JP2014131988A - Cleansing agent composition for skin or hair - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cleansing agent composition for a skin or hair, which can give excellent finger passing properties during washing, an excellent slipperiness and an excellent lasting feeling of the slipperiness during rinsing and an excellent moist feeling and uniformity after drying when used for a hair cleansing agent and can give an excellent moisturized feeling after drying when used for a skin cleansing agent, and to provide a washing method.SOLUTION: There is provided a cleansing agent composition for a skin or hair which comprises: a cellulose ether containing a cationic group (A); a surfactant (B); and an oil agent (C), wherein the cellulose ether containing a cationic group (A) has a main chain derived from an anhydroglucose represented by the general formula (1), the degree of substitution of a cationized oxyalkylene group per the anhydroglucose unit is 0.01 or more and to 1.0 or less, the degree of substitution of a glycerol group is 0.5 or more and 5.0 or less and the degree of substitution of a group having a hydrocarbon group having 3 or more and 18 or less carbon atoms represented by the general formulas (6) to (8) is 0.0001 or more and 0.2 or less.

Description

  The present invention relates to a cleaning composition for skin or hair.

Hair is damaged by the living environment (ultraviolet rays and heat from sunlight, drying), daily hair care behavior (friction from washing and brushing, heat from a dryer), and chemical treatment (coloring, permanent, etc.). When they rub against each other in a wet state, a large frictional force is generated on the surface, and squeaks and tangles are felt during hair washing. In hair cosmetics, in addition to the basic function of removing dirt on the hair, it is generally represented by cationized hydroxyethyl cellulose as a conditioning agent in order to improve the fingering property during washing, the slipperiness during rinsing, and the continuity of slipping. A cationic polymer is incorporated.
For example, Patent Document 1 discloses a hydrophob-substituted water-soluble cationic polysaccharide, and examples are prepared by reacting a cellulosic starting material with glycidol, followed by quaternization / alkylation. Illustrated are water-soluble cationic polysaccharides. 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 2, it is substituted with 0.0003 to 0.08 mole of a substituent containing an alkyl or arylalkyl group having 8 to 24 carbon atoms and a quaternary nitrogen-containing substituent per mole 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 3 includes cationized glycerolated cellulose in which the average addition mole number of the cationic group is 0.2 to 0.5 and the average addition mole number of the glycerol group 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.

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

However, the techniques of Patent Documents 1 to 3 are not sufficiently satisfactory in terms of the smoothness and continuity during rinsing and the smoothness and uniformity after drying.
When used in a hair cleaning agent, the present invention is excellent in fingering at the time of washing, can provide excellent slipperiness at the time of rinsing and its long-lasting feeling, and moist feeling and uniformity after drying. When it uses for an agent, it aims at providing the cleaning composition for skin or hair which can provide the outstanding moisturizing feeling after drying.

The present inventors have found that the above-described problems can be solved by a skin or hair cleaning composition containing a specific cationic group-containing cellulose ether, a surfactant and an oil.
That is, the present invention provides the following [1] to [3].
[1] A skin or hair cleaning composition containing a cationic group-containing cellulose ether (A), a surfactant (B), and an oil (C), the cationic group-containing cellulose ether (A) Has a main chain derived from anhydroglucose represented by the following general formula (1), the degree of substitution of the cationized oxyalkylene group per anhydroglucose unit is 0.01 or more and 1.0 or less, Degree of substitution of a group containing a hydrocarbon group having 3 to 18 carbon atoms and having a glycerol group substitution degree of 0.5 to 5.0 and represented by the following general formulas (6) to (8) Is a cleansing composition for skin or hair (hereinafter also referred to as the cleaning composition of the present invention).

(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 hair washing method (hereinafter, also referred to as a hair washing method of the present invention) in which hair is washed with the cleaning composition of [1], followed by rinsing and drying.
[3] A skin cleaning method (hereinafter, also referred to as a skin cleaning method of the present invention) in which the skin is cleaned using the cleaning composition of [1], followed by rinsing and drying.

The cleaning composition of the present invention, when used in a hair cleaning agent, has excellent fingering at the time of washing the hair, excellent slipperiness at the time of rinsing after treating the hair and its long lasting feeling, and excellent moistness after drying A feeling and uniformity can be imparted, and when used in a skin cleanser, an excellent moisturizing feeling after drying can be imparted (hereinafter, these effects are also referred to as effects of the present invention).
In addition, the uniformity after drying means that the touch is uniform from the root of the hair bundle to the hair tip.

[Cleaning composition]
The cleaning composition of the present invention contains a cationic group-containing cellulose ether (A), a surfactant (B), and an oil agent (C), and the cationic group-containing cellulose ether (A) has the general formula The main chain derived from anhydroglucose represented by (1), wherein the degree of substitution of the cationized oxyalkylene group per unit of anhydroglucose is from 0.01 to 1.0, and the degree of substitution of the glycerol group Is 0.5 or more and 5.0 or less, and the degree of substitution of the group containing a hydrocarbon group having 3 to 18 carbon atoms represented by the general formulas (6) to (8) is 0.0001 or more 0.2 or less.

(Cationic group-containing cellulose ether (A))
The cationic group-containing cellulose ether (A) (hereinafter also referred to as “CCE (A)”) used in the cleaning composition of the present invention is an anhydroglucose-derived main chain represented by the following general formula (1). The degree of substitution of the cationized oxyalkylene group per anhydroglucose unit 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 degree of substitution of the group containing a hydrocarbon group having 3 to 18 carbon atoms represented by the general formulas (6) to (8) is 0.0001 to 0.2.

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 of each other and may be the same as 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 in the present invention has the structural unit, it is excellent when it is used as a detergent for hair, especially when it is washed with hair, when it is rinsed, and when it is rinsed. In addition, excellent moist feeling and uniformity after drying can be imparted.
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, tridecyl group, tetradecyl group, hexadecyl group, vinyl group, 1-propenyl group, 2-propenyl group, Examples include 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, the water solubility of CCE (A), and when used as a hair cleanser, excellent fingering during washing, excellent slipping and rinsing feeling during rinsing, and excellent moistness after drying From the viewpoint of imparting feeling and uniformity, an alkyl group having 1 to 14 carbon atoms or an alkenyl group having 2 to 14 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Group 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 or an alkenyl group having 2 to 5 carbon atoms is more preferable. 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, a methyl group More preferably more ethyl group, an ethyl group is even 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, hexadecyl group, stearyl 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, phenyl group, methylphenyl group, benzyl group, etc. It is. Among these, the water solubility of CCE (A), excellent fingering during washing when used as a hair washing agent, excellent slipping and continuation feeling during rinsing, and excellent moist feeling after drying And from the viewpoint of imparting uniformity, preferably 3 to 14 carbon atoms, more preferably 3 to 12 carbon atoms, still more preferably 3 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms, still more preferably Is preferably one or more selected from alkyl groups, alkenyl groups, and phenyl groups having 3 to 6 carbon atoms, more preferably 3 to 6 carbon atoms, and alkyl groups and alkenyls having 3 to 6 carbon atoms. One or more selected from a group 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. If MS (N +) is within this range, good fingering at the time of washing the hair, good slipperiness at the time of rinsing after treating the hair and its long-lasting feeling, and moistness and uniformity after drying are sufficient. In addition, a moisturizing feeling after washing the skin can be obtained. In this respect, MS (N +) is preferably 0.04 or more, more preferably 0.05 or more, still more preferably 0.07 or more, still more preferably 0.09 or more, still more preferably 0.10 or more, more More preferably, it is 0.12 or more, More preferably, it is 0.18 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 0.6 or less, still more preferably 0.5 or less, still more preferably 0.35 or less, More preferably, it is 0.3 or less, More preferably, it is 0.20 or less.
From these viewpoints, MS (N +) is preferably in the range of 0.04 to 0.6, more preferably in the range of 0.07 to 0.5, and still more preferably in the range of 0.09 to 0.35. More preferably, it is the range of 0.10-0.3, More preferably, it is the range of 0.10-0.20, More preferably, it is the range of 0.12-0.20, More preferably, it is 0.18-0. .20 range.

