JP2014193840A - Hair treating agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair treating agent composition which can impart an excellent slipperiness, an excellent coated feeling, and excellent softness to the hair during rinsing.SOLUTION: A hair treating agent composition comprises a cellulose ether containing a cationic group (A) and at least one treating agent (B) selected from a dye for hair dyeing, an oxidizing agent, an alkali agent, and a keratin-reducing agent.

Description

  The present invention relates to a hair treatment composition and a method for producing the same.

In recent years, with the diversification of hairstyles, chemical treatment with hair dyes, hair bleaching agents, permanent wave agents, straight permanent agents, long-lasting hair setting agents, curly hair straighteners, etc., excessive brushing and blowing Such daily hair care behavior or living environment such as ultraviolet rays makes hair easily damaged. Therefore, in order to coat the surface of the hair and return it to a smooth feel, the hair treatment composition has been devised in various ways.
For example, in the hair conditioning agent, a cationic polymer, an oil agent such as silicone, ester oil, mineral oil or the like is blended in order to improve the fingering property, softness, feeling of unity, and the like. However, when the blending amount is increased, stickiness occurs after hair drying, the feeling of use is lowered, and when the blending amount is decreased, the conditioning effect becomes insufficient.
Therefore, a hair treatment composition having a high conditioning effect is desired.

For example, Patent Document 1 discloses a cellulosic polymer such as hydroxypropyl cellulose as a hair dye / bleaching agent composition that has excellent base mixing properties, improved feel during rinsing, and improved hair feel after treatment. A hair dye / bleaching agent composition comprising an alkaline agent, a cationic surfactant, a first agent containing a higher alcohol and having a pH of 8 to 13, and an oxidizing agent and a second agent having a pH of 2 to 5 is disclosed .
Patent Document 2 discloses a hydrophobe-substituted water-soluble cationic polysaccharide. In the examples, after reacting glycidol with a cellulosic starting material, quaternization / alkylation is performed. The produced water-soluble cationic polysaccharide is exemplified. Further, it is mentioned that the aqueous solution of the cationic polysaccharide is capable of strong viscosity and forming, and is useful as a hair composition such as shampoo and rinse.
In Patent Document 3, substituted with a substituent containing an alkyl or arylalkyl group having 8 to 24 carbon atoms and a quaternary nitrogen-containing substituent in an amount of 0.0003 to 0.08 mol per mol of anhydroglucose unit. Cellulose ethers and hair care compositions such as shampoos containing the same are disclosed, and it is disclosed to improve combing properties when wet and dry.
Patent Document 4 includes cationized glycerolated cellulose in which the average addition mole number of cationic groups is 0.2 to 0.5 and the average addition mole number of glycerol groups is 1 to 2.5. A hair cosmetic composition is disclosed, and it is mentioned that the hair combing property is excellent at the time of washing.

JP 2007-126415 A Japanese Patent Laid-Open No. 61-181801 JP 2006-527785 A German Patent No. 3131667

However, the conventional hair treatment composition is not fully satisfactory in terms of use such as the slipperiness of the hair at the time of treatment rinsing and the feeling of coat, and the development of a hair treatment composition having a higher conditioning effect is desired. It is.
This invention makes it a subject to provide the hair treatment agent composition which can provide favorable slipperiness, a coating feeling, and softness to the hair at the time of a process rinse.

The present inventors have found that the above-described problems can be solved by incorporating a specific cationic group-containing cellulose ether into the hair treatment composition.
That is, the present invention provides the following [1] and [2].
[1] A hair treatment composition containing a cationic group-containing cellulose ether (A), and one or more treatment agents (B) selected from hair dyes, oxidizing agents, alkaline agents, and keratin reducing agents. The cationic group-containing cellulose ether (A) has a main chain derived from anhydroglucose represented by the following general formula (1), and substitution of a cationized oxyalkylene group per anhydroglucose unit The degree of substitution is 0.01 or more and 1.0 or less, the degree of substitution of the glycerol group is 0.5 or more and 5.0 or less, and the carbon number is 3 or more represented by the following general formulas (6) to (8) A hair treatment composition wherein the substitution degree of a group containing 18 or less hydrocarbon groups is 0.0001 or more and 0.3 or less.

(In the formula, R ¹ , R ² and R ³ each independently represent a substituent composed of one or more structural units selected from the following general formulas (2) to (8), or a hydrogen atom. (The average degree of polymerization of the main chain derived from anhydroglucose is shown and is a number of 100 or more and 12000 or less.)

(In the formula, the structural unit represented by the formula (2) or (3) represents a cationized oxyalkylene group, the structural unit represented by the formula (4) or (5) represents a glycerol group, and the formula (6 ) To (8) represent a group containing a hydrocarbon group having 3 to 18 carbon atoms, and R ^{4 to} R ⁹ are each independently a straight chain or branched chain having 1 to 3 carbon atoms. X ^- and Y ^- represent an anion, and r and s are each an integer of 0 to 3. R ¹⁰ and R ¹¹ are each independently a straight chain or branched chain having 1 to 16 carbon atoms. Or a linear or branched alkenyl group having 2 to 16 carbon atoms, R ¹² represents an alkyl group, alkenyl group, aralkyl group, or aryl group having 3 to 18 carbon atoms, and p is Represents an integer of 0 or 1. In the structural units represented by formulas (2) to (7) The oxygen atom is bonded to a hydrogen atom or a carbon atom of the structural unit.)
[2] A method for treating hair that is rinsed and dried after treating the hair with the hair treatment composition (hereinafter also referred to as the hair treatment method of the present invention).

  According to the present invention, it is possible to provide a hair treatment composition capable of imparting good slipperiness, coat feeling and softness to the hair at the time of treatment rinsing (hereinafter, these effects are obtained according to the present invention). Also called an effect.) In addition, the coat feeling at the time of a process rinse means the touch coat | covered with the hair treatment agent composition, The touch of the damaged hair can be improved, so that a coat feeling is strong.

[Hair treatment composition]
The hair treatment composition of the present invention (hereinafter also referred to as the treatment composition of the present invention) comprises a specific cationic group-containing cellulose ether (A) (hereinafter also referred to as “CCE (A)”), as well as a dye. It contains one or more treatment agents (B) selected from hair dyes, oxidizing agents, alkaline agents, and keratin reducing agents. When the hair treatment composition of the present invention contains CCE (A), it is possible to impart good slipperiness, coat feeling and softness to the hair at the time of treatment rinsing.

In the present invention, the hair treatment composition includes hair dyes such as hair dyes and hair bleaching agents, permanent wave agents, permanent permanent agents, permanent hair set agents, permanent hair setting agents, and permanent agents such as hair straighteners. It means a treating agent composition in a broad sense. As the hair treatment composition of the present invention, one or more selected from hair dyes and permanent agents are preferred.
≪Hair hair dye≫
In addition to CCE (A), the hair dye contains one or more treatment agents (B) selected from hair dyes, oxidizing agents, and alkaline agents. In the following, the term “hair dye” is a concept including a hair dye containing a dye and a hair decolorant containing no dye, and includes an agent that decolorizes and dyes hair.
Examples of the hair coloring agent include the following one-component hair coloring agents (a) and (b) and the following multi-component hair coloring agents (c) and (d). Among these, from the viewpoint of hair decolorization and dyeability, the following multi-component hair dyes (c) and (d) are preferable, and the multi-component hair dye (d) is more preferable.
(A) A one-component hair dye containing a hair dye and optionally an oxidizing agent.
(B) A one-pack hair hair dye that does not contain a hair dye and contains an oxidizing agent.
(C) A two-component hair dye comprising a first agent containing an alkali agent and / or a hair dye, and a second agent containing an oxidizing agent.
(D) A three-component hair dye comprising a first agent containing an alkaline agent and / or a hair dye, a second agent containing an oxidizing agent, and a third agent containing an oxidizing aid.

The hair dye can be applied to any type such as those used at room temperature and those used by heating.
In the two-component hair dye, the content ratio (mass ratio) of the first agent and the second agent [first agent / second agent] is preferably 2/8 to 6/4, and preferably 3/7 to 5/5 is more preferable, and 3.5 / 6.5 to 4.5 / 5.5 is still more preferable.

  The pH of the hair dye is preferably 3 or more and 9 or less in the case of a one-component hair dye in order to suppress damage to skin and hair. In the first agent of the two-component hair dye, the pH is preferably from 8 to 13, and in the second agent, the pH is preferably from 2 to 5. The pH of 8 to 13 is preferable for the first agent of the three-component hair dye, and the pH of 2 to 5 is preferable for the second agent. The pH can be adjusted using a known pH adjusting agent.

≪Permanent agent≫
A permanent agent contains 1 or more types of processing agents (B) chosen from a keratin reducing agent, an alkaline agent, and an oxidizing agent as a processing agent (B) other than CCE (A). The “perm agent” is a concept including a permanent wave agent, a straight permanent agent, and a hair straightener, and includes a first agent containing a keratin reducing agent and an alkali agent, and a second agent containing an oxidizing agent. It is a two-part type.
The pH of the permanent agent is preferably 6 or more and 12 or less for the first agent, and preferably 3 or more and 9 or less for the second agent in order to suppress damage to the skin or hair. The pH can be adjusted using a known pH adjusting agent.
The permanent agent can be applied to any type such as those used at room temperature, those used by heating, those intended for wave formation, and those intended for straightening hair.
In the permanent wave agent, the use amount ratio (mass ratio) of the first agent and the second agent [first agent / second agent] is preferably 3/7 to 7/3, more preferably 4/6 to 6/4. 4.5 / 5.5 to 5.5 / 4.5 is more preferable.

  From the above, the hair treatment composition of the present invention contains CCE (A) and one or more treatment agents (B) selected from hair dyes, oxidizing agents, alkaline agents, and keratin reducing agents. To do. In addition, when the hair treatment composition is a multi-drug type obtained by mixing two or more agents, the first agent is used from the viewpoint of imparting good slipperiness, coat feeling and softness to the hair during the treatment rinsing. It is preferable to blend CCE (A) with

Hereinafter, each component contained in the hair treatment composition of the present invention will be described.
(Cationic group-containing cellulose ether (A))
In the present invention, the cationic group-containing cellulose ether (A) has a main chain derived from anhydroglucose represented by the following general formula (1), and is a cationized oxyalkylene group per anhydroglucose unit. The substitution degree is 0.01 or more and 1.0 or less, the substitution degree of the glycerol group is 0.5 or more and 5.0 or less, and the carbon number is 3 represented by the following general formulas (6) to (8) The degree of substitution of the group containing a hydrocarbon group of 18 or less is 0.0001 or more and 0.3 or less.

In general formula (1), R ¹ , R ² and R ³ each independently represent a substituent composed of one or more structural units selected from the following general formulas (2) to (8), or a hydrogen atom. . n represents the average degree of polymerization of the main chain derived from anhydroglucose, and is a number of 100 or more and 12000 or less.

In the formula, the structural unit represented by the formula (2) or (3) represents a cationized oxyalkylene group, the structural unit represented by the formula (4) or (5) represents a glycerol group, and the formula (6) The structural unit represented by (8) represents a group containing a hydrocarbon group having 3 to 18 carbon atoms. R ^{4 to} R ⁹ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, X ⁻ and Y ⁻ represent anions, and r and s are integers of 0 to 3 inclusive. R ¹⁰ and R ¹¹ each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. R ¹² represents an alkyl group, an alkenyl group, an aralkyl group, or an aryl group having 3 to 18 carbon atoms, and p represents an integer of 0 or 1. In the structural units represented by formulas (2) to (7), the oxygen atom is bonded to a hydrogen atom or a carbon atom of the structural unit.

<Substituents R ¹ , R ² and R ³ >
In the general formula (1), when the substituent R ¹ is a substituent composed of one or more structural units selected from the formulas (2) to (8), the substituent R ¹ is represented by the formula (2) to It may be a substituent composed of a plurality of structural units selected from (8), or a substituent in which a hydrogen atom is bonded to an oxygen atom of only one structural unit selected from formulas (2) to (8). There may be.
When the substituent R ¹ is a substituent composed of a plurality of structural units selected from the formulas (2) to (7), the structural units include an oxygen atom of one structural unit and a carbon of the other structural unit. An oxygen atom which is bonded to an atom and which is not bonded to a carbon atom of another structural unit, for example, an oxygen atom located at the end of a substituent is bonded to a hydrogen atom.
The combination of the structural units is not particularly limited, and a plurality of one type of structural units selected from the formulas (2) to (8) may be bonded, or 2 selected from the formulas (2) to (8). ~ 7 types of structural units may be bonded. In the general formula (1), R ¹ is a substituent having two or more groups selected from the group comprising the cationized oxyalkylene group, the glycerol group, and the hydrocarbon group having 3 to 18 carbon atoms. In some cases, the bonding mode may be block bonding, random bonding, or alternating bonding, but block bonding is preferable from the viewpoint of ease of manufacture.

When the substituent R ¹ is a substituent composed of one or more structural units selected from the formulas (2) to (8), the terminal carbon atom is an oxygen atom of the hydroxyl group of the main chain derived from anhydroglucose. Are connected.
Incidentally, when the substituent R ¹ is a substituent consisting of one or more structural units selected from the formulas (2) to (8), the substituent as long as it does not impair the effects of the present invention, the formula ( Structural units other than the structural units of 2) to (8) may be included.
When the substituent R ² is a substituent composed of one or more structural units selected from the formulas (2) to (8), the embodiment of the substituent is such that the substituent R ¹ is represented by the formulas (2) to ( This is the same as in the case of the substituent consisting of one or more structural units selected from 8).
When the substituent R ³ is a substituent composed of one or more structural units selected from the formulas (2) to (8), the embodiment of the substituent is such that the substituent R ¹ is the formula (2) to ( This is the same as in the case of the substituent consisting of one or more structural units selected from 8).
The substituents R ¹ , R ² , and R ³ are independent and may be the same or different from each other.

<Cationized Oxyalkylene Group Represented by Formula (2) or (3)>
In the formulas (2) and (3), R ^{4 to} R ⁹ are each independently a linear or branched alkyl group having 1 to 3 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, Examples include an n-propyl group and an isopropyl group. In these, a methyl group or an ethyl group is preferable from a viewpoint of the availability of a reaction agent, and a methyl group is more preferable.
In the formulas (2) and (3), X ⁻ and Y ⁻ represent an anion which is a counter ion of a quaternary ammonium ion. X ⁻ and Y ⁻ are not particularly limited as long as they are anions. Specific examples include alkyl sulfate ions having 1 to 3 carbon atoms, sulfate ions, phosphate ions, fatty acid ions having 1 to 3 carbon atoms, and halides. One or more selected from ions and the like can be mentioned.
Among these, from the viewpoint of ease of production, one or more selected from alkyl sulfate ions having 1 to 3 carbon atoms, sulfate ions, and halide ions are preferable, and halide ions are more preferable. The halide ion includes one or more selected from fluoride ion, chloride ion, bromide ion and iodide ion. From the viewpoint of water solubility and chemical stability of CCE (A), chloride ion is used. And one or more selected from bromide ions are preferred, and chloride ions are more preferred.
r and s each represent an integer of 0 or more and 3 or less. From the viewpoint of easy availability of raw materials, r and s are preferably 1.

<Group containing a hydrocarbon group having 3 to 18 carbon atoms>
In the present invention, the group containing a hydrocarbon group having 3 to 18 carbon atoms refers to a structural unit represented by the general formulas (6) to (8). When CCE (A) used for this invention has this structural unit, when using for a hair-treatment agent composition especially, at the time of a process rinse, favorable sliding property, a coating feeling, and softness can be provided.
From the above viewpoint, the number of carbon atoms of the hydrocarbon group having 3 to 18 carbon atoms is preferably 3 or more and 7 or less, more preferably 3 or more and 6 or less, and further preferably 3 or more and 4 or less.
In the formulas (6) and (7), R ¹⁰ and R ¹¹ are each independently a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. Therefore, the formulas (6) and (7) contain a hydrocarbon group having 3 to 18 carbon atoms. Specific examples of R ¹⁰ and R ¹¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and isopentyl group. , Neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, nonyl group, decyl group, dodecyl group, vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 2-heptenyl group, octenyl group and the like. Among these, from the viewpoint of imparting the water-solubility of CCE (A) and the effects of the present invention, an alkyl group having 1 to 14 carbon atoms or an alkenyl group having 2 to 14 carbon atoms is preferable, and one or more carbon atoms are preferable. An alkyl group having 10 or less carbon atoms or an alkenyl group having 2 to 10 carbon atoms is more preferable, an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms is more preferable, and an alkyl group having 1 to 5 carbon atoms. Group or an alkenyl group having 2 to 5 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. More preferably, a methyl group or an ethyl group is still more preferable, and an ethyl group is still more preferable.
In the formula (8), R ¹² is an alkyl group, alkenyl group, aralkyl group, or aryl group having 3 to 18 carbon atoms. Specific examples thereof include an n-propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, nonyl group, decyl group, dodecyl Group, tridecyl group, tetradecyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, Examples include 1-heptenyl group, 2-heptenyl group, octenyl group, phenyl group, methylphenyl group, and benzyl group. Among these, from the viewpoints of imparting good slipperiness, coat feeling, and softness when treated with water-soluble CCE (A) and a hair treatment composition, preferably 3 carbon atoms. 14 or less, more preferably 3 or more and 10 or less, more preferably 3 or more and 7 or less, and even more preferably 3 or more and 6 or less, an alkyl group, an alkenyl group, or a phenyl group. One or more selected from an alkyl group and an alkenyl group having 3 to 6 carbon atoms is more preferable, and an alkyl group having 3 to 6 carbon atoms is more preferable.

