10> The method for treating keratin fibers as described in any one of <1> to <9>, wherein the composition (1) further contains an antioxidant as a component (E). <11> The method for treating keratin fibers as described in <10>, wherein the component (E) contains L-ascorbic acid, sulfurous acid, pyrosulfurous acid, bisulfite or salts thereof, ascorbyl glucoside and sulfur dioxide One or more than two types in the group formed. <12> The method for treating keratin fibers as described in any one of <1> to <11>, wherein the composition (1) further contains an anionic surfactant as a component (F). <13> The method for treating keratin fibers according to any one of <1> to <12>, wherein the composition (1) is a cleaning agent. <14> The method for treating keratin fibers according to any one of <1> to <13>, wherein the composition (2) is a conditioner, conditioner or care agent. <15> The method for treating keratin fibers according to any one of <1> to <14>, which has a step of rinsing keratin fibers with water between step (i) and step (ii). <16> The method for treating keratin fibers as described in <15>, which is subjected to step (ii) while maintaining a wet state after the step of rinsing. <17> The method for treating keratin fibers according to any one of <1> to <14>, which includes the following step (i-1), step ( i-2) and step (i-3). Step (i-1): a step of standing after applying the composition (1); a step of foaming the composition (1); and a step of foaming the composition (1) and then standing Step (i-2): Step of rinsing composition (1) on keratin fibers with water Step (i-3): Step of drying keratin fibers <18> Keratin fibers as described in <17> A processing method, wherein it is provided in step (ii) while maintaining a wet state. <19> The method for treating keratin fibers according to any one of <1> to <17>, which has the step (ii) of rinsing the composition (2) on the keratin fibers with water after the step (ii) -1). <20> The keratin fiber processing method as described in <19> which has the process (process (ii-2)) of drying a keratin fiber after carrying out a process (ii-1). <21> The method for treating keratin fibers according to any one of <1> to <18>, which has a step (ii-2) of drying keratin fibers after step (ii). <22> The method for treating keratin fibers according to any one of <1> to <21>, which is a method for dyeing keratin fibers. <23> A composition set for keratin fibers comprising: a composition (1) containing the following components (A) and (B), and having a pH of 8.0 to 12.0; and a composition (2) , which contains the following components (C) and (D), and has a pH of 3.5 or more and less than 8.0. (A) Compound represented by general formula (1) or salt thereof [Chem. 10]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl group, methyl group or ethyl group] (B) Alkaline agent (C) Cationic surfactant (D) Higher alcohol <24> Such as <23> Composition set for keratin fibers, wherein the combination The pH value of the substance (1) is 8.5-11.0, preferably 8.8-10.5, more preferably 9.0-10.0. <25> The composition set for keratin fiber according to <23> or <24>, wherein the pH value of the composition (2) is 4.0-7.5, preferably 4.2-7.5, more preferably 4.3-7.3, and further Preferably it is 4.8-7.3, More preferably, it is 5.0-7.3, More preferably, it is 5.0-7.1. <26> A composition set for keratin fibers comprising: a composition (1) containing the following components (A) and (B), and having a pH of 8.5 to 11.0; and a composition (2) , which contains the following components (C) and (D), and has a pH of not less than 4.2 and not more than 7.5. (A) 0.05 to 3% by mass of the compound represented by the general formula (1) or its salt [Chem. 11]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl group, methyl group or ethyl group] (B) 0.1-5% by mass of alkaline agent (C) 0.1-10% by mass of cationic surfactant (D) 1-10% by mass of higher alcohol A composition set for keratin fibers comprising: a composition (1) containing the following components (A) and (B), and having a pH of 8.8 to 10.5; and a composition (2) containing Components (C) and (D), and the pH value is not less than 5.0 and not more than 7.3. (A) Compound represented by general formula (1) or its salt 0.1 to 1.0 mass [Chem. 12]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl group, methyl group or ethyl group] (B) 0.5-3% by mass of alkaline agent (C) 0.5-5% by mass of cationic surfactant (D) 2-8% by mass of higher alcohol <28> such as The method for treating keratin fibers according to any one of <23> to <27>, wherein the composition (2) further contains an acid, and the amount of the acid in the composition (2) is 3.0% by mass or less, preferably 2.5% by mass or less, more preferably 1.5 mass % or less, further preferably 1.0 mass % or less, more preferably 0.6 mass % or less. <29> The method for treating keratin fibers as described in <28>, wherein the ratio of the content of the acid in the composition (2) to the content of the component (A) in the composition (1) [(acid)/ Component (A)] is 30 or less, preferably 20 or less, more preferably 15 or less, further preferably 10 or less, still more preferably 5 or less. <30> The method for treating keratin fibers according to any one of <23> to <27>, wherein the composition (2) does not substantially contain an acid. [Example]