<Degree of substitution of glycerol group>
In the present invention, the degree of substitution of a glycerol group (hereinafter also referred to as “MS (Gly)”) is the number of glycerol groups present in the CCE (A) molecule per anhydroglucose unit constituting the main chain. The average value for. 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. If MS (Gly) is within this range, good fingering at the time of washing the hair, good slipperiness at the time of rinsing after treating the hair and its long-lasting feeling, and moistness and uniformity after drying are sufficient. In addition, a moisturizing feeling after washing the skin can be obtained. Moreover, if MS (Gly) is this range, since the solubility to the cleaning composition of CCE (A) is high, a mixing | blending is easy. From these viewpoints, MS (Gly) is preferably 0.7 or more, more preferably 0.8 or more, still more preferably 0.9 or more, still more preferably 1.0 or more, still more preferably 1.3 or more, Still more preferably, it is 1.8 or more, More preferably, it is 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 3.8 or less, still more preferably 3.5 or less, still more preferably 3.0 or less, More preferably, it is 2.5 or less, More preferably, it is 2.3 or less.
From these viewpoints, MS (Gly) is preferably in the range of 0.5 to 4.0, more preferably in the range of 0.7 to 3.8, still more preferably in the range of 0.9 to 3.8. Even more preferably in the range of 1.0 to 3.0, even more preferably in the range of 1.0 to 2.3, even more preferably in the range of 1.3 to 2.3, even more preferably in the range of 2.1 to The range is 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 0.2 or less. If MS (HC) is within this range, good fingering at the time of washing the hair, good slipperiness at the time of rinsing after treating the hair and its long-lasting feeling, and moistness and uniformity after drying the hair are sufficient. In addition, a moisturizing feeling after washing the skin can be obtained. 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. In view of the above viewpoint and the production cost of CCE (A), MS (HC) is preferably 0.15 or less, more preferably 0.10 or less, still more preferably 0.08 or less, still more preferably 0.06 or less, More preferably, it is 0.04 or less.
From these viewpoints, MS (HC) is preferably in the range of 0.0005 to 0.2, more preferably in the range of 0.001 to 0.15, and still more preferably in the range of 0.005 to 0.15. More preferably, it is in the range of 0.01 to 0.10, more preferably in the range of 0.01 to 0.08, still more preferably in the range of 0.01 to 0.06, and still more preferably in the range of 0.02 to 0.06. It is a range, More preferably, it is the range of 0.02-0.04.

  CCE (A) is a good finger-washing method, a good slipperiness after rinsing after hair treatment and its long-lasting feeling, and a moist feeling and uniformity after hair drying, and the skin. From the viewpoint of obtaining a moisturizing feeling after washing, MS (N +) is preferably 0.04 or more and 0.6 or less, MS (Gly) is 0.5 or more and 4.0 or less, and MS (HC) Is CCE of 0.01 or more and 0.10 or less, more preferably MS (N +) is 0.07 or more and 0.5 or less, MS (Gly) is 0.7 or more and 3.8 or less, and MS ( HC) is CCE of 0.01 to 0.06, more preferably MS (N +) is 0.09 to 0.35, MS (Gly) is 1.0 to 3.8, and CCE with MS (HC) of 0.01 to 0.06, even more preferred CCE having MS (N +) of 0.10 or more and 0.20 or less, MS (Gly) of 1.0 or more and 2.3 or less, and MS (HC) of 0.02 or more and 0.06 or less, More preferably, MS (N +) is 0.12 or more and 0.20 or less, MS (Gly) is 1.3 or more and 2.3 or less, and MS (HC) is 0.02 or more and 0.06 or less. More preferably, MS (N +) is 0.18 or more and 0.20 or less, MS (Gly) is 2.1 or more and 2.3 or less, and MS (HC) is 0.02 or more and 0. .04 or lower CCE.

In the case where the cleaning composition of the present invention is used for a hair cleaning agent, when a silicone oil such as dimethylpolysiloxane (dimethicone) is contained as the oil agent (C) described later, the silicone oil such as dimethicone to the hair From the viewpoint of improving the persistence and moist feeling, the MS (N +) of CCE (A) is preferably 0.40 or more, more preferably 0.45 or more, and further preferably 0.50 or more. From the viewpoint of the production cost of A), MS (N +) of CCE (A) is preferably 0.90 or less, more preferably 0.80 or less, and further preferably 0.75 or less.
Moreover, MS (Gly) of CCE (A) is preferably 0.6 or more, more preferably 0.7 or more, and further preferably from the viewpoint of improving the persistence and moist feeling of silicone oil such as dimethicone to the hair. From the viewpoint of the above and the production cost of CCE (A), the MS (Gly) of CCE (A) is preferably 3.0 or less, more preferably 2.5 or less, and still more preferably Is 2.3 or less.
Further, the MS (HC) of CCE (A) is preferably 0.01 or more, more preferably 0.02 or more, and still more preferably from the viewpoint of improving the persistence and moist feeling of silicone oil such as dimethicone to the hair. In view of the above and the production cost of CCE (A), the MS (HC) of CCE (A) is preferably 0.06 or less, more preferably 0.05 or less, and still more preferably Is 0.04 or less.
CCE (A) is preferably MS (N +) of 0.40 or more and 0.90 or less from the viewpoint of improving the persistence and moist feeling of silicone oil such as dimethicone to the hair, and MS (Gly) Is not less than 0.6 and not more than 3.0, and MS (HC) is not less than 0.01 and not more than 0.06, more preferably MS (N +) is not less than 0.45 and not more than 0.80, and MS ( Gly) is 0.7 or more and 2.5 or less and MS (HC) is 0.02 or more and 0.05 or less, more preferably MS (N +) is 0.50 or more and 0.75 or less, MS (Gly) is 0.8 or more and 2.3 or less, and MS (HC) is CCE of 0.03 or more and 0.04 or less.

<Cation charge density>
CCE (A) used in the present invention obtains good fingering during hair washing, good slipperiness during rinsing after treatment of hair and its long lasting feeling, and moist feeling and uniformity after hair drying From the viewpoint of obtaining moisturizing feeling after washing the skin, the cationic charge density is preferably 0.05 mmol / g or more, more preferably 0.15 mmol / g or more, still more preferably 0.2 mmol / g or more, 0 More preferable is 3 mmol / g or more. From the above viewpoint, the cation charge density of CCE (A) 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. g or less. From these viewpoints, 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, still 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.

In addition, when the cleaning composition of the present invention is used for a hair cleaning agent, when it contains a silicone oil such as dimethylpolysiloxane (dimethicone) as an oil agent (C) described later, the cationic charge of CCE (A) A higher density is preferable because the residual amount of silicone oil such as dimethicone after hair treatment is improved. The moist feeling is improved by improving the residual amount of silicone oil such as dimethicone on the hair. From the viewpoint of improving the persistence of silicone oil such as dimethicone on the hair and improving the moist feeling, the cationic charge density of CCE (A) is preferably 0.4 mmol / g or more, more preferably 0.8 mmol / g or more. 0 mmol / g or more is still more preferable, 1.2 mmol / g or more is further more preferable, and 1.3 mmol / g or more is further more preferable. Further, from the viewpoint of obtaining good slipperiness during hair rinsing and its sustainability, 2.0 mmol / g or less is preferable. In addition, from the viewpoint of achieving both the persistence of silicone oil such as dimethicone, moist feeling, good slipperiness during hair rinsing and a feeling of persistence, CCE (A) has a cationic charge density of 0.4 to 2.0 mmol / g. Is preferred, 0.8 to 2.0 mmol / g is more preferred, 1.0 to 2.0 mmol / g is more preferred, 1.2 to 2.0 mmol / g is still more preferred, 1.3 to 2.0 mmol / G is even more preferable.
In addition, the persistence of silicone oil such as dimethicone on the hair can be specifically evaluated by the method described in the examples.