<Substitution degree of cationized oxyalkylene group>
In the present invention, the degree of substitution of the cationized oxyalkylene group (hereinafter also referred to as “MS (N +)”) is the number of cationized oxyalkylene groups present in the molecule of CCE (A) and constitutes the main chain. The average value per anhydroglucose unit. MS (N +) is measured and calculated by the method described in Examples below.
MS (N +) in CCE (A) used for this invention is 0.01 or more and 1.0 or less. When MS (N +) is within this range, good slipperiness, coat feeling, and softness can be obtained when rinsing the hair with the hair treatment composition. From this viewpoint, MS (N +) is preferably 0.04 or more, more preferably 0.05 or more, further preferably 0.10 or more, and further preferably 0.12 or more. Moreover, from the viewpoint of the above viewpoint and the production cost of the CCE (A) of the present invention, it is preferably 0.9 or less, more preferably 0.7 or less, still more preferably 0.6 or less, still more preferably 0.5 or less, More preferably, it is 0.3 or less, More preferably, it is 0.22 or less.
From these viewpoints, MS (N +) is preferably in the range of 0.04 to 0.9, more preferably in the range of 0.04 to 0.7, and still more preferably in the range of 0.04 to 0.6. More preferably, it is in the range of 0.04 to 0.5, more preferably in the range of 0.04 to 0.3, still more preferably in the range of 0.04 to 0.22, and still more preferably in the range of 0.12 to 0.22. It is a range.

<Degree of substitution of glycerol group>
In the present invention, the degree of substitution of the glycerol group (hereinafter, also referred to as “MS (Gly)”) is the number of glycerol groups present in the molecule of CCE (A), one anhydroglucose unit constituting the main chain. This is the average value for hits. MS (Gly) is measured and calculated by the method described in Examples below.
The MS (Gly) of CCE (A) used in the present invention is 0.5 or more and 5.0 or less. When MS (Gly) is within this range, good slipperiness, coat feeling, and softness can be obtained when rinsing the hair with the hair treatment composition. Moreover, if MS (Gly) is this range, since the solubility to the hair-treatment agent composition of CCE (A) is high, a mixing | blending is easy. From these viewpoints, MS (Gly) is preferably 0.8 or more, more preferably 1.0 or more, still more preferably 1.8 or more, and still more preferably 2.1 or more. From the above viewpoint and the viewpoint of the production cost of CCE (A), MS (Gly) is preferably 4.0 or less, more preferably 3.5 or less, still more preferably 3.0 or less, still more preferably 2.5 or less, More preferably, it is 2.3 or less.
Further, from these viewpoints and the viewpoint of ease of blending, MS (Gly) is preferably in the range of 0.5 to 4.0, more preferably in the range of 0.8 to 3.5, and still more preferably 1. It is in the range of 0 to 3.0, more preferably in the range of 1.8 to 2.5, and still more preferably in the range of 2.1 to 2.3.

<Substitution degree of group containing hydrocarbon having 3 to 18 carbon atoms>
In the present invention, the degree of substitution of a group containing a hydrocarbon having 3 to 18 carbon atoms (hereinafter also referred to as “MS (HC)”) is the above formula (6) present in the CCE (A) molecule. The average value of the number of groups containing a hydrocarbon having 3 to 18 carbon atoms represented by (8) with respect to one anhydroglucose unit constituting the main chain. MS (HC) is measured and calculated by the method described in Examples below.
The MS (HC) of CCE (A) used in the present invention is 0.0001 or more and 0.3 or less. When MS (HC) is within this range, good slipperiness, coat feeling, and softness can be obtained when rinsing the hair with the hair treatment composition. From these viewpoints, MS (HC) is preferably 0.0005 or more, more preferably 0.001 or more, still more preferably 0.005 or more, still more preferably 0.01 or more, still more preferably 0.02 or more, and further Preferably it is 0.03 or more. From the above viewpoint and the viewpoint of the production cost of CCE (A), MS (HC) is preferably 0.25 or less, more preferably 0.2 or less, still more preferably 0.15 or less, still more preferably 0.10 or less, More preferably, it is 0.08 or less, More preferably, it is 0.06 or less.
Further, from the viewpoint of the above and the production cost of CCE (A), MS (HC) is preferably in the range of 0.0005 to 0.25, more preferably in the range of 0.001 to 0.25, and still more preferably. Is in the range of 0.005 to 0.25, more preferably in the range of 0.01 to 0.25, more preferably in the range of 0.01 to 0.2, still more preferably in the range of 0.01 to 0.15, More preferably, it is in the range of 0.01 to 0.10, more preferably in the range of 0.02 to 0.08, still more preferably in the range of 0.02 to 0.06, and still more preferably in the range of 0.03 to 0.06. It is a range.

<Cation charge density>
CCE (A) used in the present invention preferably has a cationic charge density of 0.05 mmol / g or more from the viewpoint of obtaining good slipperiness, coat feeling, and softness when rinsing the hair with the hair treatment composition. More preferably, it is 0.15 mmol / g or more, more preferably 0.2 mmol / g or more, and 0.3 mmol / g or more. From the above viewpoint, the cation charge density is preferably 2.0 mmol / g or less, more preferably 1.5 mmol / g or less, still more preferably 1.2 mmol / g or less, and still more preferably 0.9 mmol / g or less.
From the above viewpoint, the cation charge density of CCE (A) is preferably 0.05 to 2.0 mmol / g, more preferably 0.15 to 1.5 mmol / g, and still more preferably 0.2 to 1.2 mmol. / G, more preferably 0.3 to 0.9 mmol / g.
In the present invention, the cation charge density means the number of moles of a cationic group contained per gram of CCE (A), and is calculated from the following calculation formula.
Cationic charge density (mmol / g) = MS (N +) / (74.1 × MS (Gly) + a × MS (HC) + b × MS (N +) + 162.1) × 1000
(Wherein, a represents the molecular weight of a group containing a hydrocarbon group, and b represents the molecular weight of a cationized oxyalkylene group.)

  The cationic charge density of the CCE (A) can also be measured by a colloid titration method.

  CCE (A) preferably has an MS (N +) of 0.04 or more and 0.6 or less from the viewpoint of obtaining good slipperiness, coat feeling, and softness when rinsing the hair with the hair treatment composition. , MS (Gly) is 0.5 or more and 4.0 or less, and MS (HC) is 0.01 or more and 0.10 or less, more preferably MS (N +) is 0.04 or more and 0.22 or less. MS (Gly) is 1.0 or more and 3.0 or less and MS (HC) is 0.01 or more and 0.1 or less, more preferably MS (N +) is 0.12 or more and 0.00. The CCE is 22 or less, the MS (Gly) is 2.1 or more and 2.3 or less, and the MS (HC) is 0.02 or more and 0.06 or less.

<Average degree of polymerization of CCE (A)>
In CCE (A) used in the present invention, the average polymerization degree n of the main chain derived from anhydroglucose means the viscosity average polymerization degree measured by the copper-ammonia method described in the examples. When the etherification reaction is performed in an inert gas such as nitrogen, the depolymerization of cellulose does not proceed, and the average degree of polymerization of the raw material cellulose and CCE (A) can be regarded as equivalent. In the present invention, the average degree of polymerization of cellulose which is a raw material of CCE is regarded as the average degree of polymerization n of CCE. Moreover, in this invention, the average degree of polymerization of a cellulose means the viscosity average degree of polymerization of a cellulose, and can be specifically measured by the method as described in an Example.
The average degree of polymerization n varies depending on the average degree of polymerization of cellulose used as a raw material for CCE (A) and the method for producing CCE (A), but the effect of the present invention can be obtained if it is 100 or more and 12000 or less.
The average degree of polymerization n is preferably 200 or more, more preferably 500 or more, and still more preferably 1000 or more, from the viewpoint of imparting the effects of the present invention. From the above viewpoint and the viewpoint of improving the handling properties of CCE (A) and the treatment agent composition, the average degree of polymerization n is preferably 10,000 or less, more preferably 5000 or less, and still more preferably 2500 or less.
From these viewpoints, the average degree of polymerization n is preferably in the range of 200 to 10,000, more preferably in the range of 500 to 5000, and still more preferably in the range of 1000 to 2500.

<Viscosity of 1 mass% aqueous solution of CCE (A)>
The CCE (A) used in the present invention preferably has a 1 mass% aqueous solution viscosity at 25 ° C. of CCE (A) of 10 mPa · s from the viewpoint of obtaining good slipperiness during rinsing, a feeling of coating, and softness. As mentioned above, More preferably, it is 50 mPa * s or more, More preferably, it is 100 mPa * s or more, More preferably, it is 150 mPa * s or more. In addition, from the viewpoints described above and from the viewpoint of improving the handling properties of CCE (A) and the treatment agent composition, it is preferably 10,000 mPa · s or less, more preferably 5000 mPa · s or less, still more preferably 3000 mPa · s or less, and still more. Preferably it is 2000 mPa * s or less.
From these viewpoints, the viscosity of the 1 mass% aqueous solution of CCE (A) at 25 ° C. is preferably in the range of 10 to 10000 mPa · s, more preferably in the range of 50 to 5000 mPa · s, and still more preferably 100 to 3000 mPa · s. It is the range of s, More preferably, it is the range of 150-2000 mPa * s. In addition, the aqueous solution viscosity of CCE (A) is measured by the method as described in an Example.

<Manufacture of CCE (A)>
The CCE (A) used in the present invention comprises a cellulose, a cationizing agent corresponding to the cationized oxyalkylene group of the CCE (A) (hereinafter also simply referred to as “cationizing agent”), a glycerolating agent, and carbon. It can be produced by reacting with an introducing agent of a group containing a hydrocarbon group of several 3 or more and 18 or less (hereinafter also simply referred to as “hydrocarbon group-containing group”). Here, the order of the cationization reaction, glycerolation reaction, and hydrocarbon group-containing group introduction reaction is not particularly limited, any of which may be performed first, may be performed simultaneously, or may be performed repeatedly in any order. Also good. If the cationized oxyalkylene group or the hydrocarbon group-containing group is first introduced into the cellulose, the yield of the glycerolation reaction based on the glycerolating agent tends to decrease. It is preferable to perform a cationization reaction and a hydrocarbon group-containing group introduction reaction thereafter.
In general, cellulose has high crystallinity and therefore lacks reactivity. Therefore, it is preferable to reduce the crystallinity and improve the reactivity before the reaction. Examples of such a method for producing CCE (A) include the following methods (i) to (iii).
Method (i): Activation method generally called arserization or mercerization, that is, after mixing raw material cellulose with a large amount of water and a large excess of alkali metal hydroxide to obtain alkali cellulose, glycerolating agent , A cationizing agent, and a hydrocarbon group-containing group introduction agent.
Method (ii): Cellulose, for example, dimethyl sulfoxide containing tetrabutylammonium fluoride, dimethyl sulfoxide containing paraformaldehyde, dimethylacetamide containing lithium chloride, “encyclopedia of cellulose, editor: Cellulose Society, publisher: Asakura Shoten ", Macromol. Chem. Phys. 201, 627-631 (2000) or the like, a solvent capable of dissolving cellulose is used to dissolve raw material cellulose, and then raw material cellulose, a glycerolating agent, a cationizing agent, and a hydrocarbon group-containing group-introducing agent are introduced. How to react.
Method (iii): Powdery or cotton-like raw material cellulose and glycerolating agent, cation without using a special solvent capable of dissolving excess alkali or cellulose as in the above methods (i) and (ii) And a method of reacting a hydrocarbon group-containing group introduction agent in the presence of an alkali.
Hereinafter, the cellulose, the glycerolating agent, the cationizing agent, and the hydrocarbon group-containing group-introducing agent used as the raw material for producing CCE (A) will be described in detail.

[Raw material cellulose]
Although there is no restriction | limiting in particular in the kind of cellulose (henceforth "raw material cellulose") used for the raw material of CCE (A), From a viewpoint of cellulose purity, a polymerization degree, and availability, various wood chips; Pulp such as wood pulp produced and cotton linter pulp obtained from fibers around cotton seeds is preferred.
The average degree of polymerization of the raw material cellulose is preferably 100 or more, more preferably 200 or more, and still more preferably 500 from the viewpoint of obtaining good slipperiness, coat feeling, and softness when rinsing the hair with the hair treatment composition. More preferably, it is 1000 or more, and preferably 12000 or less, more preferably 10,000 or less, still more preferably 5000 or less, and still more preferably, from the viewpoints described above and from the viewpoint of improving the handling properties of CCE (A) and the treatment agent composition. Preferably it is 2500 or less.
From these viewpoints, the average degree of polymerization of the raw material cellulose is preferably in the range of 100 to 12000, more preferably in the range of 200 to 10,000, still more preferably in the range of 500 to 5000, and still more preferably in the range of 1000 to 2500. It is.
The average degree of polymerization of the raw material cellulose refers to the viscosity average degree of polymerization measured by the copper-ammonia method described in the examples.
The shape of the raw material cellulose is not particularly limited as long as the introduction into the production apparatus is not hindered, but from the viewpoint of operation, it is preferably a sheet shape, a pellet shape, a chip shape, a cotton shape, or a powder shape. , Cotton or powder is more preferred, and cotton or powder is even more preferred. Chip-like cellulose can be obtained, for example, by cutting raw material cellulose. Cotton-like or powdery cellulose can be obtained, for example, by subjecting raw material cellulose or raw material cellulose subjected to a cutting treatment to a pulverization treatment after performing a drying treatment as necessary.

[Cutting]
Depending on the type and shape of the raw material cellulose, it is preferable to perform a cutting treatment as a pretreatment for the pulverization treatment. The method for cutting the raw material cellulose can be selected as appropriate depending on the type and shape of the raw material cellulose. For example, a method using one or more cutting machines selected from a shredder, a slitter cutter and a rotary cutter is mentioned. It is done.
When using sheet-form raw material cellulose, it is preferable to use a shredder or a slitter cutter as a cutting machine, and it is more preferable to use a slitter cutter from a viewpoint of productivity.
The slitter cutter is a cutting machine that cuts vertically with a roll cutter in the longitudinal direction along the longitudinal direction of the sheet to form a long and narrow strip, and then cuts it shortly along the width direction of the sheet with a fixed blade and a rotating blade. By using a slitter cutter, the shape of the raw material cellulose can be changed to a dice shape. As the slitter cutter, a sheet pelletizer manufactured by Horai Co., Ltd. can be preferably used. When this apparatus is used, the sheet-like raw cellulose can be cut into about 1 to 20 mm square.

When cutting wood such as thinned wood, pruned branches, construction waste, or other raw material cellulose, it is preferable to use a rotary cutter. The rotary cutter is composed of a rotary blade and a screen, and by using the rotary cutter, raw cellulose that is cut by the rotary blade into a size smaller than the mesh of the screen can be easily obtained. In addition, if necessary, a fixed blade may be provided and cutting may be performed with a rotary blade and a fixed blade.
When a rotary cutter is used, the size of the coarsely pulverized product obtained can be controlled by changing the opening of the screen. The opening of the screen is preferably 1 mm or more, more preferably 2 mm or more, further preferably 3 mm or more, more preferably 70 mm or less, more preferably 50 mm or less, and further preferably 40 mm or less. If the opening of the screen is 1 mm or more, a coarsely pulverized product having an appropriate bulkiness is obtained, and the handleability is improved. If the opening of the screen is 70 mm or less, the subsequent pulverization process has an appropriate size as a pulverization raw material, and thus the load can be reduced.

  The size of the raw material cellulose obtained after the cutting treatment is preferably 1 mm square or more, more preferably 2 mm square or more, preferably 70 mm square or less, more preferably 50 mm square or less. By cutting to 1 mm square or more and 70 mm square or less, the load required for pulverization in the subsequent pulverization process can be reduced, and the drying process described later can be performed efficiently and easily.

