WO2022163731A1

WO2022163731A1 - Keratin fiber treatment method

Info

Publication number: WO2022163731A1
Application number: PCT/JP2022/002970
Authority: WO
Inventors: 真吾駒場; 綾子島津
Original assignee: 花王株式会社
Priority date: 2021-01-29
Filing date: 2022-01-27
Publication date: 2022-08-04
Also published as: TW202245733A; CN116829120A; JP2022117478A

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 π 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 keratin fiber treatment method.

Air oxidation type hair dyes using 5,6-dihydroxyindole, 5,6-dihydroxyindoline or derivatives thereof, which are melanin precursors, are conventionally known as hair dyes for dyeing gray hair. Since these melanin precursors do not use an oxidizing agent, they cause little damage to keratin fibers when used in hair dyes, and are highly convenient as dyes for hair dyes.
For example, JP-A-62-238878 (Patent Document 1), JP-A-2-218606 (Patent Document 2), JP-A-5-058860 (Patent Document 3) and JP-A-2018-052833 (Patent Document Document 4) discloses a composition containing the melanin precursor and a method for dyeing keratin fibers using the composition.
On the other hand, it has been proposed that a composition for keratin fibers such as shampoo, which everyone uses in daily hair washing, is blended with a melanin precursor to easily exhibit high hair dyeing properties for gray hair in a short period of time. (For example, see Japanese Patent Application Laid-Open No. 2019-094326 (Patent Document 5)).

The present invention relates to a keratin fiber treatment method having the following steps (i) and (ii) in sequence.
Step (i): A step of applying a composition (1) containing the following components (A) and (B) and having a pH of 8.0 to 12.0 to keratin fibers (A) General formula (1 ) a compound represented by or a salt thereof

[In formula (1), the dashed line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group). and R ³ represents a hydrogen atom, an acetyl group, a methyl group or an ethyl group. ]
(B) Alkaline agent step (ii): A step of applying a composition (2) containing the following components (C) and (D) and having a pH of 3.5 or more and less than 8.0 to keratin fibers (C ) Cationic surfactant (D) higher alcohol

Hair dyes containing melanin precursors have a slightly slower dyeing property (hair dyeing property) than ordinary oxidative hair dyes, and are characterized by gradual dyeing of keratin fibers with repeated use. be.
However, when a composition containing a melanin precursor is used, as in the shampoo composition shown in the examples of Patent Document 5, the color of the keratin fibers that are dyed does not match the original color to be dyed. It turned out that it may be yellowish compared to the color (natural gray to black). As a result of examining various compositions used before and after the use of the composition, the present inventors found that after the use of the composition, other acidic compositions such as conditioners, rinses and treatments, especially those with a pH of 4 at 25°C. If other compositions with less than 9 are used, the coloring of the keratin fibers gradually becomes yellowish, and the keratin fibers are difficult to dye to the original color that is expressed by the oxidation of melanin precursors. I found the problem.

Patent Documents 1, 2, 3, and 4 also describe hair dyeing using a composition containing a melanin precursor and another composition, but do not describe the above problem. Moreover, there is no description of solving the above problem by specifying the composition and physical properties of the conditioning agent or treatment agent used after applying the melanin precursor to the keratin fibers.
The present invention provides a keratin fiber treatment method in which a step of applying a composition containing a melanin precursor to keratin fibers and a step of applying a composition that imparts a conditioning effect or a treatment effect to keratin fibers to the keratin fibers are performed in this order. Even if the process is repeated, the decrease in dyeability is suppressed, the original color expressed by oxidizing melanin precursors with little yellowness can be dyed, and the finger combability can be improved. Keratin. It relates to providing a textile treatment method.

The present inventors have found a first composition (composition (1)) containing a predetermined melanin precursor and an alkaline agent and having a predetermined pH, a cationic surfactant and a higher alcohol, and a predetermined By applying the second composition (composition (2)) having a pH of to keratin fibers in this order, even if these applications are repeated, the decrease in dyeability is suppressed, and melanin with less yellowness The present inventors have found that a method for treating keratin fibers can be provided, which can dye the precursor to its original color (natural gray to black) and improve finger combability.
That is, the present invention relates to the following [1] to [2].
[1] A keratin fiber treatment method comprising the following steps (i) and (ii) in this order.
Step (i): Step (A) of applying a composition (1) containing the following components (A) and (B) and having a pH of 8.0 or more and 12.0 or less to keratin fibers. ) a compound represented by or a salt thereof

[In formula (1), the dashed line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group). and R ³ represents a hydrogen atom, an acetyl group, a methyl group or an ethyl group. ]
(B) Alkaline agent step (ii): A step of applying a composition (2) containing the following components (C) and (D) and having a pH of 3.5 or more and less than 8.0 to keratin fibers (C ) Cationic surfactant (D) Higher alcohol [2] Composition (1) having a pH of 8.0 or more and 12.0 or less containing the following components (A) and (B), and the following component ( A keratin fiber composition kit comprising a composition (2) containing C) and (D) and having a pH of 3.5 or more and less than 8.0.
(A) a compound represented by the general formula (1) or a salt thereof

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

According to the present invention, a step of applying a composition containing a melanin precursor to keratin fibers such as hair and a step of applying a composition that imparts a conditioning effect or a treatment effect to the keratin fibers to the keratin fibers are sequentially performed. In the treatment method, even if these steps are repeated, the decrease in dyeability is suppressed, the original color of melanin precursors with less yellowness (natural gray to black) can be dyed, and finger combability is improved. It is possible to provide a keratin fiber treatment method that can be used.

Embodiments of the keratin fiber treatment method and composition kit for keratin fibers according to the present invention are described in detail below.
In this specification, the term "A to B" regarding numerical values means "A or more and B or less" (when A<B) or "A or less than B" (when A>B). . Moreover, in the present invention, a combination of preferred aspects is a more preferred aspect.

[Keratin fiber treatment 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 the keratin fiber. In the present invention, "hair" mainly means head hair, and includes black hair, gray hair, and bleached hair. The composition for keratin fibers in the present invention is a composition used for keratin fibers.
In the following description, the dyeing effect of component (A) on keratin fibers may be simply referred to as "dyeability".

The keratin fiber treatment method of the present invention has the following steps (i) and (ii) in order.
Step (i): A step of applying a composition (1) containing the following components (A) and (B) and having a pH of 8.0 to 12.0 to keratin fibers (A) General formula (1 ) a compound represented by or a salt thereof

The present inventors have found that when a composition containing a melanin precursor is used for keratin fibers such as hair and then another composition such as a conditioner or a treatment is repeatedly used, the dyeability decreases, and gradually Various investigations were carried out to solve the problem that the dyeing color becomes yellowish. As a result, the present inventors have found a step of applying a first composition containing a predetermined melanin precursor and an alkaline agent and having a predetermined pH to keratin fibers, and after this step, applying a cationic surfactant and applying a second composition containing a higher alcohol and having a predetermined pH to the keratin fibers.
According to the keratin fiber treatment method of the present invention, a first composition containing a melanin precursor such as a detergent is applied to the keratin fibers, followed by a second composition having a specific pH such as a conditioner or treatment. Even if the application is repeated, the decrease in dyeing property is suppressed, and the original color (natural gray to black) expressed by oxidizing melanin precursors with less yellowness can be dyed, and the finger can be dyed. It is possible to provide a keratin fiber treatment method that can improve the passage.

The detailed reasons why such an effect is obtained are not clear, but one possible reason is as follows. That is, having step (i) and step (iii) in sequence, the cuticle of the keratin fibers is first opened by application of a first composition having a specific pH. Then, by applying the second composition having a specific pH lower than that of the first composition, the keratin fibers shrink, giving a smooth touch and a coat feeling, and good finger combability. can be secured. In addition, since the second composition has an appropriate pH, step (i) can be repeated without impairing the dyeability of composition (1) applied to the keratin fibers in step (i). It is thought that the yellowing of the keratin fibers can be suppressed when the keratin fibers are gradually dyed by being soaked.

(Step (i))
Step (i) is a step of applying composition (1) containing the following components (A) and (B) and having a pH of 8.0 or more and 12.0 or less to keratin fibers.
(A) a compound represented by the general formula (1) or a salt thereof

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

Through step (i), component (A), which is a melanin precursor, is supplied to keratin fibers. After component (A) permeates into keratin fibers, it is oxidatively polymerized by atmospheric oxygen to form a melanin pigment (melanin polymer). Then, by repeating the step (i), the keratin fibers are gradually dyed with the original color expressed by the oxidation of the melanin precursor. Then, by performing step (ii) described later after step (i), the composition (2) having a predetermined pH is supplied to the keratin fibers, so step (i) and step (ii) are performed. Even if it is repeated, the deterioration of dyeability and yellowing of the color of keratin fibers are suppressed.

In step (i), the composition (1) may be applied to keratin fibers and then foamed with a hand or a brush. The composition (1) may be foamed by rubbing the palms or both hands together in advance, or may be foamed out from a foamer container, or the composition (1) foamed in advance may be applied to the keratin fibers. Also, after applying to keratin fibers, it may be left for a certain period of time. The total 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 30 seconds to 2 minutes, from the viewpoint of both convenience and dyeability. More preferred.
From the viewpoint of usability, the amount of the composition (1) applied to the keratin fibers is preferably 0.01 to 2, more preferably 0.05 to 1, when the mass of the keratin fibers is 1. .
Prior to step (i), it is preferable to untangle the keratin fibers using a tool such as a brush from the viewpoint of easiness in spreading the composition (1) over the keratin fibers. From the same point of view, it is preferable to wet the keratin fibers with water in advance.
The keratin fibers may be washed with a detergent such as shampoo before step (i). After washing, it is preferable to have a step of rinsing with water.