<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 viewpoints described above and from the viewpoint of improving the handling properties of CCE (A) and the detergent 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)>
CCE (A) used in the present invention obtains good fingering during hair washing, good slipperiness during rinsing after treatment of hair and its long lasting feeling, and moist feeling and uniformity after hair drying From the viewpoint of obtaining a moisturizing feeling after washing the skin and improving the stability of the detergent composition, the viscosity of a 1% by weight aqueous solution of CCE (A) is preferably 10 mPa · s or more at 25 ° C. 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 above viewpoint and from the viewpoint of improving the handling properties of the cleaning 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. Is 2000 mPa · s or less.
From these viewpoints, the viscosity of a 1% by mass aqueous solution of CCE (A) is preferably in the range of 10 to 10000 mPa · s, more preferably in the range of 50 to 5000 mPa · s, and further preferably 100 to 3000 mPa · s at 25 ° C. -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 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. Thereafter, it is preferable to perform a cationization reaction and a hydrocarbon group-containing group introduction reaction.
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 as follows: good fingering at the time of washing the hair, good slipperiness at the time of rinsing after treating the hair and its long lasting feeling, and a moist feeling and uniformity after drying the hair; and From the viewpoint of obtaining a moisturizing feeling after washing the skin, it is preferably 100 or more, more preferably 200 or more, still more preferably 500 or more, and still more preferably 1000 or more. Further, from the above viewpoint and from the viewpoint of improving the handling properties of the CCE (A) and the cleaning composition, it is preferably 12000 or less, more preferably 10,000 or less, still more preferably 5000 or less, and still more preferably 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 still more 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. More preferably, it is 0.1% by 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 further 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. A biaxial paddle dryer manufactured by Nara Machinery Co., Ltd. can be preferably used as the biaxial horizontal stirring dryer.
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, further preferably 10 ° C. or higher, preferably Is 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. Further, from the viewpoint of improving the persistence and moist feeling of silicone oil such as dimethicone on the hair, the amount of the glycerolating agent used is preferably 10 to 60 mol, more preferably 10 to 1 mol of AGU of the raw material cellulose. 50 moles.
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 10 mol or less, more preferably 8 mol or less, still more preferably 5 mol or less. Moreover, the amount of the cationizing agent to be used is preferably 0.01 to 10 mol, more preferably 0.03 to 8 mol, and still more preferably 0.05 to 5 mol from these viewpoints. Further, from the viewpoint of improving the persistence of silicone oil such as dimethicone to hair and improving moist feeling, the amount of the cationizing agent used is preferably 5 to 60 mol, more preferably 10 to 1 mol of AGU of the raw material cellulose. 60 mol, more preferably 20 to 60 mol.
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. , Good fingering during hair washing, good slipperiness during rinsing after hair treatment and its long lasting feeling, moist feeling and uniformity after hair drying, and after washing the skin From the viewpoint of obtaining a moisturizing feeling, one or more selected from propylene oxide, 1,2-butylene oxide, 1,2-epoxypentane and 1,2-epoxyhexane are preferable, and from propylene oxide and 1,2-butylene oxide. One or more selected are 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 an alkane halide having 3 to 18 carbon atoms and a glycidyl ether having an alkyl group having 3 to 18 carbon atoms is preferable, and an alkane halide 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 kinds selected from 1-bromohexane, 1-octane chloride, 1-dodecane chloride, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, and hexyl glycidyl ether are preferable. One or more kinds selected from chlorohexan, 1-octane chloride, 1-dodecane chloride, propyl glycidyl ether and butyl glycidyl ether are more preferred, and butyl glycidyl ether is still more preferred. 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 cationization, cationization and introduction of 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, still more preferably with respect to 1 mol of AGU of the raw material cellulose. Is 0.8 to 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 cationization, cationization and introduction of 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 further 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 CCE (A) in the cleaning composition of the present invention is as follows: good slipping during hair washing, excellent slipperiness during rinsing after treating the hair, and its persistence, as well as after hair drying From the viewpoint of obtaining a moist feeling and uniformity, and from the viewpoint of obtaining a moisturizing feeling after washing the skin, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass. It is above, More preferably, it is 0.2 mass% or more. Moreover, from a viewpoint of the handleability of a cleaning composition, Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 1 mass% or less. Moreover, from these viewpoints, the content of CCE (A) in the cleaning composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and still more preferably 0.1. It is -1 mass%, More preferably, it is 0.2-1 mass%.

(Surfactant (B))
The cleaning composition of the present invention contains one or more surfactants (B).
As the surfactant (B), any surfactant can be used as long as it is usually used in pharmaceuticals, quasi drugs, cosmetics, toiletries, miscellaneous goods and the like. Specifically, one or two or more types selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants can be mentioned, and the viewpoint of obtaining the effects of the present invention. Therefore, at least one selected from anionic surfactants, nonionic surfactants, and amphoteric surfactants is preferred.

<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 Hydrophobic sites such as alkyl ester salts, polyoxyalkylene sulfosuccinic acid alkyl ester salts, alkane sulfonates, acyl isethionates, acyl methyl taurates, and internal olefin sulfonates having 12 to 24 carbon atoms described below Sulfonates; higher fatty acid salts having 8 to 16 carbon atoms; carboxylates having a hydrophobic site such as alkyl ether acetates represented by the following general formula (I); alkyl phosphates, polyoxyalkylene alkyl ether phosphoruss Sparse acid salts Phosphoric acid ester salts having a sex site; acyl glutamates, alanine derivatives, 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 of 4.0 to 16 and M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), Represents ammonium or organic ammonium)

  Except for the above-mentioned internal olefin sulfonate having 12 to 24 carbon atoms, the anionic surfactant obtains the effects of the present invention from the viewpoints of cleaning properties, foamability and foam quality of the cleaning composition. From the viewpoint, it is preferable to have an alkyl group or alkenyl group having 8 to 20 carbon atoms as the 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 the above anionic surfactants, alkyl sulfates such as sodium lauryl sulfate, polyoxyethylene lauryl ether sulfate (laureth- (1) ammonium sulfate, laureth- (1) sodium sulfate, laureth- (2) sodium sulfate Polyoxyethylene alkyl ether sulfates such as laureth- (3) sodium sulfate), higher fatty acid salts having 8 to 16 carbon atoms such as potassium laurate, laureth- (4,5) sodium acetate, laureth- (10) Alkyl ether acetates represented by the above general formula (I) such as sodium acetate, sulfosuccinic acid alkyl ester salts such as sodium laureth-2 sulfosuccinate, acyl glutamates such as sodium N-acyl-L-glutamate (sodium cocoylglutamate) N-Lauroyl Sarco Glycine derivatives such as emissions sodium, one or more is preferably selected from 14 or more 16 or less α- olefin sulfonates and internal olefin sulfonates having 12 or more 24 or less carbon atoms.

[Internal olefin sulfonate]
The detergent composition of the present invention, as an anionic surfactant, has environmental stability and low irritation, etc., improved detergency, improved foam quality, improved foamability, good foam sustainability and rinsing Perspective of imparting improved smoothness, excellent fingering during hair washing, excellent slipperiness during rinsing after hair treatment and its long lasting feeling, and excellent moist feeling, uniformity and cohesiveness after drying The skin contains an internal olefin sulfonate having 12 to 24 carbon atoms (hereinafter also simply referred to as “internal olefin sulfonate”) from the viewpoint of imparting excellent moisturizing feeling and moist feeling after drying. May be.

  In the present invention, the internal olefin sulfonate is a sulfonate obtained by sulfonating, neutralizing and hydrolyzing an internal olefin (olefin having a double bond inside the olefin chain) as a raw material. In addition, such an internal olefin has a broad meaning including the case where it contains a trace amount of what is called an alpha olefin in which the position of a double bond exists in the 1st position of a carbon chain. That is, when the internal olefin is sulfonated, β-sultone is quantitatively produced, and a part of β-sultone is changed to γ-sultone and olefin sulfonic acid, and these are further converted into hydroxy in the neutralization / hydrolysis step. Conversion to alkane sulfonate and olefin sulfonate (eg, J. Am. Oil Chem. Soc. 69, 39 (1992)). Here, the hydroxy group of the resulting hydroxyalkane sulfonate is inside the alkane chain, and the double bond of the olefin sulfonate is inside the olefin chain. The resulting product is mainly a mixture of these, and some of them are hydroxyalkane sulfonates having a hydroxy group at the end of the carbon chain, or olefin sulfonic acids having a double bond at the end of the carbon chain. There may be a trace amount of salt. In this specification, each of these products and mixtures thereof are collectively referred to as internal olefin sulfonates. The hydroxyalkanesulfonate is referred to as a hydroxy form of internal olefin sulfonate (hereinafter also referred to as HAS), and the olefin sulfonate is referred to as an olefin form of internal olefin sulfonate (hereinafter also referred to as IOS).

The carbon number of the internal olefin sulfonate improves the foaming property, foam persistence and rinsing properties of the cleaning composition, excellent sliding properties after rinsing the hair, and uniformity after drying and From the viewpoint of imparting unity and from the viewpoint of imparting excellent moisturizing feeling and moist feeling after drying of the skin, it is preferably 12 or more, more preferably 14 or more, and still more preferably 16 or more. In addition, the carbon number of the internal olefin sulfonate is excellent as a finger when washing hair, excellent slipperiness during rinsing after hair treatment and its long lasting feeling, and excellent moist feeling and uniformity after drying. From the viewpoint of imparting cohesiveness, an excellent moisturizing feeling after drying the skin, and a moist feeling, it is preferably 24 or less, more preferably 20 or less, and still more preferably 18 or less. These hydroxy bodies and olefin bodies having various carbon numbers are derived from internal olefins used as raw materials, and hydroxy bodies and olefin bodies having carbon numbers other than those described above may be included.
An internal olefin sulfonate may be used individually by 1 type, and may be used in combination of 2 or more type.