Hereinafter, examples of the present invention will be described, but the present invention is not limited to the scope of the examples. In addition, in this Example, pH measurement and dyeability evaluation were performed by the following method. [pH measurement] The pH of the composition for keratin fibers at 25° C. was measured using a pH meter (F-51, manufactured by Horiba Seisakusho Co., Ltd.).

[Evaluation of dyeability] In the evaluation of dyeability, 1 g of goat hair (10 cm, manufactured by Beaulax Co., Ltd.) with an L value of 85.1 to 86.1, a value of 0.5 to 1.0, and b value of 12.2 to 13.4 was used. bundle. The composition ( 1) After making it fuse with the hair bundle for 30 seconds, perform foaming for 30 seconds, and rinse with warm water (40° C.) for 30 seconds. Next, gently wring the rinsed goat hair to remove excess water, and then immediately apply the composition (2) in a bath ratio of 1:1:0.2 (goat hair bundle: water: composition (2)), After allowing it to fuse with the hair bundle for 60 seconds, rinse with warm water (40° C.) for 30 seconds. After repeating this operation 10 times, the goat hair was dried. For the hue (L ^* , a ^* , b ^* ) of the goat hair bundle before the above-mentioned dyeing treatment and the goat hair bundle after the above-mentioned dyeing treatment, use a color difference meter (CR-400, Konica Minolta Co., Ltd.) to compare Six points were measured for each goat hair bundle to obtain an average value, and the color difference ΔE was calculated from the following formula (9) using the average value. The larger the value of ΔE, the better the dyeability is evaluated. Moreover, saturation (C ^* ) was calculated according to the following formula (10). ΔE＝[(ΔL ^* ) ² ＋(Δa ^* ) ² ＋(Δb ^* ) ² ] ^1/2 Formula (9) (Δ: the change of each hue before and after dyeing) C ^* ＝[(a ^* ) ² ＋ (b ^* ) ² ] ^1/2 formula (10)

[hue evaluation] In the color tone evaluation, whether the 5 professional sensory inspectors feel yellow to the goat hair after the dyeing treatment is sorted by the following 5 grades, and the evaluation grade with the most sensory inspectors concentrated among A~E is used as the evaluation Evaluation of target goat hair bundles. ・A: A natural gray that does not feel yellow at all ・B: Gray that hardly feels yellow ・C: A little yellow is felt, but it is an acceptable grade ・D: A lighter gray with a slight yellow feel ・E: Stronger yellow color is felt

[comb evaluation] In the evaluation of combability, a hair bundle of hair dyed by the following method was used. First, apply Blaune Cream Hair Color as a hair dye to Japanese women's black hair with a length of 10 cm and a mass of 10 g at a liquor ratio of 1:1 (hair bundle: hair dye) No. 6 (manufactured by Kao Co., Ltd.), left at 30°C for 15 minutes, and rinsed with warm water (40°C) for 30 seconds. Further, using a commercially available shampoo (Essential, manufactured by Kao Co., Ltd.), the hair bundles of the above-mentioned treated hair were washed, rinsed with warm water (40° C.), and the above-mentioned operation was repeated twice, and then air-dried. A hair bundle of dyed hair was obtained. For the hair bundles of the above-mentioned dyed hairs that were previously rinsed and wetted with warm water (40° C.) for 15 seconds, the bath ratio was 1:1:0.2 (hair bundles: water: composition (1)). Mode After applying the composition (1) and allowing it to fuse with the hair bundle for 30 seconds, foaming was performed for 30 seconds, and rinsed with warm water (40° C.) for 30 seconds. Next, twist the hair bundle after washing gently, without drying, immediately apply the composition (2) in a bath ratio of 1:1:0.2 (hair bundle: water: composition (2)), and make it blend with the hair bundle. After 60 seconds of bundle fusion, rinse with warm water (40° C.) for 30 seconds. Five professional sensory inspectors evaluate the combability of the above-mentioned treated hair bundles, and rank them in the following 6 grades, and set the evaluation grade with the most sensory inspectors' evaluations from 5 points to 0 points as the evaluation object Evaluation of the combability of hair bundles. More than 3 points are ideal. ・5 points: softness and smooth combability ・4 points: smooth combing ・3 points: Combability without dryness ・2 points: Combability with a slight sense of dryness ・1 point: Combability with a strong sense of dryness ・0 points: Hair is tangled and cannot be combed with fingers