[Drying treatment]
The water content when pulverizing raw material cellulose is preferably as low as possible. The lower limit of the water content during the pulverization treatment is 0% by mass with respect to the raw material cellulose, but from the viewpoint of productivity, the water content is preferably 0.01% by mass or more, more preferably 0.05% by mass. As mentioned above, More preferably, it is 0.1 mass% or more. Further, from the viewpoint of the pulverization efficiency of the raw material cellulose, the water content is preferably 10% by mass or less, more preferably 7% by mass or less, and still more preferably 6% by mass or less. From the above viewpoint, the water content during the pulverization treatment is preferably 0.01 to 10% by mass, more preferably 0.05 to 7% by mass, and still more preferably 0.1 to 6% by mass.
In general, raw material cellulose such as commercially available pulps, papers used as biomass resources, woods, plant stems / leaves, plant shells and the like contain water exceeding 5% by mass, and usually 5 to 30%. It contains about mass% moisture. Therefore, it is preferable to adjust the moisture content of the raw material cellulose by drying the raw material cellulose, preferably the raw material cellulose obtained after the cutting treatment.

As a drying method, a known drying means may be appropriately selected. For example, hot air heat receiving drying method, conductive heat receiving drying method, dehumidified air drying method, cold air drying method, microwave drying method, infrared drying method, sun drying method , Vacuum drying method, freeze drying method and the like.
In the above drying method, a known dryer can be appropriately selected and used. For example, “Introduction to Powder Engineering” (Edited by Japan Powder Industry Technology Association, Powder Technology Information Center 1995) page 176 And the like.
These drying methods and dryers may be used alone or in combination of two or more. The drying process can be either a batch process or a continuous process, but a continuous process is desirable from the viewpoint of productivity.

As the continuous dryer, a conductive heat receiving horizontal stirring dryer is preferable from the viewpoint of heat transfer efficiency. Further, a biaxial horizontal stirrer is preferable from the viewpoint of the stability of continuous discharge because fine powder is hardly generated. As the biaxial horizontal stirrer / dryer, a biaxial paddle dryer manufactured by Nara Machinery Co., Ltd. can be preferably used.
The temperature in the drying treatment cannot be determined unconditionally depending on the drying means, drying time, etc., but is preferably 10 ° C. or higher, more preferably 25 ° C. or higher, still more preferably 50 ° C. or higher, and preferably 250 ° C. or lower. More preferably, it is 180 degrees C or less, More preferably, it is 150 degrees C or less. The treatment time is preferably 0.01 hours or more, more preferably 0.02 hours or more, and preferably 48 hours or less, more preferably 24 hours or less. The drying treatment may be performed under reduced pressure as necessary. The pressure is preferably 1 kPa or more, more preferably 50 kPa or more, and preferably 120 kPa or less, more preferably 105 kPa or less.

[Crushing treatment]
There is no restriction | limiting in particular in the grinder used by a grinding | pulverization process, What is necessary is just an apparatus which can pulverize or flocify raw material cellulose.
Specific examples of the pulverizer include a high pressure compression roll mill, a roll mill such as a roll rotating mill, a vertical roller mill such as a ring roller mill, a roller race mill or a ball race mill, a rolling ball mill, a vibration ball mill, a vibration rod mill, and a vibration tube. Container driven medium mill such as mill, planetary ball mill or centrifugal fluidization mill, tower crusher, stirring tank mill, medium stirring mill such as flow tank mill or annular mill, compaction such as high-speed centrifugal roller mill and ang mill Examples include a shear mill, a mortar, a stone mill, a mass collider, a fret mill, an edge runner mill, a knife mill, a pin mill, and a cutter mill.
Among these, from the viewpoint of the efficiency of pulverization of cellulose, productivity, and the efficiency of the introduction agent such as subsequent glycerolation, a container-driven medium mill or a medium stirring mill is preferable, and a container-driven medium mill is more preferable. A vibration mill such as a vibration ball mill, a vibration rod mill, or a vibration tube mill is more preferable, and a vibration rod mill is still more preferable. The pulverization method may be either batch type or continuous type.

There are no particular limitations on the material of the apparatus used for the pulverization treatment and the material of the medium, for example, iron, stainless steel, alumina, zirconia, silicon carbide, silicon nitride, glass, etc., from the viewpoint of the pulverization efficiency of the raw material cellulose, Iron, stainless steel, zirconia, silicon carbide and silicon nitride are preferable, and iron or stainless steel is particularly preferable from the viewpoint of industrial use.
From the viewpoint of grinding efficiency of raw material cellulose, when the apparatus used is a vibration mill and the medium is a rod, the outer diameter of the rod is preferably 0.1 mm or more, more preferably 0.5 mm from the viewpoint of grinding efficiency. From the above viewpoint, it is preferably 100 mm or less, and more preferably 50 mm or less.
The rod filling ratio varies depending on the type of vibration mill, but is preferably 10% or more, more preferably 15% or more, and still more preferably 50% or more, from the viewpoint of cellulose grinding efficiency and productivity. In addition, it is preferably 97% or less, more preferably 95% or less. From the above viewpoint, the filling rate of the rod is preferably 10 to 97%, more preferably 15 to 97%, and still more preferably 50 to 95%.
When the filling rate is within this range, the contact frequency between the cellulose and the rod is improved, and the grinding efficiency can be improved without hindering the movement of the medium. Here, the filling rate refers to the apparent volume of the rod relative to the volume of the stirring section of the vibration mill.

Although there is no particular limitation on the temperature during the pulverization treatment, from the viewpoint of suppressing the decomposition of cellulose and from the viewpoint of operation cost, it is preferably −100 ° C. or higher, more preferably 0 ° C. or higher, and further preferably 10 ° C. or higher. From the viewpoint, it is preferably 200 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 70 ° C. or lower. From the above viewpoint, the temperature during the pulverization treatment is preferably −100 to 200 ° C., more preferably 0 to 100 ° C., and still more preferably 10 to 70 ° C.
What is necessary is just to adjust the time of a grinding | pulverization process suitably so that raw material cellulose may be pulverized or cotton-like. The pulverization time varies depending on the pulverizer used, the amount of energy used, and the like, but is usually from 10 seconds to 12 hours. The pulverization time is preferably 15 seconds or more, more preferably 20 seconds or more from the viewpoint of sufficiently pulverizing the raw material cellulose or cotton, and from the viewpoint of productivity, preferably 3 hours or less, more preferably 1 Less than time, more preferably less than 20 minutes. From the above viewpoint, the pulverization time is preferably 15 seconds to 3 hours, more preferably 15 seconds to 1 hour, and still more preferably 20 seconds to 20 minutes.

[Glycerol agent]
Glycidol: 3-halo-1,2-propanediol such as 3-chloro-1,2-propanediol and 3-bromo-1,2-propanediol is used as the glycerolating agent used in the production of CCE (A). Glycerol; 1 or more types chosen from glycerol carbonate etc. are mentioned. Among these, glycidol is preferable from the viewpoint of no salt by-product and reactivity.
These glycerolating agents can be used alone or in combination of two or more.
The amount of the glycerolating agent to be used may be appropriately selected in consideration of the desired MS (Gly). From the viewpoint of the water solubility of CCE (A) and the effect of the present invention, anhydroglucose of the raw material cellulose The amount is preferably 0.2 mol or more, more preferably 1 mol or more, still more preferably 3 mol or more, still more preferably 5 mol or more, per 1 mol of the unit (hereinafter also referred to as “AGU”). From the viewpoint of the production cost of CCE (A), it is preferably 60 mol or less, more preferably 50 mol or less, still more preferably 45 mol or less, and still more preferably 40 mol or less.
From these viewpoints, the amount of the glycerolating agent to be used is preferably 0.2 to 60 mol, more preferably 1 to 50 mol, still more preferably 3 to 45 mol, relative to 1 mol of AGU of the raw material cellulose. More preferably, it is 5-40 mol.
The method for adding the glycerolating agent may be any of batch, intermittent and continuous, but continuous addition is preferred from the viewpoint of increasing the reaction yield of the glycerolating agent to the raw material cellulose.

[Cationizing agent]
Examples of the cationizing agent used in the production of CCE (A) include compounds represented by the following general formula (9) or (10).

In General Formulas (9) and (10), R ^{13 to} R ¹⁸ and preferred embodiments thereof are the same as R ^{4 to} R ^{9 in} General Formulas (2) and (3). t, u and preferred embodiments thereof are the same as r in the general formula (2) and s in the general formula (3). Q ⁻ , W ⁻ and preferred embodiments thereof are the same as X ^{− in the} general formula (2) and Y ^{− in the} general formula (3). Z represents a halogen atom. R ^{13 to} R ¹⁸ may be the same as or different from each other.

Specific examples of the compound represented by the general formula (9) or (10) include chloride, bromide or iodide of glycidyltrimethylammonium, glycidyltriethylammonium and glycidyltripropylammonium, and 3-chloro-2- Hydroxypropyltrimethylammonium, 3-chloro-2-hydroxypropyltriethylammonium, or 3-chloro-2-hydroxypropyltripropylammonium chloride, 3-bromo-2-hydroxypropyltrimethylammonium, 3-bromo-2- Hydroxypropyltriethylammonium or 3-bromo-2-hydroxypropyltripropylammonium bromide, 3-iodo-2-hydroxypropyltrimethylammonium, 3-iodo, respectively 2-hydroxypropyl triethyl ammonium, or 3-iodo-2-hydroxypropyl respectively iodide tripropyl ammonium.
Among these, from the viewpoint of easy availability of raw materials and chemical stability, chloride or bromide of glycidyltrimethylammonium or glycidyltriethylammonium; 3-chloro-2-hydroxypropyltrimethylammonium or 3-chloro-2- Hydroxypropyltriethylammonium chloride; preferably one or more selected from 3-bromo-2-hydroxypropyltrimethylammonium or bromide of 3-bromo-2-hydroxypropyltriethylammonium, glycidyltrimethylammonium chloride and 3-chloro-2 One or more selected from -hydroxypropyltrimethylammonium chloride is more preferable, and glycidyltrimethylammonium chloride is more preferable.
These cationizing agents can be used alone or in combination of two or more.

The amount of the cationizing agent to be used may be appropriately selected in consideration of the desired MS (N +) and reaction yield. From the viewpoint of the water solubility of CCE (A) and the effect of the present invention, the raw material Preferably, it is 0.01 mol or more, more preferably 0.03 mol or more, and still more preferably 0.05 mol or more, with respect to 1 mol of AGU of cellulose. Is 60 mol or less, more preferably 10 mol or less, still more preferably 8 mol or less, and still more preferably 5 mol or less. Further, the amount of the cationizing agent to be used is preferably 0.01 to 60 mol, more preferably 0.01 to 10 mol, still more preferably 0.03 to 8 mol, and still more preferably 0, from these viewpoints. 0.05 to 5 moles.
The method of adding the cationizing agent may be any of batch, intermittent and continuous.

[Introducing agent for hydrocarbon group-containing group]
The hydrocarbon group-containing group-introducing agent used in the production of CCE (A) may be any one that can introduce the structural units represented by the general formulas (6) to (8).
Examples of the introducing agent capable of introducing the structural unit represented by the general formula (6) or (7) include compounds represented by the following general formula (11) or (12).

In general formulas (11) and (12), R ¹⁹ , R ²⁰ and preferred embodiments thereof are the same as R ^{10 in} general formula (6) and R ^{11 in} general formula (7). A represents a halogen atom.
Specific examples of the compound represented by the general formula (11) include propylene oxide, 1,2-butylene oxide, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,2-epoxyoctadecane and the like can be mentioned.
Specific examples of the compound represented by the general formula (12) include 1-chloro-2-propanol, 1-chloro-2-butanol, 1-bromo-2-butanol, 1-chloro-2-pentanol, 1-chloro-2-hexanol, 1-chloro-2-heptanol, 1-chloro-2-octanol, 1-chloro-2-nonanol, 1-chloro-2-decanol, 1-chloro-2-undecanol, 1- Chloro-2-dodecanol, 1-chloro-2-tridecanol, 1-chloro-2-tetradecanol, 1-chloro-2-pentadecanol, 1-chloro-2-hexadecanol, 1-chloro-2- Examples include 1-halo-2-alkanol having 3 to 18 carbon atoms such as heptadecanol and 1-chloro-2-octadecanol.
Among these, the compound represented by the general formula (11) is preferable from the viewpoints of no salt by-product during the reaction, easy availability of raw materials, and chemical stability. From the viewpoint of obtaining good slipperiness, coat feeling and softness at the time of rinsing with the hair treatment composition of the present invention, propylene oxide, 1,2-butylene oxide, 1,2-epoxypentane and 1 1, 2-epoxyhexane is preferable, one or more selected from propylene oxide and 1,2-butylene oxide is more preferable, and 1,2-butylene oxide is still more preferable.
These can be used alone or in combination of two or more.

  Examples of the introduction agent capable of introducing the structural unit represented by the general formula (8) include compounds represented by the following general formulas (13) to (15).

In the general formulas (13) to (15), R ²¹ , R ²² , R ²³ , R ²⁴ and preferred embodiments thereof are the same as R ^{12 in the} general formula (8). q and preferred embodiments thereof are the same as p in the general formula (8). B represents a halogen atom. In the general formula (15), R ²³ and R ²⁴ may be different but are preferably the same.
When the compound represented by the general formula (14) is used, the glycerol group represented by the general formula (4) or (5) and the structural unit represented by the general formula (8) (provided that p Is 0) at the same time.
Specific examples of the compound represented by the general formula (13) include 1-chloropropane, 1-propane bromide, 1-butane chloride, 1-butane bromide, 1-pentane chloride, 1-pentane bromide, 1-chlorohexane, 1-hexane bromide, 1-heptane chloride, 1-heptane bromide, 1-octane chloride, 1-chlorodecane, 1-chloride dodecane, 1-chloride tetradecane, 1-hexadecane chloride, 1-chloride Alkanes having 3 to 18 carbon atoms such as octadecane, 1-chloro-3-butene, benzyl chloride, halides of alkenes, alkenes or arylalkanes; Carboxyl having 4 to 19 carbon atoms such as butanoic acid chloride and hexanoic acid chloride And acid halides. Among these, it is preferable to use an alkane halide having 3 to 7 carbon atoms.
Specific examples of the compound represented by the general formula (14) include propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, lauryl glycidyl ether. , Glycidyl ether having an alkyl group having 3 to 18 carbon atoms, such as tetradecyl glycidyl ether and stearyl glycidyl ether; glycidyl ether having an alkenyl group having 3 to 18 carbon atoms; phenyl glycidyl ether, tolyl glycidyl ether, benzyl glycidyl Examples include ether.
Specific examples of the compound represented by the general formula (15) include butanoic anhydride, hexanoic anhydride, octanoic anhydride, decanoic anhydride, lauric anhydride, tetradecanoic anhydride, stearin Examples thereof include carboxylic acid anhydrides having an alkyl group having 3 to 18 carbon atoms, such as acid anhydrides.
Among these, from the viewpoint of easy availability of raw materials and chemical stability, the compound represented by the general formula (13) or (14) is preferable, the water solubility of CCE (A), and the present invention. From the viewpoint of the effect, one or more selected from halides of alkanes having 3 to 18 carbon atoms and glycidyl ethers having an alkyl group having 3 to 18 carbon atoms are preferable, and halides of alkanes having 3 to 7 carbon atoms. And one or more selected from glycidyl ethers having an alkyl group having 3 to 7 carbon atoms, more preferably glycidyl ethers having an alkyl group having 3 to 7 carbon atoms. Specifically, one or more selected from 1-bromohexane, 1-octane chloride, 1-dodecane chloride, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, and stearyl glycidyl ether are preferable. 1 or more types chosen from propyl glycidyl ether and butyl glycidyl ether are more preferable, and butyl glycidyl ether is still more preferable.
These can be used alone or in combination of two or more.

The amount of the hydrocarbon group-containing group-introducing agent to be used may be appropriately selected in consideration of the desired MS (HC) and reaction yield. From the viewpoints described above and the production cost of CCE (A), the amount is preferably 0.01 mol or more, more preferably 0.03 mol or more, still more preferably 0.1 mol or more, relative to 1 mol of AGU of the raw material cellulose. Therefore, it is preferably 5 mol or less, more preferably 3 mol or less, and still more preferably 2 mol or less. From these viewpoints, the amount of the hydrocarbon group-containing group-introducing agent to be used is preferably 0.01 to 5 mol, more preferably 0.03 to 3 mol, and still more preferably with respect to 1 mol of AGU of the raw material cellulose. Is 0.1 to 2 mol.
The method for adding the hydrocarbon group-containing group introduction agent may be any of batch, intermittent, and continuous.