When two or more internal olefin sulfonates are used in combination, the foam persistence and rinsability are improved, excellent fingering during hair washing, and excellent slipping during rinsing after treating the hair. From the viewpoint of imparting its long-lasting feeling, excellent moist feeling and uniformity after drying, and cohesiveness, and excellent moisturizing feeling and moist feeling after drying the skin, an internal olefin sulfonate having 16 carbon atoms. And an internal olefin sulfonate having 18 carbon atoms are preferably used in combination.
In this case, in the cleaning composition of the present invention, the mass ratio of the content of the internal olefin sulfonate having 16 carbon atoms and the content of the internal olefin sulfonate having 18 carbon atoms (internal olefin sulfonate having 16 carbon atoms). / Inner olefin sulfonate having 18 carbon atoms) is preferably 50/50 to 99/1, more preferably 60/40 to 95/5, still more preferably 70/30 to 90 from the above viewpoint. / 10, more preferably 75/25 to 90/10, still more preferably 75/25 to 85/15, and still more preferably 78/22 to 85/15.
The mass ratio can be measured by a high performance liquid chromatography mass spectrometer (hereinafter also referred to as “HPLC-MS”). Specifically, an internal olefin sulfonate having 16 carbon atoms and an internal olefin sulfonate having 18 carbon atoms are separated from the internal olefin sulfonate or the resulting detergent composition by HPLC, and each is subjected to MS. Thus, the mass ratio can be determined from the HPLC-MS peak area.

The content of the internal olefin sulfonate having a sulfonic acid group at the 2-position with respect to the total amount of the internal olefin sulfonate in the cleaning composition of the present invention is improved in foaming property, foam quality and rinsing property, hair washing Excellent slipperiness at the time of rinsing after treatment of hair, its long lasting feeling, excellent moist feeling and uniformity after drying, cohesiveness, excellent after dry skin From the viewpoint of imparting a moisturizing feeling and moist feeling, it is preferably 25% by mass or less, more preferably 23% by mass or less.
The lower limit of the content of the internal olefin sulfonate in which the sulfonic acid group is located at the 2-position with respect to the total amount of the internal olefin sulfonate in the cleaning composition of the present invention is a reduction in production cost, an improvement in productivity, and Perspective of imparting long-lasting foam, excellent fingering during hair washing, excellent slipperiness during rinsing after treatment of hair and its long-lasting feeling, and excellent moist feeling, uniformity and cohesiveness after drying Therefore, it is preferably 5% by mass or more, and more preferably 8% by mass or more.
The content of the internal olefin sulfonate having a sulfonic acid group at the 2-position can be measured by a method such as nuclear magnetic resonance spectrum. Specifically, it can be measured by a method using gas chromatography described in Examples described later.

  The internal olefin sulfonate is preferably a mixture of hydroxy and olefin. The mass ratio (hydroxy body / olefin body) of the content of the hydroxy group of the internal olefin sulfonate and the content of the olefin body of the internal olefin sulfonate in the cleaning composition is from the viewpoint of improving productivity and reducing impurities. The ratio is preferably 50/50 to 100/0, more preferably 70/30 to 100/0, and still more preferably 75/25 to 95/5.

  The mass ratio of the content of the hydroxy body of the internal olefin sulfonate and the content of the olefin body of the internal olefin sulfonate in the cleaning composition of the present invention is the internal olefin sulfonate or the cleaning composition containing this. After separating the hydroxy form and the olefin form from the product by HPLC, it can be measured by the method described in Examples.

  The internal olefin sulfonate can be obtained by sulfonating a raw material internal olefin having 12 to 24 carbon atoms, neutralizing, and then hydrolyzing. The conditions for sulfonation, neutralization, and hydrolysis are not particularly limited. For example, Japanese Patent No. 1633184, Japanese Patent No. 2625150, Tenside Surf. Det. Reference can be made to the conditions described in 31 (5) 299 (1994).

  In the present invention, the raw material internal olefin refers to an olefin having a double bond substantially inside the olefin chain as described above. The carbon number of the raw material internal olefin improves the foaming property, foam persistence and rinsing property of the cleaning composition, excellent slipping property at the time of rinsing after treating the hair, and uniformity and cohesiveness after drying. From the viewpoint of imparting an excellent moisturizing feeling after drying of the skin and a moist feeling, it is preferably 12 or more, more preferably 14 or more, and even more preferably 16 or more, which is excellent when washing hair. As per finger, excellent slipperiness at the time of rinsing after treating the hair and its long-lasting feeling, as well as excellent moistness and uniformity after drying, a viewpoint of imparting cohesiveness, excellent moisturizing feeling after drying the skin, From the viewpoint of moist feeling, it is preferably 24 or less, more preferably 20 or less, and still more preferably 18 or less. The internal olefin used as a raw material may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the internal olefin in which the double bond in the raw material internal olefin is located at the 2-position provides foaming properties and a creamy and easy-to-clean foam quality, and improves rinsing properties, excellent fingering during hair washing, Provides excellent slipperiness and persistence during rinsing after treatment, as well as excellent moistness and uniformity after drying, a viewpoint of imparting cohesiveness, and excellent moisturizing and moisturizing feeling after drying the skin. From the viewpoint, it is preferably 40% by mass or less, more preferably 35% by mass or less, after reduction of production cost, improvement of productivity and persistence of foam, excellent fingering during hair washing, and after treating hair From the viewpoint of imparting excellent slipperiness at the time of rinsing and its long-lasting feeling, and excellent moist feeling after drying, uniformity and cohesiveness, it is preferably 5% by mass or more, more preferably 9 wt%, more preferably at least 15 wt%.

  The distribution of double bonds in the raw material internal olefin can be measured by, for example, a gas chromatograph mass spectrometer (hereinafter also referred to as “GC-MS”). Specifically, each component having a different carbon chain length and double bond position is accurately separated by a gas chromatograph analyzer (hereinafter also referred to as “GC”), and each is separated by a mass spectrometer (hereinafter also referred to as “MS”). ), The double bond position can be identified, and the respective ratios can be determined from the GC peak area.

  The sulfonation reaction can be performed by reacting 1.0 to 1.2 mol of sulfur trioxide gas with respect to 1 mol of the raw material internal olefin. The reaction temperature is preferably 20 to 40 ° C.

  Neutralization is carried out by reacting an alkaline aqueous solution such as sodium hydroxide, ammonia, 2-aminoethanol, etc. in an amount of 1.0 to 1.5 mol times the theoretical value of the sulfonic acid group.

  The hydrolysis reaction may be performed at 90 to 200 ° C. for 30 minutes to 3 hours in the presence of water. These reactions can be performed continuously. Moreover, after completion | finish of reaction, it can refine | purify by extraction, washing | cleaning, etc.

  In addition, in producing the internal olefin sulfonate, the raw material internal olefin having a distribution of 12 to 24 carbon atoms may be used for sulfonation, neutralization, and hydrolysis treatment, and it has a single carbon number. The raw material internal olefin may be used for sulfonation, neutralization, and hydrolysis, and a plurality of types of internal olefin sulfonates having different carbon numbers produced in advance may be mixed as necessary.

<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 fatty acid alkanolamides.
The nonionic surfactant is an alkyl having 8 to 20 carbon atoms as a hydrophobic site from the viewpoint of the cleaning properties of the hair cleaning agent, the amount of foam at the time of cleaning, the foam quality, and the effect of the present invention. It preferably has a group or an alkenyl group.
Among these, at least one selected from polyoxyalkylene alkyl ether, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide, and alkyl glycoside is preferable, and has 8 to 18 carbon atoms such as lauryl glucoside and decyl glucoside, preferably C8-C12 alkyl glucoside, polyoxyethylene lauryl ether (laureth-3), polyoxyethylene alkyl ethers such as polyoxyethylene cetostearyl ether, coconut oil fatty acid monoethanolamide, and coconut oil fatty acid N-methyl mono One or more selected from fatty acid monoalkanolamides such as ethanolamide are more preferred.