[Preparation of composition (1A)] As composition (1), composition (1A) which is a cleaning agent was prepared as follows with the composition shown in Table 1. First, among the components shown in Table 1, components other than the 5,6-dihydroxyindole solution and L-ascorbic acid were mixed and uniformly dissolved to obtain a mixed solution. Next, in this mixed solution, L-ascorbic acid was mixed under a nitrogen atmosphere, and then a 5,6-dihydroxyindole solution was mixed to prepare a composition (1A). The formulation amounts (parts by mass) recorded in Table 1 are all wet weights.

[Preparation of composition (2A)] With the composition shown in Table 1 as composition (2), composition (2A) as a conditioner was prepared as follows. First, after adding methylparaben to purified water, it heated to 80 degreeC and dissolved it, and obtained the methylparaben aqueous solution. Next, heat distearyldimethylammonium chloride, stearyltrimethylammonium chloride, cetearyl alcohol, and propylene glycol to 80°C and mix them, and add the mixed solution to the above-mentioned methylparaben After mixing uniformly in the aqueous ester solution, the temperature was lowered to 35°C. Then mix high degree of polymerization aminoethylaminopropylmethylsiloxane-dimethylsiloxane copolymer emulsion, and then mix lactic acid and monoethanolamine to prepare a composition (2A) with a pH value of 4.2. The formulation amounts (parts by mass) recorded in Table 1 are all wet weights.

[Preparation of compositions (2B) and (2C)] Compositions (2B) and (2C) were prepared in the same procedure as composition (2A), except that the compounding amounts of lactic acid were changed to 0.85 parts by mass and 0.79 parts by mass, respectively, to prepare compositions (2B) and pH 5.3 Composition (2C) with a value of 7.1.

[Preparation of Composition (2D)] Composition (2D), except that the compounded amount of monoethanolamine was changed to 1.0 parts by mass, and the compounded amount of lactic acid was changed to 2.98 parts by mass, a composition (2D) with a pH value of 4.1 was prepared in the same procedure as composition (2A). ).

[Preparation of Composition (2E)] Composition (2E) Except not having used monoethanolamine and lactic acid, the composition (2E) whose pH was 4.9 was prepared by the procedure similar to composition (2A).

[Preparation of compositions (2F) and (2G)] Compositions (2F) and (2G) were prepared in the same procedure as composition (2A) except that the compounded amounts of lactic acid were changed to 0.75 parts by mass and 4.73 parts by mass, respectively, to prepare compositions (2F) and pH 8.2 Composition (2G) with a value of 3.1.

The prepared composition (1A) and compositions (2A)-(2G) were stored under a nitrogen atmosphere, and were collected at any time during pH measurement, dyeability evaluation, color tone evaluation, and combability evaluation. Table 1 shows the composition and pH of the composition (1A) and the compositions and pH of the compositions (2A) to (2G).

[Examples 1 to 5, Comparative Examples 1 and 2] Let the situation of using each of composition (1A) and compositions (2A) to (2E) be Examples 1 to 5, and use each of composition (1A) and compositions (2F) and (2G) The cases were set as Comparative Examples 1 and 2, and dyeability evaluation, color tone evaluation, and combability evaluation were performed. The results are shown in Table 1.