Between step (i) and step (ii), it is preferred to have a step of rinsing the keratin fibers with water. Moreover, after the rinsing step, a step of drying the keratin fibers (hereinafter also simply referred to as a “drying step”) can be provided. The step of drying the keratin fibers is a step of reducing the water content of the keratin fibers. The drying step includes, for example, a method of squeezing the keratin fibers to remove excess water. Moreover, in order to positively reduce the water content of the keratin fibers, towel drying, dryer (cold or hot air) drying, air drying, and a combination of two or more of these drying treatments are included.
From the viewpoint of easiness in spreading the composition (2) on the keratin fibers, it is preferable to apply the composition (2) to the step (ii) while maintaining a wet state after the rinsing step. When the mass of the keratin fibers subjected to step (ii) after step (i) is taken as 1, the water content in the keratin fibers is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably is 0.5 or more, more preferably 0.8 or more. Although the upper limit of the water content in the keratin fibers subjected to step (ii) after step (i) is not particularly limited, it is usually 5 or less to suppress dripping of water from the keratin fibers. , preferably 3 or less, more preferably 2 or less, and still more preferably 1.2 or less from the viewpoint of improving the operability.
As a method for measuring the amount of water in the keratin fibers, the mass of the keratin fibers in each treatment step is dried by applying hot air from a dryer for 30 minutes, and left to stand for a day or more at a temperature of 25 ° C. and a relative humidity of 65%. It can be measured from the difference in mass from completely dried keratin fibers.

More specifically, it is preferable to have the following steps (i-1), (i-2) and (i-3) between steps (i) and (ii).
- Step (i-1): Any one of the steps of: leaving the composition (1) to stand after applying the composition (1), foaming the composition (1), and foaming the composition (1) and then leaving it to stand. (i-2): Step of rinsing composition (1) on keratin fibers with water Step (i-3): Step of drying keratin fibers In step (i-1), when lathering with hands In addition, lathering may be performed using fingers or the palm of the hand, or a tool such as a brush may be used for lathering.
In step (i-2), the temperature of the water during rinsing is preferably 0° C. or higher, more preferably 5° C. or higher, still more preferably 10° C. or higher, from the viewpoint of efficiently washing away the composition (1). It is preferably 45° C. or lower, more preferably 40° C. or lower.
In step (i-3), the keratin fibers are completely dried (that is, specifically, when the mass of the keratin fibers is 1, the water content in the keratin fibers is 0.01 or less). Alternatively, the keratin fibers may be squeezed to remove excess water and remain moist.
Also, between step (i) and step (ii), step (i) may optionally be repeated again, applying a composition other than composition (1) and composition (2) to the keratin fibers. You may have a process.

<Composition (1)>
Composition (1) used in step (i) is not particularly limited as long as it contains component (A) and component (B). Due to the gradual staining characteristic, multiple uses may be required. Therefore, the composition (1) is preferably provided as a composition for keratin fibers such as a detergent such as a shampoo, a rinse agent, a conditioning agent, a treatment agent, etc., which can be easily dyed by daily hair care activities. Among these, the composition (1) is more preferably a detergent from the viewpoints of easy dyeing by daily hair care actions and good dyeability.
The dosage form of composition (1) is not particularly limited, and may be in any dosage form such as liquid, foam, paste, cream, solid, and powder. From the viewpoint of applicability to keratin fibers, it is preferably in the form of liquid, paste or cream.

The composition (1) used in step (i) contains components (A) and (B) described below, and has a pH of 8.0 or more and 12.0 or less.
When the pH of the composition (1) is 8.0 or more, the effect of promoting the polymerization reaction and improving the dyeability is obtained, and the pH of the composition (1) is 12.0 or less. Thus, damage to keratin fibers can be suppressed while improving dyeability.
The pH of the composition (1) is preferably 8.5 or higher, more preferably 8.8 or higher, and even more preferably 9.0 or higher, from the viewpoint of further promoting the polymerization reaction and further improving the dyeability. This is because component (A), which is a melanin precursor, reacts with oxygen in the air under basic conditions and is easily converted into a melanin pigment. The pH is preferably 11.0 or less, more preferably 10.5 or less, and even more preferably 10.0 or less, from the viewpoint of further enhancing the dyeability and the ability to suppress damage to keratin fibers. Specifically, the pH is preferably 8.5 to 11.0, more preferably 8.8 to 10.5, still more preferably 9.0 to 10.0.
The above pH is a value measured at 25° C., and can be specifically measured by the method described in Examples.

<Component (A)>
Composition (1) used in step (i) contains component (A) which is a compound represented by the following general formula (1) or a salt thereof. Component (A) is a melanin precursor that is polymerized by air oxidation and converted into a melanin pigment, and acts as a dyeing agent for keratin fibers.

[In formula (1), the dashed line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group). and R ³ represents a hydrogen atom, an acetyl group, a methyl group or an ethyl group. ]
The melanin precursor of component (A) is an indole derivative or an indoline derivative, which is a compound represented by the general formula (1), or a salt thereof, and in the present invention, one or a combination of two or more thereof is used. be able to. Component (A) is more preferably an indole derivative (that is, a π bond is present in the dashed line portion in general formula (1)) from the viewpoint of dyeability.
From the viewpoint of availability and dyeability of component (A), in general formula (1), R ¹ is preferably a hydroxyl group, R ² is preferably a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group), more preferably a hydrogen atom or —COOH. ^R3 is preferably a hydrogen atom.

Examples of the compound represented by the general formula (1) include 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, methyl 5,6-dihydroxyindole-2-carboxylate, 5,6- Ethyl 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, N-acetyl-5,6-dihydroxyindole-2-carboxylic acid, 5-acetoxy-6-hydroxyindole, 5 - acetoxy-6-hydroxyindole-2-carboxylic acid, 5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, methyl 5,6-dihydroxyindoline-2-carboxylate, 5,6-dihydroxy Ethyl indoline-2-carboxylate, N-methyl-5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline-2-carboxylic acid, N-ethyl-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-acetoxy-6-hydroxyindoline, 5- acetoxy-6-hydroxyindoline-2-carboxylic acid, and the like.

Examples of the salt of the compound represented by the general formula (1) include hydrochloride, hydrobromide, sulfate, phosphate, acetate, propionate, lactate, citrate and the like of the compound. Among them, hydrobromide is preferable from the viewpoint of availability.
Further, when R ² is —COOH in general formula (1), the salt of the compound represented by general formula (1) may be a carboxylate (R ² is —COO ⁻ X ⁺ (X ⁺ is Na ⁺ , K ⁺ and other alkali metal ions, Ca ⁺ and Mg ⁺ and other alkaline earth metal ions, and ammonium ions and other cations).

From the viewpoint of dyeing keratin fibers in a natural shade (gray to black), component (A) includes 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 5,6-dihydroxyindoline, 5, One or more selected from the group consisting of 6-dihydroxyindole-2-carboxylic acid and salts thereof are preferred, and 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, and 5 ,6-Dihydroxyindole hydrobromide, more preferably one or more selected from the group consisting of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid. It is more preferable to use one or two, and it is even more preferable to use 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid in combination.
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, preferably 80:20 to 99:1. and more preferably 85:15 to 95:5. When the molar ratio of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid is within the above range, the finished keratin fiber after dyeing approaches a natural color.
The molar ratio of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid can be determined by reverse phase HPLC.

The content of component (A) in composition (1) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of improving dyeability. From the viewpoint of economy, the content is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1.0% by mass or less, even more preferably 0.8% by mass or less, and even more preferably 0.8% by mass or less. It is 5% by mass or less, more preferably 0.3% by mass or less. Also, it is preferably 0.05% by mass to 5% by mass, more preferably 0.05% by mass to 3% by mass, still more preferably 0.1% by mass to 1.0% by mass, and still more It is preferably 0.1% by mass to 0.8% by mass, still more preferably 0.1% by mass to 0.5% by mass, and even more preferably 0.1% by mass to 0.3% by mass. be.

<Component (B)>
Composition (1) used in step (i) contains component (B), which is an alkaline agent. The alkaline agent swells the keratin fibers to open the cuticles, allowing the dye component such as the component (A) to penetrate into the keratin fibers, and also promotes the polymerization reaction of the component (A) to improve dyeability. have As the alkali agent, any alkali agent that is commonly used in hair dyes can be used without particular limitation.
Alkanolamines such as mono-, di- or trimethanolamine, mono-, di- or triethanolamine; methylamine, dimethylamine, ethylamine, diethylamine, N-methylethylamine, propyl Alkylamines such as amine and butylamine; aralkylamines such as benzylamine; inorganic alkali compounds such as sodium hydroxide and potassium hydroxide; The carbon number of the alkanolamine, alkylamine or aralkylamine is preferably 10 or less, more preferably 8 or less, from the viewpoint of water solubility.
Among them, from the viewpoint of dyeability, the alkaline agent is preferably one or more selected from the group consisting of ammonia, alkanolamine, alkylamine, aralkylamine, sodium hydroxide, and potassium hydroxide. It more preferably contains one or more selected from the group consisting of amines, more preferably contains monoalkanolamine, and even more preferably contains monoethanolamine.
In particular, component (B), which is an alkaline agent, is preferably one or more selected from the group consisting of ammonia and alkanolamine.

The content of component (B) in composition (1) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.5% by mass, from the viewpoint of expressing high dyeability. % by mass or more. From the viewpoint of suppressing irritation, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. Also, it is preferably 0.01% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, and still more preferably 0.5% by mass to 3% by mass.
In addition, the ratio of the content of component (B) to the content of component (A) in composition (1) [component (B)/component (A)] is determined from the viewpoint of expressing high dyeability and good hair. From the viewpoint of ensuring good finger combability, it is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more, and preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less. Also, it is preferably 2 to 100, more preferably 5 to 50, still more preferably 8 to 30.