<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 detergency of the cleaning composition and the amount of foam at the time of washing, foam quality, and the effect of the present invention, imidazoline-based betaine, alkyldimethylaminoacetic acid betaine, fatty acid amidopropyl betaine, And at least one selected from alkylhydroxysulfobetaines, specifically, one selected from coconut oil fatty acid amidopropylbetaine, laurylcarboxymethylhydroxyimidazolium betaine, lauryldimethylaminoacetic acid betaine, and laurylhydroxysulfobetaine. The above is preferable.

<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, okdadecyloxypropyltrimethylammonium 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 imparting the effects of the present invention, mono long-chain alkyltrimethylammonium salts such as behenyltrimethylammonium chloride and cetyltrimethylammonium chloride are preferable.

<Content of surfactant (B)>
The content of the surfactant (B) in the cleaning composition of the present invention is as follows: good finger cleaning at the time of hair washing, excellent slipperiness at the time of rinsing after treating the hair, and its long-lasting feeling, and hair drying From the viewpoint of obtaining a moist feeling and uniformity of time, and from the viewpoint of obtaining an excellent moisturizing feeling after treating, rinsing and drying the skin, preferably 1% by mass or more, more preferably 5% by mass or more, From the above viewpoint, it is preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 36% by mass or less. From the above viewpoint, the content of the surfactant (B) is preferably in the range of 1 to 80% by mass, more preferably 5 to 50% by mass, and still more preferably 5 to 36% by mass.
When the detergent composition of the present invention is used as a hair detergent, the content of the surfactant (B) is more preferably 5% by mass or more, and still more preferably 8 from the viewpoint of obtaining the effects of the present invention. It is at least 10% by mass, more preferably at least 10% by mass, even more preferably at most 25% by mass, even more preferably at most 20% by mass. From the above viewpoint, the content of the surfactant (B) is more preferably 5 to 25% by mass, still more preferably 8 to 20% by mass, and 10 to 20% by mass. It is even more preferable.
When the detergent composition of the present invention is used as a skin cleanser, the content of the surfactant (B) is excellent after the skin is rinsed, rinsed and dried with the detergent composition of the present invention. From the viewpoint of obtaining a feeling, it is more preferably 10% by mass or more and 36% by mass or less.

(Oil agent (C))
The cleaning composition of the present invention is excellent in moist feeling after treatment drying, a viewpoint of obtaining softness when used as a hair cleaning agent, and after treating and drying the skin when used as a skin cleaning agent. From the viewpoint of obtaining a moisturizing feeling, the oil (C) is contained.
The oil agent (C) is an oily component that is usually used in pharmaceuticals, quasi drugs, cosmetics, toiletries, miscellaneous goods, etc., and has a solubility in water of 100 g of water at 20 ° C. of 0 g or more and 1 g or less. Alternatively, any water-insoluble oil agent can be used. From the above viewpoint, the amount of the oil agent (C) 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.
From the above viewpoint, the oil agent (C) is substituted with (i) ester oil, (ii) silicone oil, (iii) ether oil, (iv) hydrocarbon oil, (v) higher alcohol, and (vi) hydroxyl group. It is preferably at least one selected from carboxylic acids having a hydrocarbon group having 17 to 23 carbon atoms which may be present.

<(I) Ester oil>
(I) As an ester oil, from the viewpoint of imparting the effects of the present invention, an ester oil represented by the following general formula (16), (17) or (19), and a hydrophobic carboxylic acid ester of dipentaerythritol, And the dialkyl carbonate compound represented by the following general formula (20) is preferable.

[Ester oil represented by general formula (16), (17)]
R ²⁵ —COO—R ²⁶ (16)
(In the formula, R ²⁵ represents a linear or branched alkyl group having 7 to 22 carbon atoms, and R ²⁶ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms.)
The number of carbon atoms in R ²⁵ in formula (16), from the above viewpoints, preferably 10 or more, more preferably 12 or more. Moreover, 20 or less is preferable and 18 or less is more preferable. The number of carbon atoms of R ^25, from the above viewpoint, preferably 10 to 20, 12 to 18 is more preferable.
From the above viewpoint, the number of carbon atoms of R ²⁶ is preferably 1 or more, preferably 20 or less, and more preferably 18 or less. The number of carbon atoms of R ²⁶ is preferably 1 to 20, 1 to 18 is more preferable. R ²⁶ is more preferably a propyleneoxy group or a linear or branched alkyl group or alkenyl group having 1 to 18 carbon atoms which may be separated by a phenyl group.

  Specific examples of the ester oil represented by the general formula (16) include beeswax, lanolin, reduced lanolin, lanolin fatty acid octyldodecyl, eicosenate caprylyl, 2-ethylhexanoate myristyl, 2-ethylhexanoate cetyl, 2-ethyl Stearyl hexanoate, octyl octoate, lauryl octoate, myristyl octoate, isocetyl octoate, octyl propyl heptanoate, cetostearyl isononanoate, isononyl isononanoate, isotridecyl isononanoate, methyl laurate, hexyl laurate, octyl laurate , Isopropyl myristate, octyl myristate, myristyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, octyl palmitate, Cetyl luminate, methyl oleate, oleyl oleate, decyl oleate, isobutyl oleate, methyl stearate, 2-ethylhexyl stearate, octyl stearate, isocetyl stearate, stearyl stearate, butyl stearate, isotridecyl stearate, Examples include isopropyl isostearate, isocetyl isostearate, isostearyl isostearate, 2-ethylhexyl hydroxystearate, oleyl erucate, and the like.

  Among the ester oils represented by the general formula (16), from the viewpoint of excellent moist feeling after drying, uniformity and moisturizing feeling when using the surfactant composition of the present invention, octyl laurate, Isopropyl myristate, octyl myristate, myristyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, octyl palmitate, cetyl palmitate, methyl stearate, 2-ethylhexyl stearate, octyl stearate, isocetyl stearate, stearic acid One or more selected from stearyl, butyl stearate, isotridecyl stearate, and 2-ethylhexyl hydroxystearate are preferable. From myristyl myristate, isopropyl palmitate, cetyl palmitate, and stearyl stearate Least one barrel more preferable.

(In the formula, R ²⁷ , R ²⁸ and R ²⁹ are each independently a hydrogen atom or a group represented by the following general formula (18), and all of them are not hydrogen atoms.)
-CO-R ³⁰ (18)
(Wherein R ³⁰ represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms which may be divided by a carboxylic acid ester group and optionally substituted by a hydroxyl group.)
In the general formula (18), the carbon number of R ³⁰ is preferably 8 or more and 20 or less, and more preferably 8 or more and 18 or less from the above viewpoint.

  Specific examples of the ester oil represented by the general formula (17) include castor oil, cacao oil, mink oil, avocado oil, olive oil, sunflower oil, camellia oil, kyounin oil, almond oil, wheat germ oil, theobro magundiflor. Sesame seed oil, grape seed oil, babas oil, jojoba oil, macadamia nut oil, yucha oil, shea fat oil, camellia seed oil, meadow foam oil, glyceryl tribehenate, triisostearin and the like.

  Among the ester oils represented by the general formula (17), sunflower oil and avocado are used from the viewpoint of excellent moist feeling after drying, uniformity and moisturizing feeling when the surfactant composition of the present invention is used. One or more selected from oil, camellia oil, macadamia nut oil, and shea fat oil are more preferable, and one or more selected from sunflower oil, avocado oil, and macadamia nut oil are more preferable.

[Ester oil represented by general formula (19)]
^{R 31 O- (AO) m-} COR 32 (19)
(In the formula, R ³¹ represents a hydrocarbon group having 6 to 20 carbon atoms and containing at least one aromatic ring which is substituted or unsubstituted, and R ³² is a linear or branched chain having 1 to 25 carbon atoms. Represents an alkyl group or an alkenyl group, AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and m represents a number of 1 to 50. When m is 2 or more, m AO groups are the same. But it may be different.)
From the above viewpoint, R ^{31 in the} general formula (19) is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and further preferably a benzyl group. .
From the above viewpoint, R ³² is preferably an alkyl group having 7 or more carbon atoms, more preferably an alkyl group having 11 or more carbon atoms, preferably an alkyl group having 21 or less carbon atoms, more preferably 15 or less carbon atoms. It is an alkyl group. R ³² is preferably an alkyl group having 7 to 21 carbon atoms, and more preferably an alkyl group having 11 to 15 carbon atoms.
From the above viewpoint, the AO group is preferably a propyleneoxy group, and m is preferably from 1 to 10, and more preferably from 1 to 5.
Preferable examples of the ester oil represented by the general formula (19) include propylene oxide 3-mole adduct of benzyl alcohol and ester of myristic acid (manufactured by Croda: Crodamol STS), propylene oxide 3-mole adduct of benzyl alcohol, An ester of 2-ethylhexanoic acid (manufactured by Croda: Kurodamol SFX) is exemplified.