[Alkali compounds]
CCE (A) is preferably prepared by reacting powdered cellulose or cotton-like cellulose obtained by the above pulverization treatment with the above-mentioned glycerolating agent, cationizing agent and hydrocarbon group-containing group-introducing agent. It can be obtained by carrying out the reaction of introducing a cationization reaction, a cationization reaction and a hydrocarbon group-containing group.
These reactions are all carried out in the presence of an alkali compound. Examples of the alkali compound used in the reaction include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, trimethylamine, and triethylamine. And tertiary amines. Among these, alkali metal hydroxides or alkaline earth metal hydroxides are preferred from the viewpoint of reaction rate of glycerolation reaction, cationization reaction and introduction reaction of hydrocarbon group-containing group, and alkali metal hydroxides are preferred. Are more preferable, and sodium hydroxide and potassium hydroxide are more preferable. These alkali compounds can be used alone or in combination of two or more.
There is no particular limitation on the method of adding the alkali compound, and batch addition or divided addition may be used. In addition, the alkali compound may be added in a solid state or may be added as an aqueous solution.

Except in the case of the above method (i), the amount of the alkali compound used in the glycerolation reaction is the same as that of a monovalent basic compound such as an alkali metal hydroxide or a compound having one tertiary amine in the molecule. In this case, from the viewpoint of improving the reaction activity of cellulose and the reaction selectivity of the glycerolation reagent, it is preferably 0.2 mol or more, more preferably 0.7 mol or more, more preferably 0.1 mol or more, based on 1 mol of AGU of the raw material cellulose. Preferably it is 0.8 mol or more, and from the above viewpoint, it is preferably 2.0 mol or less, more preferably 1.3 mol or less, still more preferably 1.2 mol or less.
From the above viewpoint, the amount of the alkali compound used in the glycerolation reaction is preferably 0.2 to 2.0 mol, more preferably 0.7 to 1.3 mol, relative to 1 mol of AGU of the raw material cellulose. More preferably, it is 0.8-1.2 mol.
Except in the case of the method (i), when the cationization reaction and the hydrocarbon-containing group introduction reaction are separately performed, the amount of the alkali compound used in each reaction is the case where the alkali compound is a monovalent base compound. Is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.1 mol or more, based on 1 mol of AGU of the raw material cellulose, from the viewpoint of reaction selectivity of the reactant. From the viewpoint, it is preferably 1.0 mol or less, more preferably 0.8 mol or less, still more preferably 0.5 mol or less. From the above viewpoint, the amount of the alkali compound used in each of the cationization reaction and the hydrocarbon-containing group introduction reaction is preferably relative to 1 mol of AGU of the raw material cellulose when the alkali compound is a monovalent basic compound. It is 0.01-1.0 mol, More preferably, it is 0.05-0.8 mol, More preferably, it is 0.1-0.5 mol.
In addition, the preferable amount of the alkali compound used when the cationization reaction and the introduction reaction of the hydrocarbon-containing group are simultaneously performed is also the same as the amount of the alkali compound used for each of the cationization reaction and the introduction reaction of the hydrocarbon-containing group. It is.
When the alkali compound used in the glycerolation reaction, cationization reaction, or hydrocarbon group-containing group introduction reaction is a polyvalent base such as an alkaline earth metal hydroxide, the preferred range of the amount of the alkali compound used is The range of the preferable amount of the alkali compound in each of the above reactions is a range obtained by dividing the range by the polyvalent base valence. For example, when the alkali compound used is calcium hydroxide (divalent base), the amount of calcium hydroxide used in the glycerolation reaction is improved in the reaction activity of cellulose, except in the case of the method (i), and From the viewpoint of reaction selectivity of the glycerolation reagent, it is preferably 0.1 mol or more, more preferably 0.35 mol or more, still more preferably 0.4 mol or more, relative to 1 mol of AGU of the raw material cellulose, From the viewpoint, it is preferably 1.0 mol or less, more preferably 0.65 mol or less, and still more preferably 0.6 mol or less. From the above viewpoint, when the alkali compound is a polyvalent base, the amount of the alkali compound used in the glycerolation reaction is preferably 0.1 to 1.0 mol, more preferably 1 mol of AGU of the raw material cellulose. Is 0.35 to 0.65 mol, more preferably 0.4 to 0.6 mol.

CCE (A) is preferably prepared by reacting powdered cellulose or cotton-like cellulose obtained by the above pulverization treatment with the above-mentioned glycerolating agent, cationizing agent and hydrocarbon group-containing group-introducing agent. It can be obtained by carrying out the reaction of introducing a cationization reaction, a cationization reaction and a hydrocarbon group-containing group. Hereinafter, the glycerolation reaction, the cationization reaction, and the introduction reaction of the hydrocarbon group-containing group are collectively referred to as “reaction at the time of producing CCE (A)”.
In each reaction during the production of CCE (A), there is no particular limitation on the form of the glycerolating agent, the cationizing agent and the hydrocarbon group-containing group-introducing agent added. If the glycerolating agent, cationizing agent and hydrocarbon group-containing group introduction agent are in a liquid state, they may be used as they are, or diluted with a glycerolating agent such as water or a non-aqueous solvent or a good solvent such as a cationizing agent. It may be used in the form.
Examples of the non-aqueous solvent used for dilution include generally used secondary or tertiary lower alcohols having 3 to 4 carbon atoms such as isopropanol and tert-butanol; 3 carbon atoms such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. 6 or less ketones; ethers such as tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; and aprotic polar solvents such as dimethyl sulfoxide.
Each reaction during the production of CCE (A) is carried out by dissolving the raw material cellulose in the method (ii) using a solvent capable of dissolving cellulose during the reaction, but the methods (i) and (iii) In addition, in view of the reaction yield of the glycerolating agent, the cationizing agent and the hydrocarbon group-containing group-introducing agent, the reaction can be carried out in the presence of a non-aqueous solvent. As the non-aqueous solvent, the same non-aqueous solvent as described above can be used.
The amount of these nonaqueous solvents used is preferably 100% by mass or more, more preferably 1000% by mass or more, still more preferably 5000% by mass or more, based on the raw material cellulose, from the viewpoint of the effect of adding the nonaqueous solvent. From the viewpoint of productivity and reaction yield, it is preferably 100000 mass% or less, more preferably 50000 mass% or less, still more preferably 20000 mass% or less. Moreover, from the said viewpoint, the usage-amount of a nonaqueous solvent becomes like this. Preferably it is 100-100000 mass% with respect to raw material cellulose, More preferably, it is 1000-50000 mass%, More preferably, it is 5000-20000 mass%.

As an apparatus used for each reaction at the time of the production of CCE (A), a mixer such as a readyge mixer capable of stirring, a mixer such as a so-called kneader used for kneading powders, high-viscosity substances, resins, etc. Can be mentioned.
From the viewpoint of the reaction rate, the temperature during the reaction of each reaction during the production of CCE (A) is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and further preferably 30 ° C. or higher. Moreover, from the suppression of decomposition of the glycerolating agent, cationizing agent, or hydrocarbon group-containing group introduction agent, the temperature is preferably 200 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 80 ° C. or lower. From the above viewpoint, the temperature during the reaction is preferably 0 to 200 ° C, more preferably 20 to 100 ° C, and still more preferably 30 to 80 ° C.
What is necessary is just to adjust suitably the reaction time of each reaction at the time of CCE (A) manufacture by the reaction rate etc. of the introduction agent of a glycerolating agent, a cationizing agent, and a hydrocarbon group containing group. The reaction time is usually from 0.1 hours to 72 hours, and from the viewpoint of reaction yield and productivity, preferably 0.2 hours or more, more preferably 0.5 hours or more, still more preferably 1 hour or more, more More preferably, it is 3 hours or more. Moreover, it is preferably 36 hours or less, more preferably 18 hours or less, still more preferably 12 hours or less, and still more preferably 8 hours or less. From the above viewpoint, the reaction time is preferably 0.2 to 36 hours, more preferably 0.5 to 18 hours, still more preferably 1 to 12 hours, and still more preferably 3 to 8 hours.
In addition, it is preferable to perform each reaction at the time of CCE (A) manufacture in inert gas atmosphere, such as nitrogen, as needed from a viewpoint which suppresses coloring and the molecular weight fall of the principal chain derived from anhydroglucose.

After completion of the reaction, the alkali can be neutralized with an acid. When the glycerolation reaction, the cationization reaction, and the hydrocarbon group-containing group introduction reaction are separately performed, neutralization can be performed between each reaction. It is preferable to carry out after completion of the reaction. As the acid, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid and lactic acid can be used.
CCE (A) obtained after completion of all the reactions during the production of CCE (A) is separated by filtration or the like as necessary, or washed with hot water, hydrous isopropyl alcohol, hydrous acetone solvent, etc. The cationizing agent, the glycerolating agent, the introduction agent of the hydrocarbon group-containing group, the by-products derived from these reactants, and the salts by-produced by neutralization or the like can be removed before use. In addition, as a purification method, a general purification method such as reprecipitation purification, centrifugation, or dialysis can be used.

<Content of CCE (A)>
The content of the cationic group-containing cellulose ether (A) in the treatment composition of the present invention is preferably from the viewpoint of obtaining good slipperiness, coat feeling, and softness when rinsing the hair with the treatment composition. Is 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and further preferably 0.4% by mass or more. Further, from the viewpoints described above, and from the viewpoint of handling properties of CCE (A) and the treatment agent composition, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less, and still more preferably 1%. It is below mass%. Moreover, from these viewpoints, the content of CCE (A) in the treatment agent composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and still more preferably 0.1 to 0.1% by mass. It is 2 mass%, More preferably, it is 0.2-2 mass%, More preferably, it is 0.4-2 mass%, More preferably, it is 0.4-1 mass%.

(Treatment agent (B))
The hair treatment composition of the present invention contains one or more treatment agents (B) selected from hair dyes, oxidizing agents, alkaline agents, and keratin reducing agents in addition to CCE (A).

<Dye for hair dyeing>
The hair dye is used in a hair treatment composition such as a hair dye.
Hair dyes include direct dyes and oxidative dye intermediates.
The direct dye is not particularly limited as long as it is usually used in cosmetics, and examples thereof include nitro dyes, anthraquinone dyes, acid dyes, oil-soluble dyes, and basic dyes.
Examples of the nitro dye include HC blue 2, HC orange 1, HC red 1, HC red 3, HC yellow 2, and HC yellow 4, and the anthraquinone dye includes 1-amino-4-methylaminoanthraquinone, 1, 4-diaminoanthraquinone etc. are mentioned.
As acid dyes, red No., orange No., yellow No., green No., blue No., purple No. 401, black No. 401, Acid Blue 1, No. 3, No. 62, Acid Black 52, Acid Brown 13 Acid Green 50, Acid Orange 6, Acid Red 14, 35, 73, 184, Brilliant Black 1 and the like.
Examples of oil-soluble dyes include red No., orange No., yellow No., green No. 202, purple No. 201, blue No. 403, etc., and basic dyes such as Basic Blue 6, No. 7, No. 9, 26, 41, 99, Basic brown 4, 16, Basic brown 17, Basic green 1, Basic red 2, 12, 22, 51, 76, Basic violet 1, 3, 10, 14 and 57, basic yellow 57 and 87, basic orange 31 and the like.
The above direct dyes can be used alone or in combination of two or more.

As the oxidation dye intermediate, known precursors and couplers that are usually used in hair dyes can be used.
As the precursor, paraphenylenediamine, toluene-2,5-diamine, orthochloroparaphenylenediamine, N-phenylparaphenylenediamine, N, N-bis (hydroxyethyl) paraphenylenediamine, 3-methyl-4-aminophenol , 2-hydroxyethylparaphenylenediamine, paraaminophenol, paramethylaminophenol, 4-aminometacresol, orthoaminophenol and salts thereof.
Couplers include resorcin, 2-methylresorcin, 1-naphthol, 1,5-dihydroxynaphthalene, 5-aminoorthocresol, metaphenylenediamine, metaaminophenol, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, Examples include 2-methyl-5-hydroxyethylaminophenol, 2-amino-3-hydroxypyridine, and salts thereof.
The above oxidation dye intermediates can be used alone or in combination of two or more.

The content of the direct dye is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.1% by mass or more in the hair treatment composition from the viewpoint of dyeability to hair. Moreover, 10 mass% or less is preferable, 5 mass% or less is more preferable, and 2 mass% or less is still more preferable. In addition, from the above viewpoint, the content of the direct dye is preferably 0.005 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.1 to 2% by mass in the hair treatment composition. .
The content of the precursor and the coupler, which is an oxidative dye intermediate, is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, in the hair treatment composition, from the viewpoint of dyeability to hair. 0.1% by mass or more is more preferable, 0.2% by mass or more is further preferable, 10% by mass or less is preferable, 7.5% by mass or less is more preferable, and 5% by mass or less is further preferable, and 3% by mass. The following is more preferable, and 2% by mass or less is more preferable. Further, from the above viewpoint, the content of the precursor and the coupler is preferably 0.01 to 10% by mass, more preferably 0.05 to 7.5% by mass, and more preferably 0.1 to 5% by mass in the hair treatment composition. % Is still more preferable, 0.2-3 mass% is still more preferable, and 0.2-2 mass% is still more preferable.

<Oxidizing agent>
The oxidizing agent is used in a hair treatment composition such as a hair dye or a permanent agent. When the hair treatment composition is a permanent wave agent, it is blended with a permanent wave second agent for use in combination with the permanent wave first agent.

Oxidizing agents used for hair dyes include hydrogen peroxide, hydrogen peroxide or oxygen peroxide generators such as urea peroxide, melamine peroxide, sodium perborate, potassium perborate, sodium percarbonate, percarbonate. Potassium etc. are mentioned, It can use individually or in combination of 2 or more types. From the viewpoint of dyeability to hair, hydrogen peroxide is preferable.
When the hair treatment composition is a hair dye, the content of the oxidizing agent is determined from the viewpoint of sufficient hair dyeing / bleaching properties and reduction of hair damage and scalp irritation. 0.1% by mass or more in the product is preferable, 0.5% by mass or more is more preferable, 2% by mass or more is more preferable, 4% by mass or more is further preferable, 12% by mass or less is preferable, and 9% by mass or less. Is more preferable, and 8 mass% or less is more preferable. In addition, from the above viewpoint, the content of the oxidizing agent is preferably 0.1 to 12% by mass, more preferably 0.5 to 9% by mass, still more preferably 2 to 9% by mass in the hair treatment composition. -8 mass% is still more preferable.

Examples of the oxidizing agent used in the permanent wave second agent include potassium bromate, sodium bromate, sodium perborate, hydrogen peroxide, and the like, and these can be used alone or in combination of two or more.
The content of the oxidizing agent in the permanent wave second agent is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less. Moreover, 1-20 mass% is preferable and, as for content of the oxidizing agent in a permanent wave 2nd agent, 2-10 mass% is more preferable. Thereby, the disulfide bond of the cut | disconnected keratin in hair can fully be recombined.

<Alkaline agent>
Alkaline agents are used in hair treatment compositions such as hair dyes and permanent agents.
Examples of the alkaline agent contained in the hair coloring agent include sodium hydroxide, ammonia and salts thereof; alkanolamines such as monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol and 2-aminobutanol and salts thereof; Examples include alkanediamines such as 1,3-propanediamine and salts thereof; carbonates such as guanidine carbonate, sodium carbonate, potassium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like. These can be used alone or in combination of two or more. Of these, ammonia, alkanolamines, alkanediamines and salts thereof, and carbonates are more preferable, and ammonia, alkanolamines and salts thereof are still more preferable from the viewpoint of dyeability on hair.
When the hair treatment composition is a hair dye, the content of the alkaline agent is selected from the viewpoints of sufficient dyeability and decolorization, and reduction of hair damage and scalp irritation. The content is preferably 0.1% by mass or more and 10% by mass or less.

Examples of the alkaline agent contained in the permanent agent are the same as those for the hair dye. In the permanent agent, the alkaline agent is used together with a keratin reducing agent described later.
Among these, from the viewpoint of improving the action of the keratin reducing agent, ammonia, alkanolamines and salts thereof, and sodium hydrogen carbonate are preferable.
When the hair treatment composition is a permanent agent, the content of the alkaline agent is 0.1% by mass in the hair treatment composition from the viewpoint of curl retention after treatment and irritation to hair and skin. The content is preferably 10% by mass or less.

<Keratin reducing agent>
Keratin reducing agents are used in hair treatment compositions such as permanent agents. The keratin reducing agent can cleave the disulfide bond of keratin constituting the hair. The composition containing such a keratin reducing agent can be preferably used as the permanent wave first agent in the permanent agent composition.
Examples of the keratin reducing agent include thioglycolic acid and derivatives thereof, thiolactic acid and derivatives thereof, cysteine and derivatives thereof, or salts thereof, thioglyceryl alkyl ether of the following formula (16) or salt thereof, and of the following formula (17) Examples include mercaptoalkylamides and salts thereof.
R ⁷ OCH ₂ CH (OH) CH ₂ SH (16)
(In the formula, R ⁷ represents a hydrogen atom, a lower alkyl group or a lower alkoxy lower alkyl group.)
_{H- (CHOH) x1 - (CH} 2) y1 -CONH (CH 2) z1 -SH (17)
(In the formula, x1 is a number from 0 to 5, y1 is a number from 0 to 3, and z1 is a number from 2 to 5. However, y1 and z1 are not 0 at the same time.)