<Component (E)>
From the viewpoint of improving the stability of component (A), composition (1) used in step (i) preferably further contains an antioxidant as component (E).
Antioxidants include sulfite, pyrosulfite, hydrogen sulfite, sulfur dioxide, L-ascorbic acid, thioglycolic acid, L-cysteine, N-acetyl-L-cysteine and salts thereof and derivatives thereof. As the salt, alkali metals such as sodium and potassium can be preferably used.
Among these, sulfites, pyrosulfites, hydrogen sulfites and sulfur dioxide are used after applying composition (2) or composition (2) and other acidic compositions after applying composition (1). It is preferable as the component (E) from the viewpoint of imparting an effect of suppressing yellowing of the dyed color (hereinafter also simply referred to as "yellowness suppressing effect") when dyed. More specifically, suitable component (E) includes sodium sulfite, potassium sulfite, sodium hyposulfite, potassium hyposulfite, sulfur dioxide, potassium pyrosulfite, sodium pyrosulfite and the like. Among these, from the viewpoint of market availability, the component (E) is preferably a sulfite or a pyrosulfite, more specifically from the group consisting of sodium sulfite, potassium sulfite, sodium pyrosulfite and potassium pyrosulfite. One or two or more selected are preferable.
Further, from the viewpoint of improving dyeability, the component (E) is preferably L-ascorbic acid and its salts, and ascorbic acid glucoside, more specifically L-ascorbic acid, sodium L-ascorbate and L-ascorbic acid. One or two or more selected from the group consisting of glucosides are preferred.
Component (E) consists of L-ascorbic acid, sulfurous acid, pyrosulfite, hydrogen sulfite or salts thereof, ascorbic acid glucoside and sulfur dioxide from the viewpoint of imparting a yellow tint suppressing effect and improving dyeability. It is preferable to contain one or more selected from the group.
Component (E) is one or two selected from the group consisting of sulfites, pyrosulfites, hydrogen sulfites and sulfur dioxide, from the viewpoint of imparting a yellowing suppressing effect and of stabilizing component (A). The above first antioxidant and a second antioxidant different from the first antioxidant can be included (used together). In that case, one or more selected from the group consisting of sulfite, pyrosulfite, hydrogen sulfite and salts thereof, and 1 selected from the group consisting of L-ascorbic acid, sodium L-ascorbate and L-ascorbic acid glucoside It is preferable to include a species or two or more species.

When the composition (1) contains the component (E), the content of the component (E) in the composition (1) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more. be. The content is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less. Also, it is preferably 0.05% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, and still more preferably 0.1% by mass to 2% by mass.

<Component (F)>
The composition (1) used in the step (i) improves the foamability of the composition (1) during use and facilitates the even and uniform application of the dyeing component (A) to the keratin fibers. , preferably further contains an anionic surfactant as component (F). Component (F) imparts a cleaning effect to keratin fibers when composition (1) is a detergent. Furthermore, when a cationic polymer, which is an optional component described later, is used in combination, the combination of the cationic polymer and the component (F) causes coacervation in a system in which the composition (1) is diluted with water, By incorporating the component (A) in the coacervate at a high concentration and adsorbing it onto the surface of the keratin fibers, it is possible to achieve both a cleansing effect and high dyeability.

Examples of the anionic surfactant include alkylbenzenesulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefinsulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ethers Carboxylate, α-sulfo fatty acid salt, N-acylamino acid salt, phosphoric acid mono- or diester, sulfosuccinic acid ester and the like can be mentioned, and one or more of these can be used.
Examples of counter ions for the anionic group of the anionic surfactant include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; and alkanol groups having 2 or 3 carbon atoms. 1 to 3 alkanolamines (eg monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).
Above all, when the composition (1) is a detergent, from the viewpoint of at least one of good foaming, washability, and dyeability, the component (F) is an alkyl ether sulfate and an N-acylamino acid salt. , and alkyl ether carboxylates are preferred, and one or more selected from the group consisting of alkyl ether sulfates and alkyl ether carboxylates are more preferred. Examples of the alkyl ether sulfates include polyoxyethylene alkyl ether sulfates, and examples of the alkyl ether carboxylates include polyoxyethylene alkyl ether acetates. Examples of the N-acylamino acid salt include cocoyl glutamate.

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, More preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 17% by mass It is below. Also, preferably 0.1% by mass to 40% by mass, more preferably 0.5% by mass to 30% by mass, still more preferably 1% by mass to 20% by mass, still more preferably 1% by mass to 17% by mass. be.
Especially when the composition (1) is a detergent, the content of the component (F) in the composition (1) is preferably 3 from the viewpoint of at least one of good foaming, washability and dyeability. % by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more. In addition, from the viewpoint of improving dyeability and suppressing damage to keratin fibers, the content of component (F) in composition (1) is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 30% by mass or less. is 20% by mass or less, more preferably 17% by mass or less. Also, it is preferably 3% to 40% by mass, more preferably 5% to 30% by mass, still more preferably 8% to 20% by mass, and even more preferably 8% to 17% by mass.

<Other Components in Composition (1)>
In addition to the above components, the composition (1) used in step (i) may appropriately contain components commonly used in keratin fiber compositions or hair dyes within a range that does not impair the object of the present invention. good. Examples of such components include buffering agents, amphoteric surfactants, silicones, aromatic alcohols, dyes other than component (A), cationic polymers, polymers other than cationic polymers, nonionic surfactants, and oils. , anti-dandruff agents, vitamin agents, bactericides, anti-inflammatory agents, preservatives, chelating agents, moisturizing agents, pearl agents, ceramides, fragrances, ultraviolet absorbers, aqueous media and the like. Among these, it is preferable to contain one or more selected from the group consisting of buffers, amphoteric surfactants, cationic polymers and aqueous media.

(buffer)
Composition (1) used in step (i) preferably contains a buffer. By containing a buffer, even when the composition (1) is diluted with water at the time of use, the optimum pH range for component (A) to express high dyeability is easily maintained.
The buffering agent is not particularly limited as long as it has a pH buffering action, but component (A), which is a melanin precursor, reacts with oxygen in the air under basic conditions and is easily converted into a melanin pigment. Buffers capable of adjusting the pH of composition (1) to basic conditions are preferred.
From the above viewpoint, the buffer contains any one of carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, glycine, sodium tetraborate, or ammonium chloride as a basic component. or a buffer consisting of a combination of two or more basic components, such as sodium carbonate-sodium bicarbonate, is preferred, a buffer containing carbonate is more preferred, and a buffer containing sodium bicarbonate is more preferred. preferable.

The buffering agent may further contain a protonating agent as a constituent component of the buffering agent from the viewpoint of improving the pH buffering capacity. The protonating agent may be either a monobasic acid or a polybasic acid, and may be either an organic acid (having from 1 to 8 carbon atoms, excluding ascorbic acid) or an inorganic acid. Examples of the protonating agent include one or more selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, and citric acid, and one selected from the group consisting of phosphoric acid and citric acid. A species or two are more preferred.

From the viewpoint of improving dyeability, it is more preferable that the component constituting the buffer is 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 buffering agent, the content of the buffering agent in the composition (1) is not particularly limited as long as it is an amount that can adjust the pH of the composition (1) to the desired range. , From the viewpoint of improving the pH buffering capacity when the composition (1) is diluted with water, it is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and still more preferably 1.5% by mass. above, and particularly preferably at least 1.8% by mass. In addition, from the viewpoint of formulation stability, the content of the buffering agent in composition (1) is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and still more preferably 3.5% by mass. % or less, more preferably 3.0 mass % or less, and particularly preferably 2.5 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, still more preferably 1.5% by mass to 3.5% by mass, still more preferably 1.8% to 3.0% by weight, particularly preferably 1.8% to 2.5% by weight.
In addition, the content of the buffering agent means the total amount of active ingredients of the components constituting the buffering agent.

(Amphoteric surfactant)
Composition (1) used in step (i) may contain an amphoteric surfactant.
Examples of amphoteric surfactants include betaine surfactants such as alkyldimethylaminoacetic acid betaine, fatty acid amidopropylbetaine, alkylhydroxysulfobetaine, N-acylaminoethyl-N-2-hydroxyethylaminocarboxylate; sultaine-based surfactants such as tine; Among these surfactants, betaine-based surfactants are preferable, and fatty acid amidopropyl betaine is more preferable, from the viewpoints of compatibility with keratin fibers and good lathering. The fatty acid amidopropyl betaine preferably has an acyl group having 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, such as lauramidopropyl betaine, palm kernel oil amidopropyl betaine, and coconut amidopropyl One or more selected from the group consisting of betaine is preferred. Examples of N-acylaminoethyl-N-2-hydroxyethylaminocarboxylates include N-coconut fatty acid acyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine [sodium cocoamphoacetate, 2-alkyl -N-carboxymethyl-N-hydroxyethylimidazolinium betaine], N-coconut fatty acid acyl-N'-carboxyethyl-N'-hydroxyethylethylenediamine [thorium cocoamphopropionate], N-lauroyl -N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium [sodium lauroamphoacetate] and the like.

When the composition (1) contains an amphoteric surfactant, the content of the amphoteric surfactant in the composition (1) is from the viewpoint of the ease of compatibility with keratin fibers, good foaming, and improved feel during rinsing. Therefore, it is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, still more preferably 0.15% by mass or more, still more preferably 0.50% by mass or more, and even more preferably 1.0% by mass. % or more, preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less. Also, preferably 0.05% by mass to 15% by mass, more preferably 0.10% by mass to 12% by mass, still more preferably 0.15% by mass to 10% by mass, still more preferably 0.50% by mass to 10% by mass, more preferably 1.0% to 10% by mass.

(Cationic polymer)
Composition (1) may contain a cationic polymer. The cationic polymer causes coacervation in combination with the component (F), and causes the component (A) to be included in the coacervate at a high concentration and adsorbed onto the keratin fiber surface, thereby exhibiting high dyeability. have
In the present invention, the cationic polymer refers to a water-soluble polymer having a cationic group and exhibiting cationic properties as a whole. That is, the cationic polymer includes a cationic polymer having only cationic groups and no anionic group, and an amphoteric polymer having cationic groups and anionic groups and exhibiting cationic properties as a whole. Included in the cationic polymers of the invention.
The anionic group is an anionic group or a group that can be ionized to become an anionic group.