[Hydrophobic carboxylic acid ester of dipentaerythritol]
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.

[Dialkyl carbonate compound represented by general formula (20)]
^{_{R 33 O (CH 2 CH 2}} O) vCO (OCH 2 CH 2) w-OR 34 (20)
(In the formula, R ³³ and R ³⁴ each represent a linear or branched alkyl group and / or alkenyl group having 6 to 22 carbon atoms, and v and w are each 0 or 1 or more and 50 or less. .)
From the above viewpoint, R ³³ and R ^{34 in} the general formula (20) are preferably an alkyl group having 8 or more carbon atoms, an alkyl group having 18 or less carbon atoms is preferable, and an alkyl group having 12 or less carbon atoms is more preferable. In addition, R ³³ and R ³⁴ are preferably an alkyl group having 6 to 18 carbon atoms, and more preferably an alkyl group having 8 to 12 carbon atoms from the above viewpoint.
From the above viewpoint, v and w are preferably 0 or 1 or more and 5 or less, and more preferably 0.
Preferable examples of the dialkyl carbonate compound represented by the general formula (20) include dioctyl carbonate (manufactured by Cognis: cethiol CC).

  Examples of ester oils other than the above include esters of polyvalent carboxylic acids and alcohols, esters of polyhydric alcohols and fatty acids excluding glycerin, dipentaerythritol and saccharides, and esters of saccharides and fatty acids. Specific examples thereof include diisopropyl dimer, propanediol dicaprate, diisopropyl adipate, diethoxyethyl succinate, 2-ethylhexyl succinate, polysoy fatty acid sucrose, polybehenate sucrose, tetraisostearate sucrose, hydroxyalkyl ( C16-18) Hydroxy dimer linoleyl ether, pentaerythryl tetrastearate, glycol distearate and the like, and sucrose tetraisostearate is preferable.

<(Ii) Silicone oil>
(Ii) As silicone oil, from the viewpoint of imparting the effects of the present invention, dimethylpolysiloxane, dimethiconol (dimethylpolysiloxane having a hydroxyl group at the terminal), and amino-modified silicone (dimethylpolysiloxane having an amino group in the molecule) ), Polyether-modified silicone, glyceryl-modified silicone, amino derivative silicone, silicone wax, and silicone elastomer are preferred, and dimethylpolysiloxane is more preferred.
(Ii) The viscosity at 25 ° C. of the silicone oil is such that the hair after treatment and drying with the cleaning composition of the present invention has a good moist feeling, softness, and dispersibility when preparing the cleaning composition. From 10 mm ² / s to 15 million mm ² / s.

<(Iii) Ether oil>
(Iii) As the ether oil, from the viewpoint of imparting the effects of the present invention, a dialkyl ether compound represented by the following general formula (21) or a polyoxyalkylene alkyl ether compound represented by the following general formula (22) is used. preferable.

[Dialkyl ether compound represented by general formula (21)]
R ³⁵ —O—R ³⁶ (21)
(In the formula, R ³⁵ and R ³⁶ each represent a linear or branched alkyl group and / or alkenyl group having 6 to 22 carbon atoms.)
From the above viewpoint, R ³⁵ and R ^{36 in} the general formula (21) are preferably an alkyl group having 8 or more carbon atoms, an alkyl group having 18 or less carbon atoms is preferable, and an alkyl group having 12 or less carbon atoms is more preferable. In addition, R ³⁵ and R ³⁶ are preferably an alkyl group having 6 to 18 carbon atoms, and more preferably an alkyl group having 8 to 12 carbon atoms from the above viewpoint.
Preferable examples of the dialkyl ether compound represented by the general formula (21) include dioctyl ether (manufactured by Cognis: cethiol OE).

[Polyoxyalkylene alkyl ether compound represented by the general formula (22)]
R ³⁷ —O— (PO) _r (EO) _s —H (22)
(In the formula, R ³⁷ represents a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms. PO represents a propyleneoxy group, EO represents an ethyleneoxy group. The number r represents a number from 0.1 to 15, and the average added mole number s of EO represents a number from 0 to 10. When s is not 0, the addition form of PO and EO may be random. It may be a block, and the order of addition of PO and EO does not matter.)
In general formula (22), from the above viewpoint, R ³⁷ preferably has 8 or more carbon atoms. The carbon number of R ³⁷ is preferably 20 or less, more preferably 18 or less, and still more preferably 12 or less. From the above viewpoint, the carbon number of R ³⁷ is preferably 6 to 20, more preferably 6 to 18, and still more preferably 8 to 12.
The average added mole number r is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. The average added mole number r is preferably 13 or less, and more preferably 10 or less. From the above viewpoint, the average added mole number r is preferably 1 to 15, more preferably 2 to 13, and still more preferably 3 to 10.
The average added mole number s is preferably 10 or less, more preferably 5 or less, still more preferably 1 or less, and still more preferably 0.

Specific examples of the polyoxyalkylene alkyl ether compound represented by the general formula (22) include polyoxypropylene hexyl ether, polyoxypropylene octyl ether having an average addition mole number r of propyleneoxy group of 1 to 15, Polyoxypropylene 2-ethylhexyl ether, polyoxypropylene decyl ether, polyoxypropylene isodecyl ether, polyoxypropylene lauryl ether, polyoxypropylene myristyl ether, polyoxypropylene palmityl ether, polyoxypropylene cetyl ether, polyoxypropylene stearyl Ether, polyoxypropylene isostearyl ether, polyoxypropylene octyl decyl ether, polyoxypropylene icosyl ether, polyethylene Polyoxypropylene behenyl ether.
Among these, from the above viewpoint, at least one selected from polyoxypropylene octyl ether, polyoxypropylene decyl ether, polyoxypropylene lauryl ether having an average addition mole number r of propyleneoxy group of 3 to 10 is included. More preferred.

<(Iv) Hydrocarbon oil>
(Iv) The hydrocarbon oil is preferably a saturated or unsaturated hydrocarbon having 20 or more carbon atoms from the viewpoint of imparting the effects of the present invention.
(Iv) Specific examples of the hydrocarbon oil include squalene, squalane, liquid paraffin, liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomer, cycloparaffin, polybutene, petrolatum, paraffin wax, microcrystalline wax, polyethylene wax, ceresin. From the viewpoint of unity of hair, squalane, squalene, liquid paraffin, petroleum jelly and paraffin wax are preferred, and one or more selected from squalane, liquid paraffin, petroleum jelly and paraffin wax are more preferred.

<(V) Higher alcohol>
(V) As a higher alcohol, the alcohol which has a C6-C22 linear or branched alkyl group or alkenyl group from a viewpoint which provides the effect of this invention is preferable. 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.
(V) Specific examples of higher alcohol 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 -Octyldodecanol, icosyl alcohol, behenyl alcohol.
Among these, at least one selected from lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and 2-octyldodecanol is preferable.

<(Vi) Carboxylic acid having a hydrocarbon group having 17 to 23 carbon atoms which may be substituted with a hydroxyl group>
(Vi) The hydrocarbon group of the carboxylic acid having a hydrocarbon group having 17 to 23 carbon atoms that may be substituted with a hydroxyl group is a straight chain having 17 to 23 carbon atoms from the viewpoint of imparting the effects of the present invention. A chain or branched alkyl group or alkenyl group is 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 (C) can be used individually or in combination of 2 or more types.

<Content of oil agent (C)>
The content of the oil (C) in the cleaning composition is a moist feeling after drying after hair treatment, a point of obtaining softness when used as a hair cleaning agent, and a case of using as a skin cleaning agent From the viewpoint of obtaining an excellent moisturizing feeling after treating, rinsing and drying the skin, 0.01% by mass or more is preferable, 0.05% by mass or more is more preferable, 0.1% by mass The above is more preferable. From the viewpoint of suppressing the sticky feeling of the hair after treatment drying with a hair detergent and from the viewpoint of economy, it is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less. If these viewpoints are put together, 0.01-30 mass% is preferable, as for content of an oil agent (C), 0.05-20 mass% is more preferable, and 0.1-15 mass% is still more preferable.
In the case where the cleaning composition is a hair cleaning agent, the content of the oil agent (C) is more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more, from the above viewpoint. 5 mass% or more is still more preferable, and 1.0 mass% or more is still more preferable. Moreover, 10 mass% or less is still more preferable, 8 mass% or less is further more preferable, 5 mass% or less is further more preferable, and 3 mass% or less is still more preferable. Further, when the cleaning composition is a hair cleaning agent, the content of the oil agent (C) is more preferably 0.01 to 10% by mass, still more preferably 0.1 to 8% by mass, and 5-5 mass% is still more preferable, and 1.0-3 mass% is still more preferable.