[Table 1] Table 1 Ingredient name/pH value/evaluation result Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 composition (1) Composition name (1A) (1A) (1A) (1A) (1A) (1A) (1A) Composition (parts by mass) (A) 5,6-Dihydroxyindole solution*1 15 15 15 15 15 15 15 (B) Monoethanolamine 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (E) L-Ascorbic Acid 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (F) Sodium polyoxyethylene lauryl ether sulfate*2 40 40 40 40 40 40 40 (buffer) Sodium Bicarbonate 2 2 2 2 2 2 2 Phosphoric acid*3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (aqueous medium) Purified water*4 margin margin margin margin margin margin margin Content (mass %) of component (A) in composition (1) 0.17 0.17 0.17 0.17 0.17 0.17 0.17 Content (mass %) of component (B) in composition (1) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Content (mass %) of component (E) in composition (1) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Content (mass %) of component (F) in composition (1) 11 11 11 11 11 11 11 Content of water in composition (1) (mass %) 81.6 81.6 81.6 81.6 81.6 81.6 81.6 Ratio of content of component (B) to component (A) in composition (1) [component (B)/component (A)] 8.77 8.77 8.77 8.77 8.77 8.77 8.77 pH value 9.6 9.6 9.6 9.6 9.6 9.6 9.6 composition (2) Composition (parts by mass) Composition name (2A) (2B) (2C) (2D) (2E) (2F) (2G) (C) Distearyldimethylammonium chloride*5 3.6 3.6 3.6 3.6 3.6 3.6 3.6 Stearyltrimethylammonium chloride*6 2.7 2.7 2.7 2.7 2.7 2.7 2.7 (D) cetearyl alcohol 2 2 2 2 2 2 2 (polysiloxane) Highly polymerized aminoethylaminopropylmethicone-dimethylsiloxane copolymer emulsion*7 0.05 0.05 0.05 0.05 0.05 0.05 0.05 (Polyol) Propylene Glycol 5 5 5 5 5 5 5 (preservative) Methylparaben 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (alkaline agent) Monoethanolamine 0.2 0.2 0.2 1.0 - 0.2 0.2 (acid) Lactic acid*8 1.2 0.85 0.79 2.98 - 0.75 4.73 (aqueous medium) Purified water*9 margin margin margin margin margin margin margin Content (mass %) of component (C) in composition (2) 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Content (mass %) of component (D) in composition (2) 2 2 2 2 2 2 2 Acid content (mass %) in composition (2) 1.1 0.77 0.71 2.68 - 0.68 4.25 Content of water in composition (2) (mass %) 88.1 88.5 88.5 85.7 89.4 88.5 85.0 Ratio of content of component (D) to component (C) in composition (2) [component (D)/component (C)] 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Ratio of acid content in composition (2) to component (A) in composition (1) [(acid)/component (A)] 6.4 4.5 4.2 15.7 - 3.9 24.9 pH value 4.2 5.3 7.1 4.1 4.9 8.2 3.1 Evaluation results Dyeing evaluation L ^* 63.5 57.3 60.2 68.7 58.3 60.8 78.1 a ^* 0.0 0.0 -0.2 0.2 -0.2 -0.1 -0.1 b ^* 2.2 0.8 0.4 4.5 -0.4 0.8 8.0 ∆E ^* ab 24.7 30.6 28.3 18.5 29.9 27.7 8.9 C ^* 2.2 0.8 0.6 4.5 0.5 0.8 8.0 Hue evaluation B A A C A A D. combing evaluation 4 3 3 4 3 1 4