Examples of the cationic polymer include cationized guar gum; cationized tara gum; cationized locust bean gum; cationized polyvinyl alcohol; cationized cellulose; cationic starch; vinylpyrrolidone/N,N-dimethylaminoethyl methacrylate diethyl sulfate copolymer, N,N-dimethylaminoethyl methacrylate diethyl sulfate/N,N-dimethylacrylamide/polyethylene glycol dimethacrylate copolymer Quaternized dialkylaminoalkyl (meth)acrylate polymers such as polymers; polydiallyldimethylammonium chloride, diallyldimethylammonium chloride/acrylic acid copolymer, diallyldimethylammonium chloride/acrylamide copolymer, diallyldimethyl diallyl quaternized ammonium salt polymers such as ammonium chloride/acrylic acid/acrylamide copolymers; vinylimidazolium trichloride/vinylpyrrolidone copolymers; vinylpyrrolidone/alkylamino (meth)acrylate copolymers; vinylpyrrolidone /alkylamino (meth)acrylate/vinylcaprolactam copolymer; vinylpyrrolidone/(meth)acrylamidopropyl trimethylammonium chloride copolymer; alkylacrylamide/(meth)acrylate/alkylaminoalkylacrylamide/polyethylene glycol (meth)acrylate copolymer Coalescing; adipic acid/dimethylaminohydroxypropylethylenetriamine copolymer, cationic polymers described in JP-A-53-139734 and JP-A-60-36407, etc., and one of these Or 2 or more types can be used.

From the viewpoint of easily causing coacervation and expressing high dyeability, cationic polymers include cationized guar gum, cationized tara gum, cationized locust bean gum, cationized polyvinyl alcohol, cationized hydroxyethyl cellulose, and cationized hydroxypropyl cellulose. , vinylpyrrolidone/N,N-dimethylaminoethyl methacrylate diethyl sulfate copolymer, N,N-dimethylaminoethyl methacrylate diethyl sulfate/N,N-dimethylacrylamide/polyethylene glycol dimethacrylate copolymer, poly one or more selected from the group consisting of diallyldimethylammonium chloride, diallyldimethylammonium chloride/acrylic acid copolymer, diallyldimethylammonium chloride/acrylamide copolymer and diallyldimethylammonium chloride/acrylic acid/acrylamide polymer Preferably, cationized guar gum, cationized tara gum, cationized polyvinyl alcohol, cationized hydroxyethyl cellulose, cationized hydroxypropyl cellulose, N,N-dimethylaminoethyl methacrylate diethyl sulfate/N,N-dimethylacrylamide/polyethylene dimethacrylate 1 selected from the group consisting of glycol copolymers, polydiallyldimethylammonium chloride, diallyldimethylammonium chloride/acrylic acid copolymers, diallyldimethylammonium chloride/acrylamide copolymers and diallyldimethylammonium chloride/acrylic acid/acrylamide polymers more preferably cationized guar gum, cationized tara gum, cationized polyvinyl alcohol, cationized hydroxyethyl cellulose, cationized hydroxypropyl cellulose, N,N-dimethylaminoethyl methacrylate diethyl sulfate/N,N- More preferably, one or more selected from the group consisting of dimethylacrylamide/polyethylene glycol dimethacrylate copolymer, diallyldimethylammonium chloride/acrylic acid copolymer, and diallyldimethylammonium chloride/acrylamide copolymer.

When the composition (1) contains a cationic polymer, the content of the cationic polymer in the composition (1) is preferably 0.05% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of improving dyeability. It is 1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more. In addition, from the viewpoint of improving stability and improving dyeability, the be. Also, preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass, still more preferably 0.2% by mass to 1.5% by mass, still more preferably 0.3% by mass % to 1.0% by mass.

(aqueous medium)
Composition (1) usually contains an aqueous medium. Examples of the aqueous medium include water; lower alcohols such as ethanol and isopropyl alcohol; and low-molecular-weight diols and triols having 6 or less carbon atoms such as 1,3-butylene glycol, glycerin, ethylene glycol and propylene glycol, with water being preferred.
When the composition (1) contains an aqueous medium, the content of the aqueous medium in the composition (1) can be appropriately selected depending on the dosage form of the composition (1), but usually 1 to 95 mass % range.
When water is used as the aqueous medium, coacervation occurs when the composition (1) is diluted with water at the time of use, and the component (A) is adsorbed onto the keratin fiber surface, resulting in high dyeability. from the viewpoint of increasing the , and preferably 95% by mass or less, more preferably 90% by mass or less. Also, it is preferably 40% to 95% by mass, more preferably 50% to 95% by mass, still more preferably 60% to 90% by mass, and even more preferably 70% to 90% by mass.

The method for producing composition (1) is not particularly limited. For example, the components (A) and (B) and other components used as necessary can be blended by the method described in the Examples and mixed using a known stirring device or the like.

(Step (ii))
Step (ii) is performed after step (i), and the composition (2) containing the following components (C) and (D) and having a pH of 3.5 or more and less than 8.0 is applied to keratin fibers. This is the process to apply.
(C) Cationic Surfactant (D) Higher Alcohol Step (ii) supplies the keratin fibers with component (C), which is a cationic surfactant, and component (D), which is a higher alcohol. By supplying the component (C) and the component (D), it is possible to impart a smooth feel and ease of loosening after drying, and to ensure good combability with fingers. Moreover, the composition (2) containing the components (C) and (D) and having a predetermined pH has a high dyeability with the composition (1) applied to the keratin fibers in the step (i). It does not affect the keratin fibers and suppresses yellowing of the keratin fibers when the step (i) is repeated and the keratin fibers are gradually dyed.

In the step (ii), the amount of the composition (2) applied to the keratin fibers is preferably 0.01 to 2, more preferably 0, when the mass of the keratin fibers is 1, from the viewpoint of usability. .05 to 1.

After step (ii), it is preferable to have the following steps.
[1] When the composition (2) is used in a leave-off form Step (ii-1): A step of washing away the composition (2) on the keratin fibers with water Step (ii) immediately after step (ii) -1) may be carried out, or step (ii-1) may be carried out after standing. When left, the leaving time is preferably 5 seconds or longer, more preferably 30 seconds or longer, still more preferably 1 minute or longer, and preferably 20 minutes or shorter, more preferably 15 minutes or shorter, and still more preferably 10 minutes or shorter. is.
In step (ii-1), the temperature of the water to be washed away is preferably 0° C. or higher, more preferably 5° C. or higher, still more preferably 10° C. or higher, from the viewpoint of efficiently washing off the composition (2). 45° C. or lower, more preferably 40° C. or lower. Also, it is preferably 0°C to 45°C, more preferably 5°C to 40°C, still more preferably 10°C to 40°C.
- Step (ii-2): Step of drying keratin fibers After step (ii-1) is carried out, it is preferable to carry out a step of drying keratin fibers (step (ii-2)). The keratin fibers may be completely dried (that is, specifically, when the mass of the keratin fibers is 1, the water content in the keratin fibers is 0.01 or less), or the keratin fibers may be squeezed. It is also possible to remove the excess moisture by pressing and re-submit to the step (i) while maintaining the moist state.
Optionally, after step (ii-2), a composition other than composition (1) and composition (2) may be applied to the keratin fibers.

[2] When the composition (2) is used in a leave-on form Step (ii-2): Drying the keratin fibers Step (ii) After applying the composition (2) to the keratin fibers, drying the keratin fibers It is preferable to perform the step of allowing (step (ii-2)). In this case, from the viewpoint of fixing the composition (2) on the keratin fibers, it is more preferable to completely dry the keratin fibers.
Optionally, after step (ii-2), a composition other than composition (1) and composition (2) may be applied to the keratin fibers.

<Composition (2)>
The composition (2) used in step (ii) contains component (C) and component (D) and is not particularly limited as long as it has a predetermined pH, but is preferably a composition for keratin fibers. Examples thereof include detergents such as shampoos, rinse agents, conditioning agents, treatment agents (including leave-in type), styling agents, hair growth agents, and the like, which are used in daily hair care activities. Among these, from the viewpoint of maintaining the dyeability of keratin fibers treated with the composition (1) and ensuring good finger combability, the composition (2) is preferably a rinse agent, a conditioning agent, a treatment agent, styling agent or hair restorer, more preferably a rinse agent, a conditioning agent or a treatment agent.
The dosage form of composition (2) is not particularly limited, and may be in any dosage form such as liquid, foam, paste, cream, solid, and powder. From the viewpoint of applicability to keratin fibers, it is preferably liquid, paste or cream.

The composition (2) used in step (ii) contains components (C) and (D) described below, 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 range, the effect of suppressing a decrease in dyeability, suppressing yellowness in the color tone after dyeing, and ensuring good finger combability can be obtained.
The pH of the composition (2) is preferably 4.0 or higher, more preferably 4.2 or higher, and still more preferably 4.3 or higher, from the viewpoint of suppressing a decrease in dyeability and imparting an effect of suppressing yellowness. Even more preferably 4.8 or more, and even more preferably 5.0 or more. From the viewpoint of suppressing damage to keratin fibers and ensuring good finger combability, it is preferably 7.5 or less, more preferably 7.3 or less, and even more preferably 7.1 or less. Also, preferably 4.0 to 7.5, more preferably 4.2 to 7.5, still more preferably 4.3 to 7.3, even more preferably 4.8 to 7.3, still more preferably 5.0 to 7.3, more preferably 5.0 to 7.1.
The above pH is a value measured at 25° C., and can be specifically measured by the method described in Examples.

<Component (C)>
Composition (2) used in step (ii) contains component (C) which is a cationic surfactant.
Examples of cationic surfactants of component (C) include (i) alkyltrimethylammonium salts, (ii) alkoxyalkyltrimethylammonium salts, (iii) dialkyldimethylammonium salts, (iv) alkyldimethylamines and salts thereof, (v) alkoxyalkyldimethylamine and its salt, (vi) alkylamidoamine and its salt, and the like.

(i) Alkyltrimethylammonium salts Examples of alkyltrimethylammonium salts include those represented by the following general formula (2).
R ¹³ —N ⁺ (CH ₃ ) ₃ An ^— (2)
[In the formula, R ¹³ represents an alkyl group having 12 to 22 carbon atoms, An ^- represents a halide ion such as chloride ion and bromide ion; , methocarbonate ion and the like. ]

Specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyltrimethylammonium methosulfate, and the like.