Specific examples of the keratin reducing agent include thioglycolic acid, ammonium thioglycolate, glyceryl thioglycolate ester, L-cysteine, D-cysteine, N-acetylcysteine, ammonium salts of these cysteines, monoethanolamine, diethanolamine, Examples include ethanolamine salts such as triethanolamine, thioglyceryl alkyl ethers such as ethoxyhydroxypropanethiol, methoxyethoxyhydroxypropanethiol, and isopropoxyethoxyhydroxypropanethiol, mercaptoethylpropanamide, mercaptoethylgluconamide, and the like.
Said keratin reducing agent can be used individually or in combination of 2 or more types.
The content of the keratin reducing agent is preferably 0.1% by mass or more, preferably 1% by mass or more in the hair treatment composition from the viewpoint of cleaving disulfide bonds of keratin constituting the hair and obtaining a good permability. Is more preferable, and 3 mass% or more is still more preferable. From the same viewpoint as described above, the content of the keratin reducing agent is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and further preferably 8% by mass or less in the hair treatment composition. Is more preferable. From the above viewpoint, the content of the keratin reducing agent is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 1 to 10% by mass in the hair treatment composition. More preferably, it is 3-8 mass%.

Said processing agent (B) can be used individually or in combination of 2 or more types.
In the treatment agent composition of the present invention, the content of the treatment agent (B) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of expressing the function of the treatment agent composition. More preferably, it is 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more. From the above viewpoint, it is preferably 40% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass. % Or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. From the above viewpoint, the content of the treatment agent (B) is preferably 0.1 to 40% by mass, more preferably 0.5 to 25% by mass, still more preferably 1 to 20% by mass, and still more preferably 2 It is -20 mass%, More preferably, it is 5-20 mass%, More preferably, it is 5-15 mass%, More preferably, it is 5-10 mass%.

  In the treatment agent composition of the present invention, the mass ratio of CCE (A) to treatment agent (B) [CCE (A) / treatment agent (B)] is determined when rinsing the hair with the hair treatment agent composition of the present invention. From the viewpoint of obtaining good slipperiness, coating feeling, and softness, 0.0002 or more is preferable, 0.005 or more is more preferable, 0.01 or more is further preferable, 0.02 or more is further preferable, and 0.04. The above is more preferable, 0.1 or more is further preferable, 5 or less is preferable, 3 or less is more preferable, 1 or less is further preferable, 0.5 or less is further preferable, and 0.2 or less is still more preferable. From the above viewpoint, the mass ratio of CCE (A) to the treatment agent (B) [CCE (A) / treatment agent (B)] is preferably 0.0002 to 5, more preferably 0.005 to 3, More preferably, it is 0.01 to 1, more preferably 0.02 to 1, still more preferably 0.02 to 0.5, and still more preferably 0.02 to 0.2.

<Other ingredients>
The hair treatment composition of the present invention contains the CCE (A) and one or more treatment agents (B) selected from dyes for hair dyes, oxidizing agents, alkaline agents, and keratin reducing agents. In addition, other components usually used as cosmetic raw materials can be contained. Such optional components include: surfactants; oil agents; oxidation aids; feel improvers; thickeners; fragrances; ultraviolet absorbers; visible light absorbers; chelating agents such as EDTA; sodium sulfite and sodium ascorbate Antioxidants such as; colorants; preservatives; pH adjusters such as phosphoric acid and disodium hydrogen phosphate; viscosity adjusters; pearl brighteners; wetting agents. These can be used alone or in combination of two or more.

(Surfactant)
The treating agent composition of the present invention can contain one or more surfactants (C).
As the surfactant (C), any surfactant can be used as long as it is usually used in pharmaceuticals, quasi drugs, cosmetics, toiletries, miscellaneous goods and the like. From the viewpoint of obtaining good slipperiness, coat feeling, and softness when rinsing the hair with the hair treatment composition of the present invention, anionic surfactants, nonionic surfactants, cationic surfactants, And one or more selected from amphoteric surfactants.

[Anionic surfactant]
The anionic surfactant is preferably one or more selected from sulfate ester salts, sulfonate salts, carboxylate salts, phosphate ester salts, and amino acid salts having a hydrophobic site.
Specifically, sulfate esters having a hydrophobic site such as alkyl sulfates, alkenyl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, polyoxyalkylene alkyl phenyl ether sulfates; sulfosuccinic acid Alkyl ester salts, polyoxyalkylene sulfosuccinic acid alkyl ester salts, alkane sulfonates, acyl isethionates, sulfonates having a hydrophobic site such as acyl methyl taurate; higher fatty acid salts having 8 to 16 carbon atoms; Carboxylate having a hydrophobic site such as alkyl ether acetate represented by the general formula (I); Phosphate ester salt having a hydrophobic site such as alkyl phosphate, polyoxyalkylene alkyl ether phosphate; Acyl glutamic acid Salt, alanine Conductor, glycine derivatives, amino acid salts and the like having a hydrophobic moiety, such as arginine derivatives.

R—O— (CH ₂ CH ₂ O) _a —CH ₂ —COOM (I)
(In the formula, R represents an alkyl group having 4 to 22 carbon atoms, a represents a number from 4.0 to 16, M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), Represents ammonium or organic ammonium)

  From the viewpoint of obtaining the effects of the present invention, the anionic surfactant preferably has an alkyl group or alkenyl group having 8 to 20 carbon atoms as a hydrophobic site. The alkyl group or alkenyl group has more preferably 10 or more carbon atoms, and more preferably 16 or less carbon atoms.

  Among these, alkyl sulfates such as sodium lauryl sulfate, polyoxyethylene lauryl ether sulfate (laureth- (1) ammonium sulfate, laureth- (1) sodium sulfate, laureth- (2) sodium sulfate, laureth- (3) Polyoxyethylene alkyl ether sulfates such as sodium sulfate), higher fatty acid salts having 8 to 16 carbon atoms such as potassium laurate, laureth- (4,5) sodium acetate, laureth- (10) sodium acetate, etc. Alkyl ether acetate represented by formula (I), sulfosuccinic acid alkyl ester salt such as sodium laureth-2 sulfosuccinate, acyl glutamate such as sodium N-acyl-L-glutamate (sodium cocoylglutamate), sodium N-lauroyl sarcosine Etc. Lysine derivative, one or more is preferably selected from α- olefin sulfonates having 14 to 16 carbon atoms.

(Nonionic surfactant)
Nonionic surfactants include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, Polyethylene glycol type nonionic surfactants such as oxyalkylene (hardened) castor oil and polyhydric alcohol type nonionic surfactants such as sucrose fatty acid ester, polyglycerin alkyl ether, polyglycerin fatty acid ester, alkylglycoside, and the like And fatty acid alkanolamides.
From the viewpoint of obtaining the effects of the present invention, the nonionic surfactant preferably has an alkyl group or alkenyl group having 8 to 20 carbon atoms as a hydrophobic site.
Among these, at least one selected from polyoxyalkylene alkyl ether, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide, and alkyl glycoside is preferable.

[Amphoteric surfactant]
Examples of amphoteric surfactants include betaine surfactants such as imidazoline betaines, alkyldimethylaminoacetic acid betaines, fatty acid amidopropyl betaines, and sulfobetaines, and amine oxide surfactants such as alkyldimethylamine oxides.
Among these, from the viewpoint of obtaining the effects of the present invention, one or more selected from imidazoline-based betaines, alkyldimethylaminoacetic acid betaines, fatty acid amidopropyl betaines, and alkylhydroxysulfobetaines are preferred.

[Cationic surfactant]
Examples of the cationic surfactant include quaternary ammonium salts, pyridinium salts, or tertiary amines having a hydrocarbon group having 12 to 28 carbon atoms which may be separated by an amide group, an ester group, or an ether group. Examples thereof include salts of mineral acids or organic acids. Specifically, mono-long-chain alkyltrimethylammonium salts such as cetyltrimethylammonium salt, stearyltrimethylammonium salt, behenyltrimethylammonium salt, octadecyloxypropyltrimethylammonium salt, distearyldimethylammonium salt, diisotetradecyldimethylammonium Di-long-chain alkyldimethylammonium salts such as salts, mono-long-chain alkyldimethylamine salts such as stearyldimethylamine, behenyldimethylamine, octadecyloxypropyldimethylamine, dimethylaminopropyl stearamide hydrochloride, citric acid or lactate Is mentioned.
Among these, from the viewpoint of obtaining the effects of the present invention, mono-long-chain alkyltrimethylammonium salts such as behenyltrimethylammonium chloride and cetyltrimethylammonium chloride are preferable.

  The content of the surfactant (C) is, in the treatment composition of the present invention, from the viewpoint of obtaining good slipperiness, coat feeling, and softness when rinsing the hair with the hair treatment composition of the present invention. 0.01 mass% or more is preferable, 0.1 mass% or more is more preferable, 0.3 mass% or more is further preferable, 0.5 mass% or more is further more preferable, and 1 mass% or more is still more preferable. From the above viewpoint, 30% by mass or less is preferable, 20% by mass or less is more preferable, 10% by mass or less is further preferable, and 5% by mass or less is even more preferable. From the above viewpoint, the content of the surfactant (C) is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably in the treatment agent composition of the present invention. It is 0.3-20 mass%, More preferably, it is 0.5-10 mass%, More preferably, it is 1-10 mass%, More preferably, it is 1-5 mass%.

(Oil agent (D))
The treatment agent composition of the present invention can contain an oil agent (D) from the viewpoint of imparting the effects of the present invention, a moist feeling after treatment drying, and a softness.
As the oil agent (D), any water-insoluble or water-insoluble oil agent having a solubility in 100 g of water at 20 ° C. of 0 g or more and 1 g or less can be used. From the above viewpoint, the amount of the oil agent (D) dissolved in 100 g of water at 20 ° C. is preferably 0 g or more and 0.5 g or less, and more preferably 0 g or more and 0.1 g or less.
As the oil agent (D), from the above viewpoint, ester oil, silicone oil, ether oil, hydrocarbon oil, higher alcohol, and carboxylic acid having a hydrocarbon group having 17 to 23 carbon atoms which may be substituted with a hydroxyl group. It is preferable that it is 1 or more types chosen from.

  Specific examples of the ester oil include castor oil, cacao oil, mink oil, avocado oil, olive oil, sunflower oil, camellia oil, kyounin oil, almond oil, wheat germ oil, theobromagndiflorum seed oil, grape seed oil, Babas oil, jojoba oil, macadamia nut oil, yucha oil, shea butter oil, camellia seed oil, beet foam oil, beeswax, lanolin, reduced lanolin, lanolin fatty acid octyldodecyl, eicenoic acid caprylyl, diisopropyl acid diisopropyl, 2-ethylhexanoic acid myristyl, Cetyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, octyl octoate, lauryl octoate, myristyl octoate, isocetyl octoate, octyl propyl heptanoate, cetostearyl isononanoate, isononyl isononanoate, Isotridecyl nonanoate, methyl laurate, hexyl laurate, octyl laurate, isopropyl myristate, octyl myristate, myristyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, octyl palmitate, cetyl palmitate , Methyl oleate, oleyl oleate, decyl oleate, isobutyl oleate, methyl stearate, 2-ethylhexyl stearate, octyl stearate, isocetyl stearate, stearyl stearate, butyl stearate, isotridecyl stearate, isopropyl isostearate , Isocetyl isostearate, isostearyl isostearate, 2-ethylhexyl hydroxystearate, Loleic acid oleyl, propanediol dicapric acid ester, diisopropyl adipate, diethoxyethyl succinate, 2-ethylhexyl succinate, polysoy fatty acid sucrose, polybehenate sucrose, tetraisostearate sucrose, tribehenate glyceryl, hydroxyalkyl (C16-18) ) Hydroxy dimer linoleyl ether, triisostearin, pentaerythryl tetrastearate and the like.

As the ester oil, a hydrophobic carboxylic acid ester of dipentaerythritol can also be used. The hydrophobic carboxylic acid ester of dipentaerythritol means a compound obtained by dehydration condensation of dipentaerythritol and one or more hydrophobic carboxylic acids. Here, the hydrophobic carboxylic acid may have a hydroxyl group. A good carboxylic acid having a hydrocarbon group of 16 to 24 carbon atoms. Specific examples of the hydrophobic carboxylic acid include palmitic acid, stearic acid, oleic acid, isostearic acid, hydroxystearic acid, rosin acid, and the like.
From the viewpoint of availability, an ester composed of a mixed acid of hydroxystearic acid, stearic acid and rosin acid and dipentaerythritol is preferred.

  From the above viewpoint, the silicone oil includes dimethylpolysiloxane, dimethiconol (dimethylpolysiloxane having a hydroxyl group at the terminal), amino-modified silicone (dimethylpolysiloxane having an amino group in the molecule), polyether-modified silicone, and glyceryl. One or more selected from modified silicone, amino derivative silicone, silicone wax, and silicone elastomer are preferred.

From the above viewpoint, the ether oil is preferably a dialkyl ether compound. Preferable examples of the dialkyl ether compound include dioctyl ether (manufactured by Cognis: cethiol OE).
Further, as the ether oil, from the above viewpoint, polyoxypropylene hexyl ether, polyoxypropylene octyl ether, polyoxypropylene decyl ether, polyoxypropylene decyl ether, polyoxypropylene hexyl ether having an average added mole number of propyleneoxy group of 3, 7, 10 or 15 is used. Examples include propylene lauryl ether, dihexyl ether, dioctyl ether, didecyl ether, dilauryl ether, dimyristyl ether, dicetyl ether, distearyl ether, diicosyl ether, and dibehenyl ether. Among these, polyoxypropylene hexyl ether, polyoxypropylene octyl ether, polyoxypropylene decyl ether, polyoxypropylene lauryl ether, dioctyl ether, didecyl ether, dilauryl ether having an average addition mole number of oxypropylene of 3 are included. Preferably, at least one selected from polyoxypropylene octyl ether, polyoxypropylene decyl ether, and polyoxypropylene lauryl ether having an average addition mole number of oxypropylene of 3 is more preferable.

  From the above viewpoint, the hydrocarbon oil is preferably a saturated or unsaturated hydrocarbon having 20 or more carbon atoms. Specific examples of hydrocarbon oils include squalene, squalane, liquid paraffin, liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomer, cycloparaffin, polybutene, petrolatum, paraffin wax, microcrystalline wax, polyethylene wax, and ceresin. From the viewpoint of feeling of unity of hair, squalane, squalene, liquid paraffin, petroleum jelly and paraffin wax are preferable, and one or more selected from squalane, liquid paraffin, petroleum jelly and paraffin wax are more preferable.

  From the above viewpoint, the higher alcohol is preferably an alcohol having a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms. As for carbon number of this alkyl group or this alkenyl group, 8 or more are more preferable, 12 or more are still more preferable, 20 or less are more preferable, and 18 or less are still more preferable. From the above viewpoint, the alkyl group or the alkenyl group preferably has 8 to 20 carbon atoms, and more preferably 12 to 18 carbon atoms. Specific examples of higher alcohols include hexyl alcohol, 2-ethylhexyl alcohol, octyl alcohol, decyl alcohol, isodecyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodeca Nord, icosyl alcohol, and behenyl alcohol. Among these, one or more selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and 2-octyldodecanol are preferable.

From the above viewpoint, the hydrocarbon group of a carboxylic acid having a hydrocarbon group having 17 to 23 carbon atoms that may be substituted with a hydroxyl group is a linear or branched alkyl group having 17 to 23 carbon atoms, or Alkenyl groups are preferred. Specific examples of the carboxylic acid having a hydrocarbon group having 17 to 23 carbon atoms that may be substituted with a hydroxyl group include stearic acid, oleic acid, isostearic acid, hydroxystearic acid, behenic acid, rosin acid, and the like. . Among these, at least one selected from stearic acid, oleic acid, isostearic acid, hydroxystearic acid, and behenic acid is preferable, and at least one selected from oleic acid and isostearic acid is more preferable.
The said oil agent (D) can be used individually or in combination of 2 or more types.

  Content of oil agent (D) is 0.01 mass% or more in the processing agent composition of this invention from the viewpoint which provides the effect of this invention, the moist feeling of the hair after process drying, and the viewpoint which provides softness. Is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and still more preferably 5% by mass or more. Further, from the above viewpoint, 30% by mass or less is preferable, 20% by mass or less is more preferable, and 15% by mass or less is further preferable. Further, from the above viewpoint, the content of the oil agent (D) is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 1 to 1% in the treatment agent composition of the present invention. 15 mass%, More preferably, it is 3-15 mass%, More preferably, it is 5-15 mass%.