The components in the table are shown below. Furthermore, the compounded amounts (parts by mass) of each component in the table are all wet weights. *1: 5,6-dihydroxyindole solution: a solution prepared by the method described in Japanese Patent No. 5570161 (5,6-dihydroxyindole: 1% by mass, 5,6-dihydroxyindole Indole-2-carboxylic acid: 0.14% by mass, ethanol: 20% by mass, water: remainder) *2: Sodium polyoxyethylene lauryl ether sulfate; Emal E-27C (manufactured by Kao Co., Ltd., active ingredient amount: 27.0% by mass, water: 71.7% by mass) *3: Phosphoric acid; an aqueous solution with a phosphoric acid concentration of 75% by mass *4: Purified water; the amount adjusted so that the total amount becomes 100 parts by mass *5: Distearyldimethylammonium chloride; Quartamin D86P (manufactured by Kao Co., Ltd., active ingredient amount: 75% by mass, water: remainder) *6: Stearyltrimethylammonium chloride; Quartamin 86W (manufactured by Kao Co., Ltd., active ingredient amount: 28% by mass, water: remainder) *7: Highly polymerized aminoethylaminopropylmethicone-dimethylsiloxane copolymer emulsion; Silicone KT-0032 (manufactured by Momentive Advanced Materials Japan Co., Ltd., active ingredient amount: 40 mass %, water: 49% by mass) *8: Lactic acid; 90 mass% aqueous solution of lactic acid *9: Purified water; the amount adjusted so that the total amount becomes 100 parts by mass

In this example, in the case of performing the keratin fiber treatment method of the present invention, it was evaluated whether it was dyed to a natural gray color by colorimetric value and visual evaluation. Regarding the evaluation of the colorimetric value, the larger the b ^* of the colorimetric value, the more yellow it is. However, when the chroma increases even if the value of b ^* is small, an unnatural tone different from the original achromatic gray is perceived. Therefore, in the present invention, in the colorimetric value, it is preferable that b ^* is close to 0 and the chroma is smaller.

From Table 1 we can see the following situation. As shown in Examples 1 to 5, according to the method for treating keratin fibers of the present invention, higher dyeability of being dyed to natural gray with less yellow is exhibited. Also, the dyed color after repeating washing with the composition (1) and conditioning with the composition (2) 10 times became natural gray. Furthermore, the combability of the keratin fibers after the step (i) using the composition (1) and the step (ii) using the composition (2) can be improved. From the comparison of Examples 1-3 and Comparative Example 1 with the same composition as Examples 1-3 except that the pH value of the composition (2) was set to exceed 8.0 by changing the compounding amount of lactic acid, it can be seen that if the composition (2) ) if the pH value exceeds 8.0, there is no significant difference in dyeability and the color tone is also good after repeated 10 times of washing with the composition (1) and conditioning with the composition (2), but after using the composition ( The combability of the keratin fibers after the step (i) of 1) and the step (ii) of using the composition (2) becomes poor. From the comparison of Examples 1-3 and Comparative Example 2, which has the same composition as Examples 1-3 except that the pH value of the composition (2) is set to less than 3.5 except for changing the compounding amount of lactic acid, it can be seen that if the composition (2) ) is less than 3.5, the combability of the keratin fibers after the step (i) of using the composition (1) and the step (ii) of using the composition (2) is good, but after repeated 10 times of use After washing with the composition (1) and conditioning with the composition (2), the dyeability was greatly reduced, and it turned yellow.