(ii) Alkoxyalkyltrimethylammonium salt Examples of the alkoxyalkyltrimethylammonium salt include those represented by the following general formula (3).
R ¹⁴ —OR ¹⁵ —N ⁺ (CH ₃ ) ₃ An ^— (3)
[In the formula, R ¹⁴ represents an alkyl group having 12 to 22 carbon atoms, R ¹⁵ represents an ethylene group or a propylene group optionally substituted with a hydroxy group, An ^- represents a halogen such as a chloride ion or a bromide ion. compound ion; methosulfate ion, ethosulfate ion, methphosphate ion, ethophosphate ion, methocarbonate ion, and the like; ]

Specific examples include stearoxypropyltrimethylammonium chloride, stearoxyethyltrimethylammonium chloride, stearoxyhydroxypropyltrimethylammonium chloride, and the like.

(iii) Dialkyldimethylammonium salt Examples of the dialkyldimethylammonium salt include those represented by the following general formula (4).
(R ¹⁶ ) ₂ N ⁺ (CH ₃ ) ₂ An ⁻ (4)
[In the formula, R ¹⁶ each independently represents an alkyl group having 12 to 22 carbon atoms, An ^- represents a halide ion such as chloride ion and bromide ion; Ethophosphate ion, methocarbonate ion, etc. are shown. ]

Specific examples include distearyldimethylammonium chloride.

(iv) Alkyldimethylamine and its salt Alkyldimethylamine reacts with an acid to form a quaternary ammonium salt, which serves as a surfactant. Therefore, alkyldimethylamines and salts thereof are defined as cationic surfactants here. Moreover, the content is converted by the mass of the alkyldimethylamine. Examples of alkyldimethylamines and salts thereof include those represented by the following general formula (5) and salts thereof.
R ¹⁷ —N(CH ₃ ) ₂ (5)
[In the formula, R ¹⁷ represents an alkyl group having 12 to 22 carbon atoms. ]

Salts include salts with organic acids or inorganic acids. Examples of organic acids include monocarboxylic acids such as acetic acid and propionic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and phthalic acid; polycarboxylic acids such as polyglutamic acid; Hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid and citric acid; acidic amino acids such as glutamic acid and aspartic acid; Examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid and the like. Among these, organic acids are preferred, dicarboxylic acids, hydroxycarboxylic acids and acidic amino acids are preferred, and maleic acid and succinic acid are more preferred as dicarboxylic acids. More preferred hydroxycarboxylic acids are glycolic acid, lactic acid and malic acid. Glutamic acid is more preferred as the acidic amino acid.

Specific alkyldimethylamines and salts thereof include N,N-dimethylbehenylamine, N,N-dimethylstearylamine and organic acid salts thereof, and N,N-dimethylbehenylamine lactate, N, Lactate of N-dimethylstearylamine and the like are preferred.

(v) Alkoxyalkyldimethylamine and its salt Alkoxyalkyldimethylamine reacts with an acid to form a quaternary ammonium salt, which serves as a surfactant. Therefore, alkoxyalkyldimethylamines and salts thereof are defined as cationic surfactants herein. Moreover, the content is converted by the mass of the alkoxyalkyldimethylamine. Examples of alkoxyalkyldimethylamines and salts thereof include those represented by the following general formula (6) and salts thereof.
R ¹⁸ —OR ¹⁹ —N(CH ₃ ) ₂ (6)
[In the formula, R ¹⁸ represents an alkyl group having 12 to 22 carbon atoms, and R ¹⁹ represents an ethylene group or a propylene group optionally substituted with a hydroxy group. ]

Salts include salts with organic acids or inorganic acids. Examples of the organic acid or inorganic acid include the organic acid or inorganic acid used for neutralizing the alkyldimethylamine represented by the general formula (5).

Specific alkoxyalkyldimethylamines and salts thereof include N,N-dimethyl-3-hexadecyloxypropylamine, N,N-dimethyl-3-octadecyloxypropylamine and organic acid salts thereof, and N , N-dimethyl-3-hexadecyloxypropylamine lactate and N,N-dimethyl-3-octadecyloxypropylamine glycolate are preferred.

(vi) Alkylamidoamine and its salt Alkylamidoamine reacts with an acid to form a quaternary ammonium salt, which serves as a surfactant. Therefore, alkylamidoamines and salts thereof are defined as cationic surfactants herein. Moreover, the content is converted into the mass of the alkylamidoamine. Examples of alkylamidoamines and salts thereof include those represented by the following general formula (7) and salts thereof.
R ²⁰ -CONH-(CH ₂ ) _t -N(CH ₃ ) ₂ (7)
[In the formula, R ²⁰ represents an alkyl group having 12 to 22 carbon atoms, and t represents a number of 2 to 4. ]

Among these, those in which R ²⁰ is an alkyl group having 14 to 22 carbon atoms are preferred.
Salts include salts with organic or inorganic acids. Examples of the organic acid or inorganic acid include the organic acid or inorganic acid used for neutralizing the alkyldimethylamine represented by the general formula (5).

Specific alkylamidoamines and salts thereof include N-(3-(dimethylamino)propyl)docosanamide and salts thereof, N-(3-(dimethylamino)propyl)stearamide and salts thereof.

Among these, (i) alkyltrimethylammonium salts, (ii) alkoxyalkyltrimethylammonium salts, (v) alkoxyalkyldimethylamines and salts thereof, and (vi) alkylamidoamines and salts thereof are used from the viewpoint of improving finger combability. Preferred are (i) alkyltrimethylammonium salts, (v) alkoxyalkyldimethylamines and salts thereof, and (vi) alkylamidoamines and salts thereof. Furthermore, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, N,N-dimethyl-3-hexadecyloxypropylamine and its salts, N,N-dimethyl-3-octadecyloxypropylamine and its salts, N-(3 -(dimethylamino)propyl)docosanamide and its salts, N-(3-(dimethylamino)propyl)stearamide and its salts are preferred.

Any one of the component (C) cationic surfactants can be used alone or in combination of two or more. The content of component (C) in composition (2) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0% by mass, from the viewpoint of ensuring good finger combability. .5% by mass or more, more preferably 1.0% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 4% by mass. It is below. Also, preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, still more preferably 0.5% by mass to 5% by mass, still more preferably 1.0% by mass to 4% by mass.

<Component (D)>
Composition (2) used in step (ii) contains component (D) which is a higher alcohol.
Higher alcohols of component (D) may be linear or branched, saturated or unsaturated aliphatic alcohols, and preferably have 10 or more carbon atoms, more preferably 14 or more carbon atoms, and still more preferably 16 carbon atoms. and preferably 22 or less, more preferably 20 or less, and even more preferably 18 or less. Specific examples include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachyl alcohol, hexyldecanol, isostearyl alcohol, oleyl alcohol, 2-octyldodecanol and the like. Among these, stearyl alcohol, cetyl alcohol, and myristyl alcohol are preferred. These higher alcohols can be used singly or in combination of two or more.

The content of component (D) in (2) in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 1.5% by mass, from the viewpoint of ensuring good finger combability. % by mass or more, more preferably 2% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less. Also, preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass, still more preferably 1.5% by mass to 8% by mass, still more preferably 2% by mass to 8% by mass. be.
The ratio of the content of Component (D) to the content of Component (C) in Composition (2) [Component (D)/Component (C)] determines the stability of Composition (2) and good finger combability. From the viewpoint of ensuring the properties, it is preferably 0.2 or more, more preferably 0.3 or more, still more preferably 0.4 or more, and preferably 2.0 or less, more preferably 1.5 or less, and still more preferably 1.0 or less. Also, it is preferably 0.2 to 2.0, more preferably 0.3 to 1.5, still more preferably 0.4 to 1.0.

<Other Components in Composition (2)>
In addition to the above components, the composition (2) used in step (ii) may appropriately contain components commonly used in compositions for keratin fibers as long as they do not impair the object of the present invention. Examples of such components include anionic surfactants, nonionic surfactants, amphoteric surfactants, silicones, polyhydric alcohols, acids, alkaline agents, aromatic alcohols, dyes other than component (A), and polymers. , oils, anti-dandruff agents, vitamins, bactericides, anti-inflammatory agents, preservatives, chelating agents, moisturizers, pearl agents, ceramides, fragrances, ultraviolet absorbers, antioxidants, aqueous media and the like. Among these, it is preferable to contain one or more selected from the group consisting of silicones, polyhydric alcohols, acids, alkaline agents, preservatives and aqueous media.

(Silicones)
Composition (2) used in step (ii) preferably contains silicones in terms of smoothness when dried. Examples of such silicones include those shown below.

(1) Dimethylpolysiloxane Examples include those represented by the following general formula (8).
(CH ₃ ) ₃ SiO—[(CH ₃ ) ₂ SiO] _b —Si(CH ₃ ) ₃ (8)
[In formula (8), b represents a number from 3 to 20,000. ]

(2) Amino-modified silicone Amino-modified silicone may be in any form such as oil, emulsion, low-viscosity silicone or solution diluted with liquid paraffin. Amino-modified silicones include those listed in the INCI dictionary (United States, International Cosmetic Ingredient Dictionary and Handbook) 10th edition under the name of Amodimethicone, Aminoethylaminopropyl Dimethicone, or Aminopropyl Dimethicone. are preferred. This amino-modified silicone is preferably used as an aqueous emulsion, and commercially available amodimethicone products include "DOWSIL SM8904", "DOWSIL CB-1002" (manufactured by Dow Toray Industries, Inc.), "KT-0032", "XF42-B8922" (manufactured by Momentive Performance Materials), and the like.

(3) Other silicones In addition to the above, polyether-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, alkoxy-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic silicone, alkyl-modified silicone, etc. can be mentioned. be done.