(Oxidation aid)
The oxidation aid is contained in a treatment composition such as a hair coloring agent.
Examples of the oxidation aid include persulfate. Specific examples include ammonium persulfate, potassium persulfate, and sodium persulfate, and these are preferably in the form of a powder such as a granulated product.
The content of the oxidation aid is preferably 0.1% by mass or more in the hair treatment composition from the viewpoint of obtaining a sufficient decoloring effect in the hair coloring agent and from the viewpoint of reducing hair damage and scalp irritation. % Or more is more preferable, and 3 mass% or more is still more preferable. Further, from the above viewpoint, it is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.
In addition, from the above viewpoint, the content of the oxidation assistant is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and further preferably 3 to 25% by mass in the hair treatment composition. .

  In addition, in the said hair treatment composition, when the hair treatment composition is a multi-drug type used by mixing two or more agents, preferred contents such as CCE, treatment agent, surfactant, or oil agent are all The preferable content of CCE, treatment agent, surfactant or oil agent relative to the total amount of agent.

(Feel improver, thickener)
Examples of the touch improver and thickener include water-soluble collagen, protein hydrolyzate represented by collagen derivatives, cationic group-containing copolymer described in Japanese Patent No. 3472491, Japanese Patent Publication No. 58-35640, Cationized guar gum derivatives described in JP-A-60-46158 and JP-A-58-53996, cationized hydroxyethylcellulose described in JP-A-4-108723, sold by BASF Ruby cut sensation, cationic polymers such as Marquat 100 and 550 sold by Nalco, anionic polymers such as carboxyvinyl polymer and amphoteric polymers, water-soluble polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose and polyethylene glycol, etc. Is It is.

<Method for producing hair treatment composition>
There is no restriction | limiting in particular in the manufacturing method of the hair-treatment agent composition of this invention, It can manufacture by a conventional method. Specifically, for example, water, CCE (A), the processing agent (B) excluding the oxidizing agent and the alkaline agent, and other components are mixed, heated, and uniformly dissolved. After dissolution is confirmed, an oxidizing agent and an alkaline agent are added and mixed. In addition, when the hair treatment agent composition is a multi-drug type formed by mixing two or more agents, the first agent, the second agent, etc. are produced and mixed at the time of use to obtain the hair treatment agent composition. To do.
CCE (A) can be added after being previously dispersed or dissolved in water, if necessary. For example, when using the surfactant (C), the CCE (A) is added to the surfactant aqueous solution and uniformly dissolved or dispersed, and then cooled. If necessary, it can be prepared by adding a pearling agent, a pH adjusting agent, a fragrance, a pigment and the like.
Further, the dosage form of the hair treatment composition of the present invention is not particularly limited, and can be any dosage form such as liquid, foam, paste, cream, solid, powder, etc. It is preferable to be in the form of a paste, cream or cream, and it is particularly preferable to be in the form of a liquid. The blending amount of water is preferably 10% by mass or more and 99.5% by mass or less in the entire composition.

[Hair treatment method]
The present invention also provides a method for treating hair that is rinsed and dried after treating the hair with the hair treatment composition of the present invention. There is no restriction | limiting in particular as a hair processing method, A well-known method can be used.

In relation to the embodiment described above, the present invention discloses the following hair treatment composition and hair treatment method.
<1> A hair treatment composition containing a cationic group-containing cellulose ether (A) and one or more treatment agents (B) selected from hair dyes, oxidizing agents, alkaline agents, and keratin reducing agents. The cationic group-containing cellulose ether (A) has a main chain derived from anhydroglucose represented by the following general formula (1), and substitution of a cationized oxyalkylene group per anhydroglucose unit The degree of substitution is 0.01 or more and 1.0 or less, the degree of substitution of the glycerol group is 0.5 or more and 5.0 or less, and the carbon number is 3 or more represented by the following general formulas (6) to (8) The degree of substitution of a group containing a hydrocarbon group having 18 or less, preferably 3 to 7 carbon atoms, more preferably 3 to 6 carbon atoms, and still more preferably 3 to 4 carbon atoms is 0.0001 to 0.3. Hair that is Physical composition.

(In the formula, R ¹ , R ² and R ³ each independently represent a substituent composed of one or more structural units selected from the following general formulas (2) to (8), or a hydrogen atom. (The average degree of polymerization of the main chain derived from anhydroglucose is shown and is a number of 100 or more and 12000 or less.)

(In the formula, the structural unit represented by the formula (2) or (3) represents a cationized oxyalkylene group, the structural unit represented by the formula (4) or (5) represents a glycerol group, and the formula (6 ) To (8) is a hydrocarbon having 3 to 18 carbon atoms, preferably 3 to 7 carbon atoms, more preferably 3 to 6 carbon atoms, and still more preferably 3 to 4 carbon atoms. R ^{4 to} R ⁹ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, X ⁻ and Y ⁻ represent an anion, and r and s are 0. R ¹⁰ and R ¹¹ each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. R ¹² represents an alkyl group, an alkenyl group, or an aryl group having 3 to 18 carbon atoms. An aralkyl group or an aryl group, and p represents an integer of 0 or 1. In the structural units represented by formulas (2) to (7), an oxygen atom is bonded to a hydrogen atom or a carbon atom of the structural unit. doing.)

<2> The cationic charge density of the cationic group-containing cellulose ether (A) is 0.05 mmol / g or more, preferably 0.15 mmol / g or more, more preferably 0.2 mmol / g or more, and still more preferably 0.3 mmol / g. g or more, 2.0 mmol / g or less, preferably 1.5 mmol / g or less, more preferably 1.2 mmol / g or less, still more preferably 0.9 mmol / g or less, according to <1> above Hair treatment composition.

<3> The content of the cationic group-containing cellulose ether (A) is 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.2% by mass. More preferably, the content is 0.4% by mass or more, 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less. <1> or < The hair treatment composition according to 2>.

<4> The degree of substitution (MS (N +)) of the cationized oxyalkylene group per anhydroglucose unit of the cationic group-containing cellulose ether (A) is 0.04 or more, preferably 0.05 or more, more preferably 0.1 or more, more preferably 0.12 or more, 0.9 or less, more preferably 0.7 or less, still more preferably 0.6 or less, still more preferably 0.5 or less, still more preferably 0.3. Or less, more preferably 0.22 or less, in the range of 0.04 to 0.9, preferably in the range of 0.04 to 0.7, more preferably in the range of 0.04 to 0.6, still more preferably. It is in the range of 0.04 to 0.5, more preferably in the range of 0.04 to 0.3, more preferably in the range of 0.04 to 0.22, and still more preferably in the range of 0.12 to 0.22. <1> to <3> above The hair treatment composition of the crab according.

<5> The degree of substitution (MS (Gly)) of glycerol groups per anhydroglucose unit of the cationic group-containing cellulose ether (A) is 0.8 or more, preferably 1.0 or more, more preferably 1.8. Or more, more preferably 2.1 or more, 4.0 or less, preferably 3.5 or less, more preferably 3.0 or less, still more preferably 2.5 or less, still more preferably 2.3 or less, A range of 0.5 to 4.0, preferably a range of 0.8 to 3.5, more preferably a range of 1.0 to 3.0, still more preferably a range of 1.8 to 2.5, still more preferably. Is the range of 2.1-2.3, The hair-treatment agent composition in any one of said <1>-<4>.

<6> The degree of substitution (MS (HC)) of the group containing a hydrocarbon having 3 to 18 carbon atoms per anhydroglucose unit of the cationic group-containing cellulose ether (A) is 0.0005 or more, preferably 0.001 or more, more preferably 0.005 or more, still more preferably 0.01 or more, still more preferably 0.02 or more, still more preferably 0.03 or more, and 0.25 or less, preferably 0.2 or less. More preferably, it is 0.15 or less, More preferably, it is 0.10 or less, More preferably, it is 0.08 or less, More preferably, it is 0.06 or less, The range of 0.0005-0.25, Preferably it is 0.001. In the range of ~ 0.25, more preferably in the range of 0.005 to 0.25, still more preferably in the range of 0.01 to 0.25, still more preferably in the range of 0.01 to 0.2, and even more preferably. Is in the range of 0.01 to 0.15, more preferably in the range of 0.01 to 0.10, more preferably in the range of 0.02 to 0.08, still more preferably in the range of 0.02 to 0.06, The hair treatment composition according to any one of <1> to <5>, more preferably in the range of 0.03 to 0.06.

<7> The cationic group-containing cellulose ether (A) has an MS (N +) of 0.04 or more and 0.6 or less, an MS (Gly) of 0.5 or more and 4.0 or less, and an MS (HC ) Of 0.01 to 0.1 cationic group-containing cellulose ether, preferably MS (N +) is 0.04 to 0.22, and MS (Gly) is 1.0 to 3.0. And a cationic group-containing cellulose ether having MS (HC) of 0.01 or more and 0.10 or less, more preferably MS (N +) is 0.12 or more and 0.22 or less, and MS (Gly) is 2. The hair treatment agent according to any one of <1> to <6>, which is a cationic group-containing cellulose ether having a molecular weight of 1 to 2.3 and MS (HC) of 0.02 to 0.06. Composition.

<8> In the above formulas (6) and (7), R ¹⁰ and R ¹¹ are each an alkyl group having 1 to 14 carbon atoms or an alkenyl group having 2 to 14 carbon atoms, preferably 1 to 10 carbon atoms. An alkyl group or an alkenyl group having 2 to 10 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or carbon An alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably. The hair treatment composition according to any one of <1> to <7>, which is a methyl group or an ethyl group, and more preferably an ethyl group.

<9> In the formula (8), R ¹² has 3 to 14 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 7 carbon atoms, and still more preferably 3 to 6 carbon atoms. , One or more selected from alkyl groups, alkenyl groups, and phenyl groups, more preferably 3 or more and 6 or less carbon atoms, one or more selected from alkyl groups and alkenyl groups, and even more preferably 3 or more carbon atoms. The hair treatment composition according to any one of <1> to <8>, which is the following alkyl group.

<10> The average degree of polymerization n of the cationic group-containing cellulose ether (A) is 200 or more, preferably 500 or more, more preferably 1000 or more, and 10000 or less, preferably 5000 or less, more preferably 2500 or less. The hair treatment composition according to any one of <1> to <9> above.

<11> The cationic group-containing cellulose ether (A) has a 1% by mass aqueous solution viscosity at 25 ° C. of 10 mPa · s or more, preferably 50 mPa · s or more, more preferably 100 mPa · s or more, and even more preferably 150 mPa · s or more. The hair treatment agent according to any one of <1> to <10>, which is 10,000 mPa · s or less, preferably 5000 mPa · s or less, more preferably 3000 mPa · s or less, and still more preferably 2000 mPa · s or less. Composition.

<12> The mass ratio [CCE (A) / treatment agent (B)] of the cationic group-containing cellulose ether (A) to the treatment agent (B) is 0.0002 or more, preferably 0.005 or more, more preferably. 0.01 or more, more preferably 0.02 or more, more preferably 0.04 or more, still more preferably 0.1 or more, 5 or less, preferably 3 or less, more preferably 1 or less, still more preferably 0.00. The hair treatment composition according to any one of <1> to <11>, which is 5 or less, more preferably 0.2 or less.

<13> Further, a surfactant (C), preferably one or more surfactants (C) selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants ) The hair treatment composition according to any one of <1> to <12> above.

The content of <14> surfactant (C) is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably in the hair treatment composition. 0.5% by mass or more, more preferably 1% by mass or more, 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. The hair treatment composition according to 13>.

<15> The hair treatment composition according to any one of <1> to <14>, further containing an oil agent (D).

<16> The oil agent (D) has a dissolution amount in 100 g of water at 20 ° C. of 0 g or more and 1 g or less, preferably 0 g or more and 0.5 g or less, more preferably 0 g or more and 0.1 g or less. Hair treatment composition.

<17> The oil agent (D) is selected from ester oils, silicone oils, ether oils, hydrocarbon oils, higher alcohols, and carboxylic acids having a hydrocarbon group having 17 to 23 carbon atoms that may be substituted with a hydroxyl group. The hair treatment composition according to <15> or <16>, wherein the hair treatment composition is one or more selected from the above.

<18> Oil agent (D) content is 0.01 mass% or more in a hair-treatment agent composition, Preferably it is 0.1 mass% or more, More preferably, it is 1 mass% or more, More preferably, it is 3 mass% or more The hair treatment agent according to any one of <15> to <17>, further preferably 5% by mass or more, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less. Composition.

<19> The hair treatment composition according to any one of the above <1> to <18>, which is one or more selected from a hair dye and a permanent agent.

<20> The hair treatment composition according to the above <19>, wherein the hair dye is selected from hair dyes and hair bleaching agents.

<21> The hair treatment composition according to <19> or <20>, wherein the hair coloring agent is selected from the following (a) to (d).
(A) A one-component hair dye containing a hair dye and optionally an oxidizing agent.
(B) A one-pack hair hair dye that does not contain a hair dye and contains an oxidizing agent.
(C) A two-component hair dye comprising a first agent containing an alkali agent and / or a hair dye, and a second agent containing an oxidizing agent.
(D) A three-component hair dye comprising a first agent containing an alkaline agent and / or a hair dye, a second agent containing an oxidizing agent, and a third agent containing an oxidizing aid.

<22> The hair treatment composition according to <19>, wherein the permanent agent is selected from a permanent wave agent, a straight permanent agent, a continuous hair setting agent, and a hair straightener.

<23> A method for treating hair that is rinsed and dried after treating the hair with the hair treatment composition according to any one of <1> to <22>.

In the following production examples, examples and comparative examples, “%” means “mass%”. Various physical properties and the like were measured by the following methods.
(1) Measurement of viscosity average degree of polymerization of cellulose (copper ammonia method)
(I) Preparation of solution for measurement After adding 0.5 g of cuprous chloride and 20-30 mL of 25% aqueous ammonia to a measuring flask (100 mL) and completely dissolving, 1.0 g of cupric hydroxide and 25% Aqueous ammonia was added to make up the volume, and the mixture was stirred for 3 hours to completely dissolve.
(Ii) Preparation of Sample After adding 25 mg of the measurement sample to the measuring flask (25 mL), the solution prepared above was added until the meniscus coincided with the mark of the flask. This was stirred for 6 hours and completely dissolved.
(Iii) Measurement of viscosity average degree of polymerization The obtained copper ammonia aqueous solution was put into an Ubbelohde viscometer and allowed to stand in a thermostatic bath (20 ± 0.1 ° C.) for 1 minute, and then the flow rate of the liquid was measured. From the flow time (t (second)) of the copper ammonia solution having various sample concentrations (g / l) and the flow time (t ₀ (second)) of the copper ammonia aqueous solution with no sample added, the relative viscosity η sought _r .
η _r = t / t ₀
Next, the reduced viscosity (η _sp / c) at each concentration was determined from the following equation.
η _sp / c = (η _r −1) / c (c: sample concentration (g / dl))
Further, the reduced viscosity was extrapolated to c = 0 to determine the intrinsic viscosity [η], and the viscosity average polymerization degree (n) was determined from the following formula.
n = 2000 × [η]
In the examples, the average degree of polymerization of CCE was considered to be the same as the average degree of polymerization of raw material cellulose used in the production.

(2) Substitution degree of substitution in CCE: calculation of MS Degree of substitution of glycerol group in CCE (MS (Gly)), degree of substitution of cationized oxyalkylene group (MS (N +)), substitution of hydrocarbon group-containing group The degree (MS (HC)) was calculated by the following simultaneous equations (1) to (3) except when the hydrocarbon group-containing group was an oxypropylene group.
-A x (glycerol group content (%)) x MS (HC) + (74.1-74.1 x (glycerol group content (%))) x MS (Gly)-b x (glycerol group Content (%)) × MS (N +) = 162.1 × (glycerol group content (%)) (1)
-A x (nitrogen content (%)) x MS (HC)-74.1 x (nitrogen content (%)) x MS (Gly) + (bb-nitrogen content (mass%)) x MS (N +) = 162.1 × (nitrogen content (%)) (2)
(Aa- (content of hydrocarbon group-containing group (%))) × MS (HC) -74.1 × (content of hydrocarbon group-containing group (%)) × MS (Gly) -b × (Content of hydrocarbon group-containing group (%)) × MS (N +) = 162.1 × (Content of hydrocarbon group-containing group (%)) (3)
(Wherein, a represents the molecular weight of the hydrocarbon group-containing group, and b represents the molecular weight of the cationized oxyalkylene group.