In the cleaning composition of the present invention, the mass ratio of CCE (A), surfactant (B), and oil (C) is the same when the cleaning composition of the present invention is used as a hair cleaning composition. Treats the skin when used as a skin cleanser, as a finger when washing, excellent slipperiness at the time of rinsing after hair treatment and its long-lasting feeling, moist feeling after drying, and obtaining uniformity. From the viewpoint of obtaining an excellent moisturizing feeling after rinsing and drying, the following range is preferred.
In the cleaning composition of the present invention, the mass ratio of CCE (A) to surfactant (B) [CCE (A) / surfactant (B)] is preferably 0.0002 or more from the above viewpoint. 0.005 or more is more preferable, 10 or less is preferable, 5 or less is more preferable, and 3 or less is still more preferable. In addition, from the above viewpoint, [CCE (A) / surfactant (B)] is preferably 0.0002 to 10, more preferably 0.0002 to 5, and still more preferably 0.005 to 3.
When the cleaning composition is a hair cleaning composition, the mass ratio of CCE (A) to surfactant (B) [CCE (A) / surfactant (B)] is 0.005 or more from the above viewpoint. Is preferable, 0.010 or more is more preferable, 0.015 or more is more preferable, 0.5 or less is preferable, 0.2 or less is more preferable, and 0.1 or less is still more preferable. In addition, when the cleaning composition is a hair cleaning agent, [CCE (A) / surfactant (B)] is preferably 0.005 to 0.5, more preferably 0.010 to 0.2, 0.015-0.1 is still more preferable.

In the cleaning composition of the present invention, the mass ratio of CCE (A) to the oil (C) [CCE (A) / oil (C)] is obtained when the cleaning composition of the present invention is used as a hair cleaning composition. Of the skin when used as a washing agent for skin, and the excellent slipperiness and persistence during rinsing after hair treatment, the moist feeling after drying, and the softness. From the viewpoint of obtaining an excellent moisturizing feeling after treatment, rinsing and drying, 0.001 to 5 is preferred.
When the cleaning composition is a hair cleaning agent, the mass ratio of CCE (A) to oil (C) [CCE (A) / oil (C)] is preferably 0.001 or more from the above viewpoint. Preferably it is 0.005 or more, More preferably, it is 0.01 or more, More preferably, it is 0.03 or more, Preferably it is 5 or less, More preferably, it is 1 or less, More preferably, it is 0.6 or less. Moreover, when the cleaning composition is a hair cleaning agent, [CCE (A) / oil agent (C)] is preferably 0.001 to 5, more preferably 0.005 to 1, and 0.01 to 0.00. 6 is more preferable, and 0.03-0.6 is more preferable.

<Other ingredients>
In the cleaning composition of the present invention, glycerin, humectants, polysaccharides, polypeptides, pearling agents, solvents, dyes, fragrances, jets, which are usually blended in hair cleaning agents and skin cleaning agents. Agents, edetacetic acid salts, chelating agents such as citrates, pH adjusters, preservatives, anti-dandruff agents such as zinc pyrithione and piroctone olamine, and the like can be appropriately blended as necessary.
For example, a pearling agent is a component that can impart a pearly luster to the appearance of a surfactant composition, and is an emulsion of glycol and fatty acid esters (for example, monoesters and diesters), long-chain dialkyl ethers, water, Known compounds as pearlizing agents such as insoluble inorganic salts can be used, and glycol and fatty acid esters are preferred from the viewpoint of cost and availability. Among them, ethylene glycol monostearate, ethylene glycol distearate, and further ethylene Glycol distearate is preferred.

(Method for producing cleaning composition)
There is no restriction | limiting in particular in the manufacturing method of the cleaning composition of this invention, It can manufacture by a conventional method. Specifically, for example, in the case of a shampoo for liquid hair, water and the surfactant (B) are heated and uniformly mixed. After confirming uniform dissolution, CCE (A) is added and mixed. The order of adding CCE (A) and the surfactant may be reversed.
CCE (A) can be added after being previously dispersed or dissolved in water, if necessary. CCE (A) is added to the aqueous surfactant solution and uniformly dissolved or dispersed, and then the oil agent (C) is added and cooled. If necessary, it can be prepared by adding a humectant such as glycerin, a pearling agent, a pH adjusting agent, a fragrance, a pigment and the like.
Further, the dosage form of the cleaning 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 preferably a paste or cream, and particularly preferably a liquid. In the case of a liquid state, it is preferable to use water, polyethylene glycol, ethanol or the like as the liquid medium, and the amount of water is preferably 10% by mass or more and 90% by mass or less in the entire composition.

  Moreover, in the case of a hair cleaning agent, the pH of the cleaning composition of the present invention is preferably from pH 2 to 12 and more preferably from 3 to 10 from the viewpoint of foaming during cleaning. In the case of a skin cleanser, the pH is preferably 2 or more and 12 or less, more preferably 3 or more and 11 or less, from the viewpoint of foaming during washing and irritation to the skin.

  The cleaning composition of the present invention is a good finger when the hair is washed with the cleaning composition, excellent slipperiness at the time of rinsing after treating the hair and its long-lasting feeling, and moist after drying the hair. Since the skin is washed with the cleaning composition, rinsed and dried to give an excellent moisturizing feeling to the skin, or as a hair cleaning agent or skin cleaning agent, It can be preferably used.

A hair shampoo is mentioned as a specific example of the detergent for hair.
Specific examples of the skin cleanser include body shampoo, hand wash, face wash, and makeup remover. Among these, considering the effects of the present invention, it is preferably used as a body shampoo, hand wash, or face wash.

[Cleaning method]
The present invention also includes a method for washing hair that is rinsed and dried after washing the hair using the cleaning composition of the present invention, and a method of rinsing the skin after cleaning the skin using the cleaning composition of the present invention, A method for cleaning dry skin is provided.
There is no restriction | limiting in particular as the washing | cleaning method of hair, and the washing | cleaning method of skin, A well-known method can be used.

In relation to the above-described embodiment, the present invention discloses the following skin or hair cleaning composition and cleaning method.
<1> A detergent composition for skin or hair containing a cationic group-containing cellulose ether (A), a surfactant (B), and an oil agent (C), the cationic group-containing cellulose ether (A) Has a main chain derived from anhydroglucose represented by the following general formula (1), the degree of substitution of the cationized oxyalkylene group per anhydroglucose unit 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 represented by the following general formulas (6) to (8), having 3 to 18 carbon atoms, preferably 3 to 7 carbon atoms. A cleansing composition for skin or hair, preferably having a substitution degree of a group containing a hydrocarbon group having 3 to 6 carbon atoms, more preferably 3 to 4 carbon atoms, of 0.0001 to 0.2.

(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 is 3 to 18 carbon atoms, preferably 3 to 7 carbon atoms, more preferably 3 to 6 carbon atoms. And more preferably an alkyl group, an alkenyl group, an amine having 3 to 4 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, and 0.05 to 2 0.0 mmol / g, preferably 0.15 to 1.5 mmol / g, more preferably 0.2 to 1.2 mmol / g, still more preferably 0.3 to 0.9 mmol / g, in the above <1> The cleaning composition for skin or hair as described.

<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, preferably 10% by mass or less, preferably Is 5% by mass or less, more preferably 1% by mass or less, and 0.01 to 10% by mass, preferably 0.05 to 5% by mass, more preferably 0.1 to 1% by mass. The cleaning composition for skin or hair according to <1> or <2>.

<4> The mass ratio of the cationic group-containing cellulose ether (A) to the surfactant (B) is 0.0002 or more, preferably 0.005 or more, and 10 or less, preferably 5 or less, more preferably 3 or less. The cleaning agent for skin or hair according to any one of the above <1> to <3>, which is 0.0002 to 10, preferably 0.0002 to 5, more preferably 0.005 to 3. Composition.

<5> The content of the surfactant (B) is 1% by mass or more, preferably 5% by mass or more, 80% by mass or less, preferably 50% by mass or less, more preferably 36% by mass or less, 1 to 80% by mass, preferably 5 to 50% by mass, and more preferably 5 to 36% by mass, according to any one of <1> to <4> above, .