Silicones can be used individually or in combination of 2 or more types.
When the composition (2) contains silicones, the content of the silicones in the composition (2) is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, more preferably It is 0.015% by mass or more, more preferably 0.02% by mass or more, and preferably 10% by mass or less, more preferably 6% by mass or less, and even more preferably 3% by mass or less. Also, preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 6% by mass, still more preferably 0.015% by mass to 6% by mass, still more preferably 0.02% by mass to 3% by mass.

(polyhydric alcohol)
Examples of polyhydric alcohols include those having 2 to 20 carbon atoms, specifically ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,2-butylene glycol and 1,3-butylene. alkylene glycols such as glycol and hexylene glycol; glycerins such as glycerin, diglycerin, and polyglycerin; sugar alcohols such as xylitol, mannite, galactit, and sorbitol; One or more selected from the group consisting of propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin and dipropylene glycol is particularly preferred.
A polyhydric alcohol can be used individually or in combination of 2 or more types.
When a polyhydric alcohol is used, the content of the polyhydric alcohol in the composition (2) is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, in terms of feel during and after use, applicability and usability. is 0.5% by mass or more, preferably 20% by mass or less, more preferably 8% by mass or less. Further, it is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 8% by 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 ease of pH adjustment.
Specific examples of weak acids include carboxylic acids such as citric acid, glycolic acid, succinic acid, tartaric acid, lactic acid, acetic acid, fumaric acid, malic acid, levulinic acid, butyric acid, valeric acid, oxalic acid, maleic acid, and mandelic acid. , phosphoric acid and the like. These acids are further preferably combined with their potassium salts and sodium salts to give the system a buffering ability.
Of these, carboxylic acids are preferred, and lactic acid is more preferred, from the viewpoint of odor and irritation.
When the composition (2) further contains an acid, the content of the acid in the composition (2) is preferably 3.0 from the viewpoint of ensuring good finger combability and imparting an effect of suppressing yellowness. It is 0% by mass or less, more preferably 2.5% by mass or less, still more preferably 1.5% by mass or less, still more preferably 1.0% by mass or less, and more preferably 0.6% by mass or less.
However, from the viewpoint of imparting an effect of suppressing yellowness, it is preferable that the composition (2) does not substantially contain an acid, and more preferably the acid content in the composition (2) is 0% by mass. .

Further, when the composition (2) further contains an acid, from the viewpoint of ensuring good finger combability and imparting an effect of suppressing yellowness, the content of the component (A) in the composition (1) The acid content ratio [(acid)/component (A)] in the composition (2) is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, even more preferably 10 or less, and 5 The following are even more preferred.

(Alkaline agent)
Composition (2) can contain an alkaline agent from the viewpoint of adjusting the pH of the formulation.
Alkanolamines such as mono-, di- or trimethanolamine, mono-, di- or triethanolamine; methylamine, dimethylamine, ethylamine, diethylamine, N-methylethylamine, propyl alkylamines such as amine and butylamine; aralkylamines such as benzylamine; inorganic alkali compounds such as sodium hydroxide and potassium hydroxide; and the like, and one or more of these can be used. The carbon number of the alkanolamine, alkylamine or aralkylamine is preferably 10 or less, more preferably 8 or less, from the viewpoint of water solubility.
Among them, from the viewpoint of ease of pH adjustment, the alkaline agent is preferably one or more selected from the group consisting of ammonia, alkanolamine, alkylamine, aralkylamine, sodium hydroxide, and potassium hydroxide. , ammonia and alkanolamine, more preferably monoalkanolamine, and even more preferably monoethanolamine.

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

(Preservative)
Composition (2) may contain a preservative.
Examples of the antiseptic include methyl p-hydroxybenzoate (methyl p-hydroxybenzoate), isopropylmethylphenol, phenoxyethanol, dehydroacetic acid and salts thereof.
When the composition (2) contains a preservative, the content of the preservative in the composition (2) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and It is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. Also, it is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 2% by mass, and more preferably 0.05% by mass to 1% by mass.

(aqueous medium)
Composition (2) usually contains an aqueous medium. Examples of the aqueous medium include those exemplified for composition (1), and water is preferred.
When the composition (2) contains an aqueous medium, the content of the aqueous medium in the composition (2) can be appropriately selected depending on the dosage form of the composition (2), but usually 1 to 95 mass % range.
When water is used as the aqueous medium, the content of water in the composition (2) is Preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass % or less. Also, it is preferably 50% to 95% by mass, more preferably 60% to 95% by mass, still more preferably 70% to 90% by mass, and even more preferably 80% to 90% by mass.

The method for producing composition (2) is not particularly limited. For example, components (C), (D), and other components used as necessary can be blended by the method described in the Examples, and mixed using a known stirring device or the like.

[Keratin fiber dyeing method]
The present invention further provides a method for dyeing keratin fibers, comprising in sequence the step of applying the above composition (1) to keratin fibers and the step of applying the above composition (2) to keratin fibers.
The step of applying the composition (1) to the keratin fibers can be the same step as the step (i) described above. The step of applying the composition (2) to the keratin fibers can be the same step as the step (ii) described above. Further, in the method for dyeing keratin fibers, similarly to the method for treating keratin fibers described above, between the step of applying the composition (1) to the keratin fibers and the step of applying the composition (2) to the keratin fibers, , the steps (i-1) to (i-3) described above. In the method for dyeing keratin fibers, similarly to the method for treating keratin fibers described above, when the composition (2) is used in a leave-off form after the step of applying the composition (2) to the keratin fibers, it is described above. Steps (ii-1) to (ii-2) may be included, and step (ii-2) may be included when the composition (2) is used in leave-on form.

The present invention provides, as one embodiment of the present invention, a step of applying composition (1) to keratin fibers as a cleansing agent; applying to the keratin fibers as a seed or two or more. That is, the composition (1), which is a detergent, is applied to keratin fibers, foamed to wash the keratin fibers, and then rinsed with water. Then, the composition (2), which is one or more selected from the group consisting of the rinse agent, conditioning agent and treatment agent, is applied to the keratin fibers for a short period of time (about 1 to 5 minutes) if necessary. Rinse with water after leaving. By repeating the above steps on a daily basis, the keratin fibers can be dyed easily and in a short period of time, and yellowing of the dyed color can be suppressed.

[Keratin fiber composition kit]
The present invention also provides a keratin fiber composition kit comprising the following configuration.
Specifically, a composition (1) having a pH of 8.0 or more and 12.0 or less containing the components (A) and (B), and a pH containing the components (C) and (D) A composition kit for keratin fibers comprising a composition (2) of 3.5 or more and less than 8.0.
The composition kit for keratin fibers can be, for example, in a form in which the composition (1) and the composition (2) are housed in separate containers and these containers are combined into a set.
In another aspect, in the keratin fiber composition kit, one container has at least two compartments, and the first compartment of the compartments contains the composition (1), The composition (2) can be accommodated in a second compartment different from the first compartment among the above compartments.

With respect to the above embodiments, the present invention discloses a method for treating keratin fibers, a composition kit for keratin fibers, and a method for dyeing keratin fibers.
<1>
A keratin fiber treatment method comprising the following steps (i) and (ii) in this order.
Step (i): Step (A) of applying a composition (1) containing the following components (A) and (B) and having a pH of 8.0 or more and 12.0 or less to keratin fibers. ) a compound represented by or a salt thereof

[In formula (1), the dashed line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group). and R ³ represents a hydrogen atom, an acetyl group, a methyl group or an ethyl group. ]
(B) Alkaline agent step (ii): A step of applying a composition (2) containing the following components (C) and (D) and having a pH of 3.5 or more and less than 8.0 to keratin fibers (C ) Cationic surfactant (D) higher alcohol <2>
The keratin fiber treatment method of <1>, wherein the composition (1) has a pH of 8.5 to 11.0, preferably 8.8 to 10.5, more preferably 9.0 to 10.0.
<3>
The pH of the composition (2) is 4.0 to 7.5, preferably 4.2 to 7.5, more preferably 4.3 to 7.3, still more preferably 4.8 to 7.3, and more The keratin fiber treatment method of <1> or <2>, which is more preferably 5.0 to 7.3, more preferably 5.0 to 7.1.
<4>
A keratin fiber treatment method comprising the following steps (i) and (ii) in this order.
Step (i): A step of applying a composition (1) containing the following components (A) and (B) and having a pH of 8.5 to 11.0 to keratin fibers (A) General formula (1 ) Compound represented by or a salt thereof 0.05 to 3 mass%

[In formula (1), the dashed line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group). and R ³ represents a hydrogen atom, an acetyl group, a methyl group or an ethyl group. ]
(B) alkaline agent 0.1 to 5% by mass
Step (ii): Step (C) Cationic surfactant of applying composition (2) containing the following components (C) and (D) and having a pH of 4.2 to 7.5 to keratin fibers Agent 0.1 to 10% by mass
(D) Higher alcohol 1 to 10% by mass
<5>
A keratin fiber treatment method comprising the following steps (i) and (ii) in this order.
Step (i): Step (A) of applying a composition (1) containing the following components (A) and (B) and having a pH of 8.8 or more and 10.5 or less to keratin fibers. ) Compound represented by or a salt thereof 0.1 to 1.0 mass%