The content of glycerol group, nitrogen content, and hydrocarbon group-containing group in the above simultaneous equations are the glycerol group, the nitrogen constituting the cationized oxyalkylene group, and the hydrocarbon group contained in the CCE, respectively. The mass% of the containing group is shown and calculated by the following method.
[Measurement of content (mass%) of glycerol group and hydrocarbon group-containing group content]
The content% (mass%) of the glycerol group contained in CCE was measured in Analytical Chemistry, Vol. 51, no. 13, 2172 (1979), Zeisel method known as a technique for analyzing the average number of moles of an alkoxy group added to cellulose ether, as described in “Fifteenth revised Japanese pharmacopoeia (hydroxypropylcellulose analysis method)”, etc. It calculated according to. The procedure is shown below.
(I) 1 mL of n-tetradecane was added to a 25 mL volumetric flask, and o-xylene was added and stirred until the lower surface of the liquid meniscus coincided with the upper edge of the marked line of the volumetric flask to prepare an internal standard solution.
(Ii) The purified and dried CCE 65 mg and adipic acid 65 mg were precisely weighed into a 10 mL vial, and 2 mL of the internal standard solution prepared in (i) and 2 mL of hydroiodic acid were added and sealed.
(Iii) The mixture in the vial was heated with a block heater at 150 ° C. for 1 hour while stirring with a stirrer chip.
(Iv) The upper layer (o-xylene layer) of the mixture separated into two phases in the vial was measured by gas chromatography, and isopropyl iodide derived from glycerol group and hydrocarbon group derived from hydrocarbon group-containing group Iodide (2-iodobutyl if the hydrocarbon group-containing group is an oxybutylene group) was quantified, and from the obtained results, the content (mass%) of glycerol group in the CCE, and the hydrocarbon group, respectively. The content (% by mass) of the content group was calculated.
The analysis conditions were as follows.
Column: Agilent HP-1 (length: 30 m, inner diameter: 0.32 mm, film thickness: 0.25 mm, stationary phase: 100% methylsiloxane)
Column temperature: 40 ° C. (5 min.) → 10 ° C./min. → 230 ° C. (5 min.)
Injector temperature: 210 ° C., detector: flame ion detector (FID), detector temperature: 230 ° C., implantation amount: 1 μL, carrier gas flow rate: helium 3.0 mL / min.
[Measurement of nitrogen content (% by mass)] (Kjeldahl method)
100 mg of purified and dried CCE is precisely weighed, 10 mL of sulfuric acid and 1 tablet of degradation accelerator “Keltab Tablets” (manufactured by Nakayama Rika Seisakusho Co., Ltd.) are added, and a Kjeldahl decomposition device “K-432” (manufactured by BUCHI) is used. The complete decomposition was carried out while heating at 250 ° C. for 30 minutes, 300 ° C. for 30 minutes, and 420 ° C. for 80 minutes in this order. After completion of the decomposition reaction, 30 mL of ion-exchanged water was added to the sample, and 40 K of 30% sodium hydroxide aqueous solution was added to make it alkaline using an automatic Kjeldahl distillation and titration apparatus “K-370” (manufactured by BUCHI). The ammonia released by the above is collected in a 1% boric acid aqueous solution and titrated with 0.01N sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd., for quantitative analysis), whereby the nitrogen content (mass%) in the CCE Asked.

  In the case where the hydrocarbon group-containing group is an oxypropylene group, pretreatment according to the Zeisel method adds not only the glycerol group but also the oxypropylene group to isopropyl iodide. The group content cannot be determined independently. Therefore, when the hydrocarbon group-containing group is an oxypropylene group, the content of the oxypropylene group is first determined by the NMR method described below, and then the above [content of the content of glycerol group and hydrocarbon group-containing group] The total content of oxypropylene groups and glycerol groups was determined by the method described in (Measurement of (mass%)]. The content of glycerol groups was determined by subtracting the content of oxypropylene groups determined by the NMR method from the total content. The nitrogen content (% by mass) is measured by substituting the obtained content of each substituent into the calculation formulas (1) to (3) using the method described above and solving the simultaneous equations. , MS (PO), MS (Gly), and MS (N +) were calculated.

[Calculation of content (mass%) of oxypropylene group by NMR method]
The degree of substitution (MS (PO)) of the oxypropylene group of the obtained CCE was calculated by ¹ H-NMR. The measurement method is as follows.
Device: Mercury 400 (Varian)
Observation range: 6410.3 Hz
Data point: 65536
Pulse width: 45 °
Pulse delay time: 5s
Accumulation: 128 times Spin: No spin
Internal standard: 3- (trimethylsilyl) propionic acid-d4 sodium salt (TSP)
Sample for preparing a calibration curve: hydroxypropyl cellulose (trade name: manufactured by KLUCEL Hercules, known content of oxypropylene group: 76.15% by mass)
10 mg of purified and dried CCE was dissolved in 1 g of D ₂ O containing the internal standard, and ¹ H-NMR measurement was performed under the above measurement conditions. The content of the oxypropylene group in the CCE was calculated from the methyl group signal (1.23 ppm) in the oxypropylene group.

(3) Measurement of aqueous solution viscosity of CCE 0.5 g of CCE that had been purified and dried and 49.5 g of ion-exchanged water were placed in a cylindrical 50 mL vial with a diameter of 32 mm, and the mixture was stirred for 6 hours. % Aqueous solution or 1% by mass dispersion was prepared.
The obtained 1 mass% aqueous solution or 1 mass% dispersion was adjusted to 25 ° C. in a constant temperature water bath, and then measured using a B-type viscometer “TVB-10M” (manufactured by Toki Sangyo Co., Ltd.): 25 The viscosity was measured under the conditions of ° C., rotation speed: 30 rpm, rotor: 1, 2, 3, or 4.
In selecting the rotor to be used, the measurement was performed by selecting a rotor whose measurement result was in the range of 20 to 90% of the upper limit value in the measurement range of the viscosity with respect to the rotor used.

(4) Measurement of moisture content The moisture content of pulp, cotton-like cellulose, and powdered cellulose was measured at a measurement temperature of 120 ° C using an electronic moisture meter "MOC-120H" (manufactured by Shimadzu Corporation). About 1 g of a sample was used, and the point at which the rate of change in weight for 30 seconds was 0.1% or less was taken as the end point of measurement.

(5) Viscosity measurement The blended composition was placed in a cylindrical 50 mL vial with a diameter of 32 mm, adjusted to 25 ° C. in a constant temperature water bath, and then a B-type viscometer “TVB-10M” (manufactured by Toki Sangyo Co., Ltd.). ), The viscosity was measured under the conditions of measurement temperature: 25 ° C., rotation speed: 30 rpm, rotor: 1, 2, 3, or 4.
In selecting the rotor to be used, the measurement was performed by selecting a rotor whose measurement result was in the range of 20 to 90% of the upper limit value in the measurement range of the viscosity with respect to the rotor used.

(6) Measurement of pH In a cylindrical 50 mL vial with a diameter of 32 mm, 5 g of the blended composition and 45 g of ion-exchanged water were stirred and dispersed uniformly, and then a pH meter “PH METER HM-30G” (Toa PH measurement was performed using DK Corporation.

Production Example 1 (Production of CCE (1))
(1) Cutting process, drying process and pulverization process of cellulose Sheet-like wood pulp (manufactured by Tenbeck: BioflocXV18, average polymerization degree 1977) is processed with a sheet pelletizer “SGG-220” (manufactured by Horai Co., Ltd.) to form a chip. I made it. Then, the drying process was performed at 80 degreeC for 12 hours, and the chip-shaped dry pulp with a water content of 0.18 mass% was obtained. The obtained chip-like cellulose was put into an extreme mill “MX-1200XTM type” (manufactured by Waring, total volume 150 mL), and pulverized at 20 ° C. for 30 seconds at a rotational speed of 24,000 rpm to obtain cotton-like cellulose (average polymerization Degree 1977).
(2) Glycerization reaction In a three-necked round bottom flask, 584 g of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.), tetra (n-butyl) ammonium fluoride trihydrate (TBAF, manufactured by Kanto Chemical Co., Inc.) 116 .2 g was added and dissolved uniformly. To this was added 7.0 g of the cotton-like cellulose obtained above and stirred at room temperature for 1 hour to dissolve. Further, 2.4 g (1.0 mol / AGU 1 mol) of finely powdered potassium hydroxide was added and well dispersed. After raising the temperature to 70 ° C., a solution prepared by mixing 128 g of glycidol (40 mol / AGU 1 mol) and 128 g of dimethyl sulfoxide was added over 5 hours while stirring the reaction solution under a nitrogen stream. After completion of the dropwise addition, stirring was continued for 1 hour at 70 ° C. to complete the reaction.
Subsequently, the reaction solution is cooled to room temperature and then centrifuged. The resulting supernatant is mixed in a mixed solvent (10 L, 25 ° C.) of ion-exchanged water / acetone / methanol = 2/4/4 (volume ratio). And the precipitated polymer is filtered, washed with 1 L of the above ion exchange water / acetone / methanol mixed solvent, and dried under reduced pressure (80 ° C., 0.03 kPa, 12 hours) to be glycerolated as a white solid. 13 g of cellulose was obtained.

(3) Cationization reaction and addition reaction of hydrocarbon group-containing group A three-necked round bottom flask was charged with 1089 g of a 70% aqueous dimethyl sulfoxide solution, and 11 g of the glycerolated cellulose obtained above was added. And was uniformly dissolved. Thereafter, 1.8 g (0.25 mol / AGU 1 mol) of a 20% aqueous sodium hydroxide solution was added and stirred at room temperature. Thereafter, glycidyltrimethylammonium chloride as a cationizing agent (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., water content 20% by mass, purity 90% or more in the remaining components after deducting water) 11.1 g (2.00 mol / AGU 1 mol) In addition, 61 g (1.50 mol / AGU 1 mol) of 1,2-epoxypentane (manufactured by Wako Pure Chemical Industries, Ltd.) as a hydrocarbon group-containing group-introducing agent was added to this solution while stirring the glycerolated cellulose solution. The mixture was heated to 50 ° C. and reacted for 5 hours. Thereafter, the reaction solution was neutralized with acetic acid, poured into 10 L of ethanol / isopropanol (7/3 volume ratio) mixed solvent, the precipitated polymer was filtered, washed with 1 L of the ethanol / isopropanol mixed solvent, and then depressurized. By drying (80 ° C., 0.03 kPa, 12 hours), 17 g of CCE (1) was obtained as a white solid.
Table 1 shows the addition amount of the glycerolating agent, the cationizing agent, and the hydrocarbon group-containing group introduction agent. The degree of substitution of the glycerol group [MS (Gly)], the degree of substitution of the cationized oxyalkylene group [MS (N +) ] And the substitution degree [MS (HC)] of the hydrocarbon group-containing group are shown in Table 2.

Production Examples 2 and 12 to 13 (Production of CCE (2) and (12) to (13))
The same procedure as in Production Example 1 was conducted except that the types and addition amounts of the glycerolating agent, cationizing agent and hydrocarbon group-containing group-introducing agent were changed to the amounts shown in Table 1, respectively. CCE (2) And (12) to (13) were obtained. Table 1 shows the addition amount of the glycerolating agent, the cationizing agent, and the hydrocarbon group-containing group introduction agent. The degree of substitution of the glycerol group [MS (Gly)], the degree of substitution of the cationized oxyalkylene group [MS (N +) ] And the substitution degree [MS (HC)] of the hydrocarbon group-containing group are shown in Table 2.

Production Examples 3, 4, 5 to 11, 16 (production of CCE (3), (4), (5) to (11), CGC (1))
In production example 1, sheet wood pulp as raw material cellulose was changed to Tenfloc Biofloc HV +, average polymerization degree 1550, and the cellulose chipping / flocculation step of step (1) was performed by the following cellulose powdering step: Changed to
(1) Cutting process, drying process and pulverization process of cellulose Sheet wood pulp (manufactured by Tenbeck: Biofloc HV +, average polymerization degree 1550) is processed with a shredder “MSX2000-IVP440F” (manufactured by Meiko Shokai Co., Ltd.) to obtain a chip. I made it. Thereafter, a drying treatment was performed at 80 ° C. for 12 hours to obtain a chip-like dried pulp having a water content of 0.18%.
Next, 920 g of the obtained chip-shaped dried pulp was batch-type vibration mill “FV-10” (manufactured by Chuo Kako Co., Ltd .: container total volume 33 L, as a rod, φ30 mm, length 510 mm, and the cross-sectional shape was circular. 63 rods made of SUS304, filling rate 70% by volume). A pulverization treatment was performed for 10 minutes at a frequency of 20 Hz, a total amplitude of 8 mm, and a temperature of 10 to 40 ° C. to obtain 890 g of cellulose powder (average polymerization degree 1233).
Using the obtained cellulose powder, the same as in Production Example 1 except that the addition amount of the glycerolating agent, cationizing agent, and hydrocarbon group-containing group introduction agent was changed to the amounts shown in Table 1, respectively. To obtain CCE (3), (4), (5) to (11) and CGC (1).
Table 1 shows the addition amount of the glycerolating agent, the cationizing agent, and the hydrocarbon group-containing group introduction agent. The degree of substitution of the glycerol group [MS (Gly)], the degree of substitution of the cationized oxyalkylene group [MS (N +) ] And the substitution degree [MS (HC)] of the hydrocarbon group-containing group are shown in Table 2.

Production Examples 14 to 15 (Production of CCE (14) to (15))
Table 1 shows the raw cellulose cellulose pulp changed from Tenbeck BiofloxXV to an average degree of polymerization of 1694, and the types and amounts of glycerolating agent, cationizing agent and hydrocarbon group-containing group introduction agent. Except having changed into the amount which was carried out, it carried out similarly to manufacture example 1 and obtained CCE (14)-(15). Table 1 shows the addition amount of the glycerolating agent, the cationizing agent, and the hydrocarbon group-containing group introduction agent. The degree of substitution of the glycerol group [MS (Gly)], the degree of substitution of the cationized oxyalkylene group [MS (N +) ] And the substitution degree [MS (HC)] of the hydrocarbon group-containing group are shown in Table 2.

Examples 1 to 19 and Comparative Examples 1 and 2 (Production and evaluation of two-component hair bleaching agent)
(1) Preparation of first agent Components other than the higher alcohol, 28% aqueous ammonia solution and propylene glycol shown in Tables 3 to 4 were mixed with an appropriate amount of water and stirred. Heated to 60 ° C. to dissolve completely. Thereto, cetyl alcohol and propylene glycol previously mixed and heated to 70 ° C. were added and emulsified for 30 minutes. It cooled to 40 degreeC, 28% ammonia aqueous solution and the remaining water were added and mixed uniformly, and the 1st agent was prepared.
The detail of the component shown to Tables 3-4 is as follows.
CCE (1) to (15) (obtained in Production Examples 1 to 15)
CGC (1) (obtained in Production Example 16)
・ Cationized hydroxyethyl cellulose (Amerchol: UCARE POLYMER LR30M)
・ CETEARETH-13 (Kao Corporation: Emulgen 220)
・ Laureth-1 sodium sulfate (manufactured by Kao Corporation: Emar 170J, active ingredient 70%)

(2) Preparation of second agent Surfactant (Cetareth-13 and sodium laureth-1 sulfate) shown in Tables 3-4, other components (EDTA-2-sodium, phosphoric acid, disodium hydrogen phosphate), and appropriate amounts Were mixed and stirred, and heated to 60 ° C. for complete dissolution. A higher alcohol heated to 70 ° C. was added thereto and emulsified. After cooling to 40 ° C., a 35% hydrogen peroxide aqueous solution and the remaining water were added and mixed uniformly to prepare a second agent. The pH was 4.

(3) Evaluation of two-component hair bleaching agent Using hair with a length of 30 cm and a mass of 10 g (human hair black hair BS-B3A) that has no chemical treatment history and is commercially available from Beaulux, 3 g of this hair sample is evenly distributed. It was aligned to a width of 2 cm so as to obtain a proper thickness. A hair bundle for testing was obtained by fixing one end of hair to a plastic plate having a width of 2 cm with an adhesive.
The above-mentioned hair bundle washed with a plain shampoo having the following composition was dried with warm air from a dryer. The 1st agent and 2nd agent which were obtained by said (1) and (2) were mixed by mass ratio 2: 3, and 3 g was apply | coated to the hair | bristle bundle in total. Thereafter, the hair bundle was allowed to stand at 30 ° C. for 30 minutes to obtain an evaluation tress.
Five panelists rinsed the obtained evaluation tress with warm water for 1 minute, and evaluated the slipperiness, coat feeling, and softness during hair rinsing according to the following evaluation criteria.
The results are shown in Tables 3-4.

[Composition of plain shampoo]
(Ingredient) (%)
Polyoxyethylene (2 mol) lauryl ether sulfate Na 11.0
(Kao Corporation: Emar E-27C (active ingredient: 27%) added 40.7%)
Palm oil fatty acid N-methylethanolamide 3.0
(Kao Corporation: Aminone C11S)
Citric acid 0.2
Methylparaben 0.3
Purified water residue
Total 100.0

[Manufacture of plain shampoo]
Polyoxyethylene (2 mol) lauryl ether sulfate Na, coconut oil fatty acid N-methylethanolamide and an appropriate amount of water were mixed and dissolved uniformly. Further, methylparaben was added and dissolved uniformly. Finally, citric acid and the remaining water were added and dissolved uniformly.