In this specification, formulation examples 1-6 are shown in following Table 2 as one embodiment of this invention. [Table 2] Table 2 ingredient name Recipe Example 1 Recipe Example 2 Recipe Example 3 Recipe Example 4 Recipe Example 5 Recipe Example 6 composition (1) Composition (parts by mass) (A) 5,6-Dihydroxyindole solution*11 15 15 15 15 15 - 5,6-Dihydroxyindoline hydrobromide solution*12 - - - - - 15 (B) Monoethanolamine 1.5 1.5 1.5 1.5 1.5 1.5 (E) L-Ascorbic Acid 0.2 0.2 0.2 0.2 0.2 0.2 (F) Sodium polyoxyethylene lauryl ether sulfate*13 40 40 40 40 40 40 Sodium Cocoyl Glutamate 5 - - - - - (buffer) Sodium Bicarbonate 2 2 2 2 2 2 Phosphoric acid*14 0.3 0.3 0.3 0.3 0.3 0.3 (amphoteric surfactant) Lauramide propyl betaine*15 - 10 - - - - 2-Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine*16 - - 10 - - - (nonionic surfactant) Alkyl glucosides with 8 to 16 carbons - - - 5 - - (cationic polymer) O-[2-Hydroxy-3-(trimethyl/lauryldimethylammonio)propyl]hydroxyethylcellulose chloride*17 0.3 0.3 0.3 0.3 - - O-[2-Hydroxy-3-(trimethylammonio)propyl]guar gum chloride*18 - - - - 0.3 0.3 Dimethyl diallyl ammonium chloride-acrylic acid copolymer liquid*19 0.5 0.5 0.5 0.5 0.5 0.5 (aqueous medium) Purified water*20 margin margin margin margin margin margin Content (mass %) of component (A) in composition (1) 0.17 0.17 0.17 0.17 0.17 0.15 Content (mass %) of component (B) in composition (1) 1.5 1.5 1.5 1.5 1.5 1.5 Content (mass %) of component (E) in composition (1) 0.2 0.2 0.2 0.2 0.2 0.2 Content (mass %) of component (F) in composition (1) 16 11 11 11 11 11 Content of water in composition (1) (mass %) 76.1 77.5 75.3 76.1 81.1 81.1 Ratio of content of component (B) to component (A) in composition (1) [component (B)/component (A)] 8.77 8.77 8.77 8.77 8.77 10.00 pH value 9.6 9.6 9.6 9.6 9.6 9.6 composition (2) Composition (parts by mass) (C) Distearyldimethylammonium chloride*21 3.6 3.6 3.6 3.6 3.6 3.6 Stearyltrimethylammonium chloride*22 2.7 2.7 2.7 2.7 2.7 2.7 (D) cetearyl alcohol 2 2 2 2 2 2 (polysiloxane) Propylmethicone-Dimethicone Copolymer Emulsion*23 0.05 0.05 0.05 0.05 0.05 0.05 (Polyol) Propylene Glycol 5 5 5 5 5 5 (preservative) Methylparaben 0.1 0.1 0.1 0.1 0.1 0.1 (acid) Lactic acid*24 2 2 2 2 2 2 (alkaline agent) Sodium hydroxide*25 Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount (aqueous medium) Purified water*26 margin margin margin margin margin margin Content (mass %) of component (C) in composition (2) 3.5 3.5 3.5 3.5 3.5 3.5 Content (mass %) of component (D) in composition (2) 2 2 2 2 2 2 Acid content (mass %) in composition (2) 1.8 1.8 1.8 1.8 1.8 1.8 Content of water in composition (2) (mass %) 87.6 87.6 87.6 87.6 87.6 87.6 Ratio of content of component (D) to component (C) in composition (2) [component (D)/component (C)] 0.6 0.6 0.6 0.6 0.6 0.6 Ratio of acid content in composition (2) to component (A) in composition (1) [(acid)/component (A)] 10.5 10.5 10.5 10.5 10.5 12.0 pH value 5.0 5.0 5.0 5.0 5.0 5.0