[In formula (1), the dashed line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group). and R ³ represents a hydrogen atom, an acetyl group, a methyl group or an ethyl group. ]
(B) alkaline agent 0.5 to 3% by mass
Step (ii): Step (C) Cationic surfactant of applying composition (2) containing the following components (C) and (D) and having a pH of 5.0 or more and 7.3 or less to keratin fibers Agent 0.5 to 5% by mass
(D) Higher alcohol 2 to 8% by mass
<6>
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% by mass or less, still more preferably 0.6% by mass or less, the keratin fiber treatment method according to any one of <1> to <5>.
<7>
The ratio of the acid content in composition (2) to the content of component (A) in composition (1) [(acid)/component (A)] is 30 or less, preferably 20 or less, and 15 or less. is more preferable, 10 or less is more preferable, and 5 or less is even more preferable, the keratin fiber treatment method according to <6>.
<8>
The method for treating keratin fibers according to any one of <1> to <5>, wherein the composition (2) contains substantially no acid.
<9>
The method for treating keratin fibers according to any one of <1> to <8>, wherein component (B) is one or more selected from the group consisting of ammonia and alkanolamine.
<10>
The method for treating keratin fibers according to any one of <1> to <9>, wherein the composition (1) further contains an antioxidant as component (E).
<11>
<10>, wherein component (E) contains one or more selected from the group consisting of L-ascorbic acid, sulfurous acid, pyrosulfite, hydrogen sulfite or salts thereof, ascorbic acid glucoside and sulfur dioxide. Keratin fiber treatment method.
<12>
The method for treating keratin fibers according to any one of <1> to <11>, wherein the composition (1) further contains an anionic surfactant as component (F).
<13>
The method for treating keratin fibers according to any one of <1> to <12>, wherein the composition (1) is a detergent.
<14>
The method for treating keratin fibers according to any one of <1> to <13>, wherein the composition (2) is a rinse agent, conditioning agent or treatment agent.
<15>
The keratin fiber treatment method according to any one of <1> to <14>, comprising a step of rinsing the keratin fibers with water between step (i) and step (ii).
<16>
The method for treating keratin fibers according to <15>, wherein after the rinsing step, the keratin fiber is subjected to step (ii) while being kept in a wet state.
<17>
Any of <1> to <14> having the following steps (i-1), (i-2) and (i-3) between step (i) and step (ii) A method for treating keratin fibers as described.
Step (i-1): After application of the composition (1), any of the following steps: the step of allowing to stand, the step of foaming the composition (1), and the step of foaming the composition (1) and then allowing to stand Step (i -2): Step of rinsing composition (1) on keratin fibers with water Step (i-3): Step of drying keratin fibers <18>
The method for treating keratin fibers according to <17>, wherein the keratin fiber is subjected to step (ii) while being kept moist.
<19>
The method for treating keratin fibers according to any one of <1> to <17>, comprising a step (ii-1) of washing away the composition (2) on the keratin fibers with water after the step (ii).
<20>
The method for treating keratin fibers according to <19>, comprising a step of drying the keratin fibers (step (ii-2)) after performing step (ii-1).
<21>
The method for treating keratin fibers according to any one of <1> to <18>, comprising a step (ii-2) of drying the keratin fibers after step (ii).
<22>
The keratin fiber treatment method according to any one of <1> to <21>, which is a keratin fiber dyeing method.
<23>
Composition (1) having a pH of 8.0 or more and 12.0 or less containing the following components (A) and (B), and a pH of 3.5 containing the following components (C) and (D) A composition kit for keratin fibers, comprising the composition (2) above 8.0.
(A) a compound represented by the general formula (1) or a salt thereof

[In formula (1), the dashed line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group). and R ³ represents a hydrogen atom, an acetyl group, a methyl group or an ethyl group. ]
(B) alkaline agent (C) cationic surfactant (D) higher alcohol <24>
The composition kit for keratin fibers of <23>, wherein the composition (1) has a pH of 8.5 to 11.0, preferably 8.8 to 10.5, more preferably 9.0 to 10.0. .
<25>
The pH of the composition (2) is 4.0 to 7.5, preferably 4.2 to 7.5, more preferably 4.3 to 7.3, still more preferably 4.8 to 7.3, and more The composition kit for keratin fibers of <23> or <24>, which is more preferably 5.0 to 7.3, more preferably 5.0 to 7.1.
<26>
Composition (1) having a pH of 8.5 or more and 11.0 or less containing the following components (A) and (B), and a pH of 4.2 containing the following components (C) and (D) A composition kit for keratin fibers comprising the composition (2) of 7.5 or less.
(A) a compound represented by the general formula (1) or a salt thereof 0.05 to 3 mass%

[In formula (1), the dashed line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group). and R ³ represents a hydrogen atom, an acetyl group, a methyl group or an ethyl group. ]
(B) alkaline agent 0.1 to 5% by mass
(C) cationic surfactant 0.1 to 10% by mass
(D) Higher alcohol 1 to 10% by mass
<27>
Composition (1) having a pH of 8.8 or more and 10.5 or less containing the following components (A) and (B), and a pH of 5.0 containing the following components (C) and (D) 7. A composition kit for keratin fibers, comprising the composition (2) of 7.3 or less.
(A) a compound represented by the general formula (1) or a salt thereof 0.1 to 1.0 mass

[In formula (1), the dashed line indicates the presence or absence of a π bond, R ¹ represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group). and R ³ represents a hydrogen atom, an acetyl group, a methyl group or an ethyl group. ]
(B) alkaline agent 0.5 to 3% by mass
(C) cationic surfactant 0.5 to 5 mass%
(D) Higher alcohol 2 to 8% by mass
<28>
The composition (2) further contains an acid, and the acid content 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, and still more preferably The keratin fiber treatment method according to any one of <23> to <27>, wherein the content is 1.0% by mass or less, more preferably 0.6% by mass or less.
<29>
The ratio of the acid content in composition (2) to the content of component (A) in composition (1) [(acid)/component (A)] is 30 or less, preferably 20 or less, and 15 or less. is more preferable, 10 or less is more preferable, and 5 or less is even more preferable, the keratin fiber treatment method according to <28>.
<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.

Examples of the present invention will be described below, but the present invention is not limited to the scope of the examples. In the present Examples, pH measurement and dyeability evaluation were performed by the following methods.
[pH measurement]
Using a pH meter (F-51, manufactured by Horiba, Ltd.), the pH of the keratin fiber composition was measured at 25°C.

[Stainability evaluation]
For the evaluation of dyeability, goat wool (10 cm, Beaulux Co., Ltd.) having an L value of 85.1 to 86.1, an a value of 0.5 to 1.0, and a b value of 12.2 to 13.4 (manufacturer) A 1 g hair bundle was used.
A composition ( 1) was applied and blended for 30 seconds, followed by lathering for 30 seconds and rinsing with warm water (40°C) for 30 seconds. Next, after lightly squeezing the goat hair after rinsing to remove excess water, immediately mix the composition so that the bath ratio is 1:1:0.2 (goat hair bundle:water:composition (2)). (2) was applied and allowed to blend in for 60 seconds, followed by rinsing with warm water (40°C) for 30 seconds. After repeating this operation ten times, the goat hair was dried.
The hues (L ^* , a ^* , b ^* ) of the goat hair bundle before the dyeing treatment and the goat hair bundle after the dyeing treatment are measured using a color difference meter (CR-400, Konica Minolta, Inc.). Six points were measured for one goat hair bundle to obtain an average value, and the average value was used to calculate the color difference ΔE according to the following formula (9). It is evaluated that the larger the ΔE value, the better the dyeability. Also, the saturation (C ^* ) was calculated according to the following formula (10).
ΔE=[(ΔL ^* ) ² +(Δa ^* ) ² +(Δb ^* ) ² ] ^1/2 Equation (9)
(Δ: amount of change in each hue before and after dyeing)
C ^* = [(a ^* ) ² +(b ^* ) ² ] ^1/2 Equation (10)

[Color evaluation]
For the color evaluation, 5 expert panelists ranked goat wool after dyeing treatment in the following 5 stages as to whether or not they felt yellowness, and the most panelists gathered from A to E. The evaluation level was the evaluation of the goat hair bundle to be evaluated.
・A: Natural gray with no yellowness ・B: Gray with almost no yellowness ・C: Slightly yellowish but at an acceptable level ・D: Slightly yellowish It is light gray ・E: I feel a strong yellowness

[Evaluation of finger penetration]
For the evaluation of finger combability, hair tresses dyed by the following method were used.
First, for a Japanese woman's length of 10 cm, mass of 10 g, and a black hair tress hair bundle, the bath ratio is 1: 1 (hair bundle: hair dye) as a hair dye. Kao Corporation) was applied, left at 30°C for 15 minutes, and rinsed with warm water (40°C) for 30 seconds. Furthermore, the hair bundle after the above treatment is washed with a commercially available shampoo (Essential, manufactured by Kao Corporation) and washed with warm water (40 ° C.) twice, and then air-dried and dyed. A treated hair tress was obtained.
A bath ratio of 1:1:0.2 (hair bundle: water: composition (1)) was applied to the hair bundle that had been preliminarily rinsed with warm water (40°C) for 15 seconds and had been wetted. The composition (1) was applied to the skin so as to have a thickness of 30 seconds, followed by lathering for 30 seconds and rinsing with warm water (40° C.) for 30 seconds. Next, the composition (2) is applied to the hair tress after rinsing so that the bath ratio is 1:1:0.2 (tress:water:composition (2)) without drying by squeezing lightly. After soaking for 60 seconds, it was rinsed with warm water (40°C) for 30 seconds.
Five expert panelists evaluated the finger combability of the hair tresses after the above treatment, and ranked them in the following 6 stages. It was evaluated as a finger. A score of 3 or more is desirable.
・5 points: soft and smooth fingering ・4 points: smooth fingering ・3 points: no creaking ・2 points: slightly creaking ・1 point: strong creaking Finger passability/0 points: Hair is tangled and fingers cannot pass through

[Preparation of composition (1A)]
As composition (1), composition (1A), which is a cleaning agent, was prepared with the composition shown in Table 1 as follows.
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. Then, the mixed solution was mixed with L-ascorbic acid under a nitrogen atmosphere, and then mixed with a 5,6-dihydroxyindole solution to prepare composition (1A). All of the compounding amounts (parts by mass) shown in Table 1 are in the actual state.

[Preparation of composition (2A)]
As composition (2), composition (2A), which is a conditioning agent, was prepared with the composition shown in Table 1 as follows.
First, methyl p-hydroxybenzoate was added to purified water and then dissolved by heating to 80° C. to obtain an aqueous solution of methyl p-hydroxybenzoate. Next, distearyldimethylammonium chloride, stearyltrimethylammonium chloride, cetearyl alcohol and propylene glycol are heated to 80° C. and mixed, and the mixed solution is added to the aqueous solution of methyl p-hydroxybenzoate and mixed uniformly. After that, the temperature was lowered to 35°C. Next, after mixing a highly polymerized aminoethylaminopropylmethylsiloxane/dimethylsiloxane copolymer emulsion, lactic acid and monoethanolamine were mixed to prepare a composition (2A) having a pH of 4.2. All of the compounding amounts (parts by mass) shown in Table 1 are in the actual state.