(Evaluation criteria: Comparative example 1 is set as reference score 3)
Scores were obtained by averaging the evaluation results of five panelists.
-Sliding property 5: Very good sliding 4: Good sliding 3: Normal sliding 2: Bad sliding 1: Very poor sliding-Coat feeling 5: Excellent coating feeling 4: Excellent coating feeling 3 : Normal coat feeling 2: Bad coat feeling 1: No feeling of coat at all · Softness 5: Very good softness 4: Good softness 3: Softness is normal 2: Softness is poor 1: I can't feel the softness

  From Tables 3-4, it turns out that the hair decoloring agent of Examples 1-19 was able to provide favorable slipperiness, a coat feeling, and softness at the time of a process rinse.

Example 20 and Comparative Example 3 (Production and Evaluation of Two-Part Hair Coloring Agent)
A two-component hair dye having the composition shown in Table 5 was produced in the same manner as in Example 1. The pH of the first agent was 10, and the pH of the second agent was 4. The evaluation of Example 20 was performed in the same manner as in Example 1 with Comparative Example 3 as the reference score 3. The results are shown in Table 5.
Details of the components shown in Table 5 are as follows.
CCE (13) (obtained in Production Example 13)
・ Cationized hydroxyethyl cellulose (Amerchol: UCARE POLYMER LR30M)
・ CETEARETH-13 (Kao Corporation: Emulgen 220)
・ Laureth-1 sodium sulfate (manufactured by Kao Corporation: Emar 170J, active ingredient 70%)
From Table 5, it can be seen that the hair dye of Example 20 was able to impart good slipperiness, coat feeling and softness during the treatment rinsing.

Example 21 and Comparative Example 4 (Production and evaluation of two-component hair dye)
A two-component hair dye having the composition shown in Table 6 was produced in the same manner as in Example 1. The pH of the first agent was 10, and the pH of the second agent was 4. The evaluation of Example 21 was performed in the same manner as in Example 1 using Comparative Example 4 as the reference score 3. The results are shown in Table 6.
Details of the components shown in Table 6 are as follows.
CCE (13) (obtained in Production Example 13)
・ Hexadimesulin bromide (Sigma Aldrich)
・ Laureth-12 (Kao Co., Ltd .: Emulgen 120)
・ Oles-30 (Kao Corporation: Emulgen 430)
・ Laureth-3 (Kao Co., Ltd .: Emulgen 103)
From Table 6, it can be seen that the two-component hair dye of Example 21 was able to impart good slipperiness, coat feeling and softness during the treatment rinsing.

Example 22 and Comparative Examples 5 to 6 (Production and evaluation of two-component hair dye)
A two-component hair dye having the composition shown in Table 7 was produced in the same manner as in Example 1. The pH of the first agent was 10, and the pH of the second agent was 4. The evaluation of Example 22 was performed in the same manner as in Example 1 using Comparative Example 6 as the reference score 3. The results are shown in Table 7.
Details of the components shown in Table 7 are as follows.
CCE (13) (obtained in Production Example 13)
・ Cationized hydroxyethyl cellulose (Amerchol: UCARE POLYMER LR30M)
・ Dimethyldiallylammonium chloride-acrylamide copolymer (manufactured by Nalco: Marcote 295)
・ CETEARETH-13 (Kao Corporation: Emulgen 220)
Stearyltrimethylammonium chloride (Kao Corporation: Cotamine 86W, active ingredient 28%)
From Table 7, it can be seen that the two-component hair dye of Example 22 was able to impart good slipperiness, coat feeling and softness during the treatment rinsing.

Example 23 and Comparative Examples 7-8 (Production and Evaluation of Permanent Wave Agent)
(1) Preparation of first agent Components other than 50% ammonium thioglycolate and 28% ammonia water shown in Table 8 and an appropriate amount of water were mixed and stirred until completely dissolved. 50% ammonium thioglycolate, 28% ammonia water and the remaining water were added and stirred, and completely dissolved to prepare the first agent. The pH was 9.
Details of the components shown in Table 8 are as follows.
CCE (13) (obtained in Production Example 13)
・ Cationized hydroxyethyl cellulose (Amerchol: UCARE POLYMER LR30M)
・ Dimethyldiallylammonium chloride-acrylamide copolymer (manufactured by Nalco: Marcote 295)
・ CETEARETH-13 (Kao Corporation: Emulgen 220)

(2) Preparation of Second Agent Sodium Bromate, Propylene Glycol, Surfactant (Cetearless-13, Laureth-3), Keratin Hydrolyzate (Seiwa Kasei Co., Ltd .: Promois (Effective 10) %) Was added to 1.0%) and an appropriate amount of water was mixed and stirred until it was completely dissolved. Amodimethicone (manufactured by Toray Dow Corning Co., Ltd .: SM8904 (effective content 40%) added 1.25%) was added and mixed uniformly to prepare the second agent. The pH was 7.

(3) Evaluation of Permanent Wave Agent Using a hair with a length of 30 cm and a mass of 10 g (human hair black hair BS-B3A) with no chemical treatment history commercially available from Beaulux, 2 g of this hair sample was obtained with a uniform thickness. The width was adjusted to 2 cm. A hair bundle for testing was obtained by fixing one end of hair to a plastic plate having a width of 2 cm with an adhesive.
The prepared hair bundle was treated with the same plain shampoo as in Example 1, the moisture was removed with a towel, and the hair bundle was prepared with a comb. This hair bundle was wound around a rod having a diameter of 9 mm (manufactured by Dariya Co., Ltd .: Benezel cold rod No. 6), 2 g of the first agent was applied, allowed to stand at 30 ° C. for 15 minutes, and rinsed with warm water for 3 minutes. Further, 2 g of the second agent was applied, allowed to stand at 30 ° C. for 15 minutes, the rod was removed, and an evaluation tres was obtained.
Five panelists rinsed the obtained evaluation tress with warm water for 1 minute, and evaluated the slipperiness, coat feeling, and softness when rinsing the hair in the same manner as in Example 1. In addition, after treatment with a plain conditioner having the following composition, evaluation was made of the finger's fingering, slipperiness and sustainability during rinsing.
The evaluation of the permanent wave agent was carried out using Comparative Example 7 as the reference score 3. The same criteria as in Example 1 were used for the slipperiness, the coating feeling, and the softness during rinsing. In addition, the following criteria were used for fingering, slipperiness and sustainability during rinsing after conditioner treatment. The results are shown in Table 8.
From Table 8, it can be seen that the permanent wave agent of Example 23 was able to impart good slipperiness, coating feeling and softness during the treatment rinsing. Moreover, it turns out that the favorable fingering, slipperiness, and a lasting feeling were able to be provided at the time of the hair rinse after a conditioner.

[Composition of plain conditioner]
(Ingredient) (%)
Stearoxypropyltrimethylammonium chloride 1.0
Cetyl alcohol 0.6
Stearyl alcohol 2.3
Propylene glycol 1.0
Phenoxyethanol 0.3
Purified water residue
Total 100.0

[Manufacture of plain conditioners]
Phenoxyethanol and an appropriate amount of water were added and mixed, and the mixture was heated to 80 ° C. Thereto, stearoxypropyltrimethylammonium chloride, cetyl alcohol, stearyl alcohol, and propylene glycol mixed in advance and heated to 70 ° C. were added, emulsified, and cooled to room temperature.

(Evaluation criteria: Comparative example 7 is set as reference score 3)
Scores were obtained by averaging the evaluation results of five panelists.
・ Finger passage after conditioner 5: Finger passage is very good 4: Finger passage is good 3: Finger passage is normal 2: Finger passage is bad 1: Finger passage is very bad ・ Slip after conditioner 5: Slip Very good 4: Slip is good 3: Slip is normal 2: Slip is bad 1: Slip is very bad ・ Sustained feeling after conditioner 5: Excellent feeling of persistence 4: Excellent feeling of persistence 3: Sustained feeling Feel 2: No sense of persistence 1: No sense of persistence

Example 24 and Comparative Examples 9 to 10 (Production and Evaluation of Hair Straightener)
(1) Preparation of first agent Components other than 50% ammonium thioglycolate shown in Table 9 and an appropriate amount of water were mixed and stirred until completely dissolved. The first agent was prepared by adding 50% ammonium thioglycolate and the remaining water and stirring until completely dissolved. The pH was 9.
Details of the components shown in Table 9 are as follows.
CCE (13) (obtained in Production Example 13)
・ Cationized hydroxyethyl cellulose (Amerchol: UCARE POLYMER LR30M)
・ Dimethyldiallylammonium chloride-acrylamide copolymer (manufactured by Nalco: Marcote 295)
・ CETEARETH-13 (Kao Corporation: Emulgen 220)
(2) Preparation of the second agent Lactic acid, β-naphthalenesulfonic acid, benzyloxyethanol, ethanol, cetealess-13 shown in Table 9 and an appropriate amount of water were mixed and stirred until they were completely dissolved. Next, 48% aqueous sodium hydroxide solution was added and mixed with stirring. Furthermore, 35% hydrogen peroxide solution and the remaining water were added and stirred to completely dissolve, thereby preparing a second agent. The pH was 3.
(3) Evaluation of hair straightener A 26 cm long, 10 g mass hair provided by a Japanese adult female with comb hair was used as a specimen. This was treated with the same plain shampoo as in Example 1, washed with running water, and then air-dried. 2 g of this hair sample was aligned to a width of 2 cm so as to have a uniform thickness. A hair bundle for testing was obtained by fixing one end of hair to a plastic plate having a width of 2 cm with an adhesive.
The prepared hair bundle was treated with the same plain shampoo as in Example 1, the moisture was removed with a towel, and the hair bundle was prepared with a comb. 1.5 g of the first agent was applied to the hair bundle, allowed to stand at 25 ° C. for 15 minutes, rinsed with warm water for 30 seconds, and wiped with a towel. Then, it processed with the iron for hot hair setting set to 130 degreeC. Next, 1.5 g of the second agent was applied and allowed to stand at 25 ° C. for 5 minutes to obtain an evaluation tres.
Five panelists rinsed the obtained evaluation tress with warm water for 1 minute, and evaluated in the same manner as in Example 1. Further, in the same manner as in Example 23, evaluation was made of the finger's fingering, slipperiness, and sustainability when rinsing the hair after the conditioner. The hair straightener was evaluated using Comparative Example 9 as a reference score of 3. The results are shown in Table 9.
From Table 9, it can be seen that the hair straightener of Example 24 was able to impart good slipperiness, coat feeling and softness upon treatment rinsing. Moreover, it turns out that the favorable fingering, slipperiness, and a lasting feeling were able to be provided at the time of the hair rinse after a conditioner.

Example 25 (Production and evaluation of one-pack hair dye)
CCE (13), hydroxypropylxanthan gum (manufactured by DSP Gokyo Food & Chemical Co., Ltd .: Lavo Gum EX) and an appropriate amount of water were mixed and stirred, and heated to 60 ° C. to dissolve. 71% glycolic acid aqueous solution, black No. 401, orange No. 205, ethanol, glycerin, laureth-13 (manufactured by Kao Corporation: Emulgen 120), PEG-11 methyl ether dimethicone (manufactured by Shin-Etsu Chemical Co., Ltd .: KF-6011) Added and stirred until dissolved. After cooling to 40 ° C., an appropriate amount of water was added and mixed uniformly to produce a one-component hair dye having the composition shown below. The pH was 3.
3 g of hair bundles washed with the same plain shampoo as in Example 1 were dried with warm air from a dryer. 3 g of the one-component hair dye composition was applied to the hair bundle. Thereafter, the hair bundle was allowed to stand at 30 ° C. for 30 minutes to obtain an evaluation tress.
Evaluation was performed in the same manner as in Example 1 using the above-described evaluation tress. As a result, good slidability, coat feeling and softness could be imparted during the treatment rinsing.

(Ingredient) (%)
CCE (13) 1.0
Black 401 No. 0.5
Scarlet 205 No. 0.3
Laureth-13 0.3
PEG-11 methyl ether dimethicone 1.6
71% glycolic acid 5.7
Ethanol 7.0
Glycerin 1.0
Hydroxypropyl xanthan gum 1.4
Purified water balance
Total 100.0

Example 26 (Production and evaluation of one-component hair bleaching agent)
A one-component hair dye having the following composition was produced and evaluated.
CCE (13), Ores-30 (manufactured by Kao Corporation: Emulgen 430), PEG (60) -hydrogenated castor oil (manufactured by Kao Corporation: Emanon CH-60 (K)), polysorbate-40 (manufactured by Kao Corporation) : Rheidol TW-P120), dipropylene glycol, EDTA-2-sodium, disodium hydrogen phosphate, phosphoric acid and an appropriate amount of water were mixed and stirred. Heated to 60 ° C. to dissolve completely. Cetyl alcohol heated to 70 ° C. was added and emulsified. After cooling to 40 ° C., 35% hydrogen peroxide water and the remaining water were added and mixed uniformly to produce a one-component hair dye having the composition shown below. The pH was 3.
3 g of the hair bundle washed with the same plain shampoo as in Example 1 was dried with warm air from a dryer, and 3 g of the one-component hair bleaching composition obtained above was applied to the hair bundle. Thereafter, the hair bundle was allowed to stand at 30 ° C. for 30 minutes, and then the hair bundle was allowed to stand at 30 ° C. for 30 minutes to obtain an evaluation tres.
Evaluation was performed in the same manner as in Example 1 using the above-described evaluation tress. As a result, good slidability, coat feeling and softness could be imparted during the treatment rinsing.

(Ingredient) (%)
CCE (13) 0.5
35% hydrogen peroxide solution 16.8
Ores-30 3.0
PEG (60) -hydrogenated castor oil 0.5
Polysorbate-40 0.5
Cetyl alcohol 10.0
Dipropylene glycol 2.0
EDTA-2-sodium 0.1
Disodium hydrogen phosphate 0.1
Phosphoric acid 0.2
Purified water balance
Total 100.0

  The hair treatment composition of the present invention can be suitably used in the fields of hair dyes for hair, hair bleaching agents, permanent wave agents, straight permanent agents, long-lasting hair setting agents, hair straighteners and the like. .

Claims (6)

A hair treatment composition comprising a cationic group-containing cellulose ether (A) and one or more treatment agents (B) selected from hair dyes, oxidizing agents, alkali agents, and keratin reducing agents, The cationic group-containing cellulose ether (A) has a main chain derived from anhydroglucose represented by the following general formula (1), and the degree of substitution of the cationized oxyalkylene group per anhydroglucose unit is 0. 0.01 or more and 1.0 or less, the degree of substitution of the glycerol group is 0.5 or more and 5.0 or less, and the carbon number is 3 or more and 18 or less represented by the following general formulas (6) to (8). A hair treatment composition wherein the degree of substitution of a group containing a hydrocarbon group is 0.0001 or more and 0.3 or less.

(In the formula, R ¹ , R ² and R ³ each independently represent a substituent composed of one or more structural units selected from the following general formulas (2) to (8), or a hydrogen atom. (The average degree of polymerization of the main chain derived from anhydroglucose is shown and is a number of 100 or more and 12000 or less.)

(In the formula, the structural unit represented by the formula (2) or (3) represents a cationized oxyalkylene group, the structural unit represented by the formula (4) or (5) represents a glycerol group, and the formula (6 ) To (8) represent a group containing a hydrocarbon group having 3 to 18 carbon atoms, and R ^{4 to} R ⁹ are each independently a straight chain or branched chain having 1 to 3 carbon atoms. X ^- and Y ^- represent an anion, and r and s are each an integer of 0 to 3. R ¹⁰ and R ¹¹ are each independently a straight chain or branched chain having 1 to 16 carbon atoms. Or a linear or branched alkenyl group having 2 to 16 carbon atoms, R ¹² represents an alkyl group, alkenyl group, aralkyl group, or aryl group having 3 to 18 carbon atoms, and p is Represents an integer of 0 or 1. In the structural units represented by formulas (2) to (7) The oxygen atom is bonded to a hydrogen atom or a carbon atom of the structural unit.)   The hair treatment composition according to claim 1, wherein the cationic charge-containing cellulose ether (A) has a cationic charge density of 0.05 mmol / g or more and 2.0 mmol / g or less.   The hair treatment composition according to claim 1 or 2, wherein the content of the cationic group-containing cellulose ether (A) is 0.01% by mass or more and 10% by mass or less.   The hair treatment composition according to any one of claims 1 to 3, which is at least one selected from a hair dye and a permanent agent.   The hair treatment composition according to any one of claims 1 to 4, further comprising a surfactant (C).   A hair treatment method comprising rinsing and drying hair after treatment with the hair treatment composition according to any one of claims 1 to 5.