The components in the table are shown below. Furthermore, the compounded amounts (parts by mass) of each component in the table are all wet weights. *11: 5,6-dihydroxyindole solution: a solution prepared by the method described in Japanese Patent No. 5570161 (5,6-dihydroxyindole: 1% by mass, 5,6-dihydroxyindole Indole-2-carboxylic acid: 0.14% by mass, ethanol: 20% by mass, water: remainder) *12: 5,6-dihydroxyindoline hydrobromide solution (manufactured by AK-scientific, 5,6-dihydroxyindoline hydrobromide: 1% by mass, ethanol: 20% by mass, water: The remaining part) *13: Sodium polyoxyethylene lauryl ether sulfate; Emal E-27C (manufactured by Kao Co., Ltd., active ingredient amount: 27.0% by mass, water: 71.7% by mass) *14: Phosphoric acid; an aqueous solution with a phosphoric acid concentration of 75% by mass *15: Amphoteric surfactant (lauramide propyl betaine); Amphitol 20AB (manufactured by Kao Co., Ltd., active ingredient amount: 28.8% by mass, water: 64.0% by mass) *16: 2-Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine; Amphitol 20Y-B (manufactured by Kao Co., Ltd., active ingredient amount: 40.0% by mass, water: 42.0% by mass) *17: O-[2-hydroxy-3-(trimethyl/lauryldimethylammonio)propyl]hydroxyethylcellulose chloride; SoftCAT Polymer SL-30 (manufactured by The Dow Chemical Company, active ingredient Amount: 91.0% by mass, water: 5.0% by mass) *18: O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride (cationized guar gum); Jaguar Excel (Solvay (manufactured by Novecare)) *19: Dimethyldiallylammonium chloride-acrylic acid copolymer liquid; MERQUAT 280 NP POLYMER (manufactured by Lubrizol Advanced Materials, Inc, active ingredient amount: 41.0% by mass, water: remainder) *20: Purified water; the amount adjusted so that the total amount becomes 100 parts by mass *21: Distearyldimethylammonium chloride; Quartamin D86P (manufactured by Kao Co., Ltd., active ingredient amount: 75% by mass, water: remainder) *22: Stearyltrimethylammonium chloride; Quartamin 86W (manufactured by Kao Co., Ltd., active ingredient amount: 28% by mass, water: remainder) *23: Highly polymerized aminoethylaminopropylmethylsiloxane-dimethylsiloxane copolymer emulsion; Silicone KT-0032 (manufactured by Momentive High-Tech Materials Japan Co., Ltd., active ingredient amount: 40 mass %, water: 49% by mass) *24: Lactic acid; 90% by mass aqueous solution of lactic acid *25: Sodium hydroxide; an aqueous solution with a concentration of 48% by mass of sodium hydroxide, the amount adjusted so that the pH becomes 5.0 *26: Purified water; the amount adjusted so that the total amount becomes 100 parts by mass [Industrial availability]

According to the present invention, it can be set as the following keratin fiber treatment method, which uses, for example, the first composition that has the function of washing the hair and gradually dyes the keratin fibers, such as a shampoo, and, for example, imparts a conditioning function or repairs the hair. The second composition that has the effect of pigment etc. is applied to keratin fibers sequentially, which can inhibit the reduction of dyeability, and dye the gradually dyed keratin fibers less yellow, which is the original color of the melanin precursors that are oxidized. color and improves combability.

Claims (10)

A method for treating keratin fibers, which comprises the following steps (i) and (ii) in sequence: Step (i): Combining the following components (A) and (B) and having a pH value of 8.0 to 12.0 Compound (1) is applied to keratin fibers in step (A) a compound represented by general formula (1) or a salt thereof [Chem. 1]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl group, methyl group or ethyl group] (B) alkaline agent step (ii): the composition (2 ) Step of applying to keratin fibers (C) cationic surfactant (D) higher alcohol. The method for treating keratin fibers as claimed in claim 1, wherein component (B) is one or two or more selected from the group consisting of ammonia and alkanolamines. The method for treating keratin fibers according to claim 1 or 2, wherein the composition (1) further contains an antioxidant as component (E). The method for treating keratin fibers as claimed in item 3, wherein component (E) contains an element selected from the group consisting of L-ascorbic acid, sulfurous acid, pyrosulfurous acid, bisulfite or their salts, ascorbyl glucoside and sulfur dioxide 1 or more than 2 types. The method for treating keratin fibers according to any one of claims 1 to 4, wherein the composition (1) further contains an anionic surfactant as the component (F). The method for treating keratin fibers according to any one of claims 1 to 5, wherein the composition (1) is a cleaning agent. The method for treating keratin fibers according to any one of claims 1 to 6, wherein the composition (2) is a conditioner, conditioner or care agent. The method for treating keratin fibers according to any one of claims 1 to 7, which has a step of washing keratin fibers with water between step (i) and step (ii). The method for treating keratin fibers according to any one of claims 1 to 8, which is a method for dyeing keratin fibers. A composition set for keratin fibers comprising: a composition (1) containing the following components (A) and (B) and having a pH value of 8.0 to 12.0; and a composition (2) containing Components (C) and (D) having a pH of 3.5 or more and less than 8.0, (A) a compound represented by general formula (1) or a salt thereof [Chem. 2]

[In the formula (1), the dotted line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl or acetyloxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, methyl or ethyl group), R ³ represents Hydrogen atom, acetyl, methyl or ethyl] (B) alkaline agent (C) cationic surfactant (D) higher alcohol.