[Preparation of compositions (2B) and (2C)]
Compositions (2B) and (2C) were adjusted to a pH of 5.3 by the same procedure as composition (2A), except that the amount of lactic acid was changed to 0.85 parts by mass and 0.79 parts by mass, respectively. and a composition (2C) having a pH of 7.1 were prepared.

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

[Preparation of composition (2E)]
A composition (2E) having a pH of 4.9 was prepared in the same manner as composition (2A) except that monoethanolamine and lactic acid were not used for composition (2E).

[Preparation of compositions (2F) and (2G)]
Compositions (2F) and (2G) were adjusted to a pH of 8.2 in the same manner as composition (2A), except that the amount of lactic acid was changed to 0.75 parts by mass and 4.73 parts by mass, respectively. and a composition (2G) having a pH of 3.1 were prepared.

The prepared composition (1A) and compositions (2A) to (2G) were stored under a nitrogen atmosphere and sampled each time pH measurement, dyeability evaluation, color evaluation, and finger combing evaluation were performed. . Table 1 shows the composition and pH of composition (1A) and the compositions and pH of compositions (2A) to (2G).

[Examples 1 to 5, Comparative Examples 1 and 2]
Examples 1 to 5 are the cases where the composition (1A) and each of the compositions (2A) to (2E) are used, and the composition (1A) and each of the compositions (2F) and (2G) was used as Comparative Examples 1 and 2, and evaluation of dyeability, evaluation of color, and evaluation of finger combability were performed. Table 1 shows the results.

The components in the table are shown below. In addition, all of the compounding amounts (parts by mass) of each component in the table are in the actual state.
*1: 5,6-dihydroxyindole solution: a solution produced by the method described in Japanese Patent No. 5570161 (5,6-dihydroxyindole: 1 mass%, 5,6-dihydroxyindole-2-carboxylic acid: 0.14% by mass, ethanol: 20% by mass, water: balance)
* 2: Sodium polyoxyethylene lauryl ether sulfate; Emal E-27C (manufactured by Kao Corporation, active ingredient content: 27.0% by mass, water: 71.7% by mass)
*3: Phosphoric acid; aqueous solution with phosphoric acid concentration of 75% by mass
*4: Purified water; adjust the blending amount so that the total amount is 100 parts by mass
* 5: Distearyldimethylammonium chloride; Cortamine D86P (manufactured by Kao Corporation, amount of active ingredient: 75% by mass, water: balance)
* 6: Stearyltrimethylammonium chloride; Cortamine 86W (manufactured by Kao Corporation, active ingredient content: 28% by mass, water: balance)
* 7: High degree of polymerization aminoethylaminopropylmethylsiloxane / dimethylsiloxane copolymer emulsion; silicone KT-0032 (manufactured by Momentive Performance Materials Japan LLC, active ingredient content: 40% by mass, water: 49% by mass )
*8: Lactic acid; an aqueous solution with a lactic acid concentration of 90% by mass
*9: Purified water; adjust the blending amount so that the total amount is 100 parts by mass

In this example, whether or not the keratin fiber treatment method of the present invention dyed to a natural gray color was evaluated by colorimetric values and visual evaluation. Regarding the evaluation of the colorimetric value, the larger the b ^* of the colorimetric value, the more yellowish it is. However, even if the value of b ^* is small, when the saturation increases, an unnatural color that is different from gray, which is originally achromatic, is felt. Therefore, in the present invention, it is preferable that b ^* is close to 0 and the chroma is small as a colorimetric value.

Table 1 reveals the following.
As shown in Examples 1 to 5, according to the method for treating keratin fibers of the present invention, a high dyeability of dyeing a natural gray color with less yellowness is exhibited. In addition, after washing with the composition (1) and conditioning with the composition (2) were repeated 10 times, the finished dyed color became a natural gray color. Furthermore, it is possible to improve finger combability of keratin fibers after step (i) using composition (1) and step (ii) using composition (2).
From the comparison between Examples 1 to 3 and Comparative Example 1 having the same composition as Examples 1 to 3 except that the pH of composition (2) was changed to more than 8.0 by changing the amount of lactic acid, the composition ( When the pH of 2) is more than 8.0, there is no significant difference in dyeability even after 10 repetitions of washing with the composition (1) and conditioning with the composition (2), and the color is good. , the finger combability of keratin fibers after step (i) using composition (1) and step (ii) using composition (2) is poor.
From the comparison between Examples 1 to 3 and Comparative Example 2 having the same composition as Examples 1 to 3 except that the amount of lactic acid was changed to make the pH of the composition (2) less than 3.5, the composition ( If the pH of 2) is less than 3.5, the keratin fibers after the step (i) using the composition (1) and the step (ii) using the composition (2) have good finger combability. However, after 10 repetitions of washing with the composition (1) and conditioning with the composition (2), the stainability is greatly reduced and yellowish.

In this specification, Formulation Examples 1 to 6 are disclosed in Table 2 below as one embodiment of the present invention.

The components in the table are shown below. In addition, all of the compounding amounts (parts by mass) of each component in the table are in the actual state.
*11: 5,6-dihydroxyindole solution: a solution produced by the method described in Japanese Patent No. 5570161 (5,6-dihydroxyindole: 1 mass%, 5,6-dihydroxyindole-2-carboxylic acid: 0.14% by mass, ethanol: 20% by mass, water: balance)
*12: 5,6-dihydroxyindoline hydrobromide solution (manufactured by AK-scientific, 5,6-dihydroxyindoline hydrobromide: 1% by mass, ethanol: 20% by mass, water: balance)
* 13: Sodium polyoxyethylene lauryl ether sulfate; Emal E-27C (manufactured by Kao Corporation, active ingredient content: 27.0% by mass, water: 71.7% by mass)
*14: Phosphoric acid; aqueous solution with phosphoric acid concentration of 75% by mass
* 15: Amphoteric surfactant (lauramidopropyl betaine); Amphithol 20AB (manufactured by Kao Corporation, active ingredient content: 28.8% by mass, water: 64.0% by mass)
*16: 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine; Amphithol 20Y-B (manufactured by Kao Corporation, active ingredient content: 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 (Novecare))
*19: Dimethyldiallylammonium chloride/acrylic acid copolymer liquid; MERQUAT 280NP POLYMER (manufactured by Lubrizol Advanced Materials, Inc., active ingredient content: 41.0% by mass, water: balance)
*20: Purified water; adjust the blending amount so that the total amount is 100 parts by mass
*21: Distearyldimethylammonium chloride; Cortamine D86P (manufactured by Kao Corporation, amount of active ingredient: 75% by mass, water: balance)
* 22: Stearyltrimethylammonium chloride; Cortamine 86W (manufactured by Kao Corporation, active ingredient content: 28% by mass, water: balance)
* 23: High degree of polymerization aminoethylaminopropylmethylsiloxane / dimethylsiloxane copolymer emulsion; silicone KT-0032 (manufactured by Momentive Performance Materials Japan LLC, active ingredient content: 40% by mass, water: 49% by mass )
*24: Lactic acid; an aqueous solution with a lactic acid concentration of 90% by mass
*25: Sodium hydroxide; an aqueous solution with a sodium hydroxide concentration of 48% by mass, adjusting the blending amount so that the pH is 5.0
*26: Purified water; adjust the blending amount so that the total amount is 100 parts by mass

According to the present invention, a first composition that gradually dyes keratin fibers and also has a hair washing function such as shampoo, and a second composition that imparts effects such as conditioning function and treatment are combined. By sequentially applying to the keratin fibers, the gradual dyeing of the keratin fibers is dyed to the original color expressed by the oxidation of melanin precursors with less yellowness while suppressing the deterioration of dyeability. It is possible to provide a keratin fiber treatment method capable of improving finger combability.

Claims

A keratin fiber treatment method comprising the following steps (i) and (ii) in this order.
Step (i): A step of applying a composition (1) containing the following components (A) and (B) and having a pH of 8.0 to 12.0 to keratin fibers (A) General formula (1 ) a compound represented by or a salt thereof

[In formula (1), the dashed line indicates the presence or absence of a π bond, R 1 represents a hydroxyl group or an acetoxy group, R 2 represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group). and R 3 represents a hydrogen atom, an acetyl group, a methyl group or an ethyl group. ]
(B) Alkaline agent step (ii): A step of applying a composition (2) containing the following components (C) and (D) and having a pH of 3.5 or more and less than 8.0 to keratin fibers (C ) Cationic surfactant (D) higher alcohol
The method for treating keratin fibers according to claim 1, wherein the component (B) is one or more selected from the group consisting of ammonia and alkanolamine.
The method for treating keratin fibers according to claim 1 or 2, wherein the composition (1) further contains an antioxidant as component (E).
4. The method according to claim 3, wherein component (E) contains one or more selected from the group consisting of L-ascorbic acid, sulfurous acid, pyrosulfite, hydrogen sulfite or salts thereof, ascorbic acid glucoside and sulfur dioxide. Keratin fiber treatment method.
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 component (F).
The method for treating keratin fibers according to any one of claims 1 to 5, wherein the composition (1) is a detergent.
The method for treating keratin fibers according to any one of claims 1 to 6, wherein the composition (2) is a rinse agent, conditioning agent or treatment agent.
The keratin fiber treatment method according to any one of claims 1 to 7, comprising a step of rinsing the keratin fibers with water between step (i) and step (ii).
The keratin fiber treatment method according to any one of claims 1 to 8, which is a keratin fiber dyeing method.
A composition (1) having a pH of 8.0 or more and 12.0 or less containing the following components (A) and (B), and a pH of 3.5 containing the following components (C) and (D) A composition kit for keratin fibers, comprising the composition (2) above 8.0.
(A) a compound represented by the general formula (1) or a salt thereof

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