<6> The content of the oil agent (C) is 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and 30% by mass or less, preferably 20% by mass or less. More preferably, it is 15 mass% or less, 0.01-30 mass%, Preferably it is 0.05-20 mass%, More preferably, it is 0.1-15 mass%, <1>-< 5> The detergent composition for skin or hair in any one of 5>.

<7> The amount of oil agent (C) dissolved in 100 g of water at 20 ° C. is from 0 g to 1 g, preferably from 0 g to 0.5 g, more preferably from 0 g to 0.1 g, <1> to <6 above > The cleaning composition for skin or hair according to any of the above.

<8> The oil agent (C) 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 hydroxyl groups. The cleaning composition for skin or hair according to any one of <1> to <7>, which is one or more kinds.

<9> The mass ratio of the cationic group-containing cellulose ether (A) to the oil agent (C) [cationic group-containing cellulose ether (A) / oil agent (C)] is preferably 0.001 or more, more preferably 0.00. 005 or more, more preferably 0.01 or more, still more preferably 0.03 or more, preferably 5 or less, more preferably 1 or less, still more preferably 0.6 or less, and preferably 0.001. ~ 5, more preferably 0.005 to 1, still more preferably 0.01 to 0.6, still more preferably 0.03 to 0.6, according to any one of <1> to <8> above. A cleaning composition for skin or hair.

<10> 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. 0.07 or more, more preferably 0.09 or more, still more preferably 0.10 or more, still more preferably 0.12 or more, still more preferably 0.18 or more, 0.9 or less, preferably 0. .6 or less, more preferably 0.5 or less, still more preferably 0.35 or less, still more preferably 0.3 or less, still more preferably 0.20 or less, preferably in the range of 0.04 to 0.6, preferably The range of 0.07 to 0.5, more preferably the range of 0.09 to 0.35, still more preferably the range of 0.10 to 0.3, still more preferably the range of 0.10 to 0.20, and more Further The skin or hair cleaning composition according to any one of <1> to <9>, preferably in the range of 0.12 to 0.20, and more preferably in the range of 0.18 to 0.20. .

<11> The substitution degree (MS (Gly)) of glycerol group per anhydroglucose unit of the cationic group-containing cellulose ether (A) is 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more. More preferably 1.0 or more, still more preferably 1.3 or more, still more preferably 1.8 or more, still more preferably 2.1 or more, 4.0 or less, preferably 3.8 or less, More preferably, it is 3.5 or less, More preferably, it is 3.0 or less, More preferably, it is 2.5 or less, More preferably, it is 2.3 or less, The range of 0.5-4.0, Preferably it is 0.7- 3.8, more preferably 0.9 to 3.8, even more preferably 1.0 to 3.0, even more preferably 1.0 to 2.3, even more preferably 1. .3 to 2.3, more preferred It is in the range of 2.1 to 2.3, the <1> to the skin or hair cleanser composition according to any one of <10>.

<12> 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. 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, 0.15 or less, preferably 0.10 or less, More preferably, it is 0.08 or less, More preferably, it is 0.06 or less, More preferably, it is 0.04 or less, The range of 0.0005-0.2, Preferably it is the range of 0.001-0.15, More preferably Is in the range of 0.005 to 0.15, more preferably in the range of 0.01 to 0.10, more preferably in the range of 0.01 to 0.08, and still more preferably in the range of 0.01 to 0.06. More preferably in the range of 0.02 to 0.06, more preferably in the range of 0.02 to 0.04, the skin or hair cleaning composition according to any one of <1> to <11> above. object.

<13> 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 0.10 cationic group-containing cellulose ether, preferably MS (N +) is 0.07 to 0.5 and MS (Gly) is 0.7 to 3.8. And a cationic group-containing cellulose ether having an MS (HC) of 0.01 to 0.06, more preferably an MS (N +) of 0.09 to 0.35, and an MS (Gly) of 1. 0 to 3.8 and MS (HC) is 0.01 to 0.06 cationic group-containing cellulose ether, more preferably MS (N +) is 0.10 to 0.20, MS (Gly) is 1.0 or more 2.3 or less and MS (HC) of 0.02 or more and 0.06 or less of a cationic group-containing cellulose ether, more preferably MS (N +) of 0.12 or more and 0.20 or less. (Gly) is 1.3 or more and 2.3 or less and MS (HC) is 0.02 or more and 0.06 or less cationic group-containing cellulose ether, more preferably MS (N +) is 0.18 or more. <0, which is a cationic group-containing cellulose ether having a MS (Gly) of 2.1 or more and 2.3 or less and a MS (HC) of 0.02 or more and 0.04 or less. The cleaning composition for skin or hair according to any one of> to <13>.

<14> MS (N +) of the cationic group-containing cellulose ether (A) is preferably 0.40 or more, more preferably 0.45 or more, further preferably 0.50 or more, preferably 0.90 or less. More preferably, it is 0.80 or less, More preferably, it is 0.75 or less, The skin or hair cleaning composition in any one of said <1>-<9>.

<15> MS (Gly) of cationic group-containing cellulose ether (A) is preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and preferably 3.0 or less. More preferably, it is 2.5 or less, More preferably, it is 2.3 or less, The skin or hair cleaning composition in any one of said <1>-<9>, <14>.

<16> MS (HC) of the cationic group-containing cellulose ether (A) is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.03 or more, and preferably 0.06 or less. More preferably 0.05 or less, and still more preferably 0.04 or less, the skin or hair cleaning composition according to any of the above <1> to <9>, <14>, <15> object.

<17> The cationic group-containing cellulose ether (A) preferably has MS (N +) of 0.40 or more and 0.90 or less, MS (Gly) of 0.6 or more and 3.0 or less, and MS (HC) is 0.01 to 0.06 cationic group-containing cellulose ether, more preferably MS (N +) is 0.45 to 0.80 and MS (Gly) is 0.7 to 2. And a cationic group-containing cellulose ether having an MS (HC) of 0.02 or more and 0.05 or less, more preferably MS (N +) of 0.50 or more and 0.75 or less, and MS (Gly). Is a cationic group-containing cellulose ether having a molecular weight of 0.8 or more and 2.3 or less and an MS (HC) of 0.03 or more and 0.04 or less, according to any one of the above <14> to <16>. Cleaner for skin or hair Narubutsu.

The average polymerization degree n of the main chain derived from anhydroglucose of <18> 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, The skin or hair according to any one of <1> to <17>, more preferably 2500 or less, in the range of 200 to 10,000, preferably in the range of 500 to 5000, more preferably in the range of 1000 to 2500. Detergent composition.

<19> In any one of the above items <1> to <18>, wherein the surfactant (B) is at least one selected from an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. The cleaning composition for skin or hair as described.

<20> The above <19>, wherein the anionic surfactant has an alkyl group or alkenyl group having 8 to 20 carbon atoms as a hydrophobic site, preferably an alkyl group or alkenyl group having 10 to 16 carbon atoms. The cleaning composition for skin or hair described in 1.

<21> Anionic surfactant is alkyl sulfate, polyoxyethylene alkyl ether sulfate, higher fatty acid salt having 8 to 16 carbon atoms, alkyl ether acetate represented by general formula (I), alkyl sulfosuccinate <19> or <20 above, wherein there is at least one selected from an ester salt, an acyl glutamate, a glycine derivative, an α-olefin sulfonate having 14 to 16 carbon atoms, and an internal olefin sulfonate having 12 to 24 carbon atoms. > The cleaning composition for skin or hair described in>.

<22> The nonionic surfactant has an alkyl group or alkenyl group having 8 to 20 carbon atoms as a hydrophobic site, preferably polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide and alkyl One or more selected from glycosides, more preferably selected from alkyl glucosides, polyoxyethylene alkyl ethers, coconut oil fatty acid monoethanolamides and fatty acid monoalkanolamides having 8 to 18 carbon atoms, preferably 8 to 12 carbon atoms. The skin or hair cleaning composition according to any one of <19> to <21>, which is one or more selected from the above.

<23> One or more amphoteric surfactants selected from imidazoline-based betaines, alkyldimethylaminoacetic acid betaines, fatty acid amidopropyl betaines, and alkylhydroxysulfobetaines, preferably coconut oil fatty acid amidopropyl betaines, lauryl carboxymethyl hydroxyimidazolium The cleaning composition for skin or hair according to any one of the above <19> to <22>, which is at least one selected from betaine, lauryldimethylaminoacetic acid betaine, and lauryl hydroxysulfobetaine.

<24> The cleaning composition for skin or hair according to any one of <1> to <23>, wherein the oil (C) contains a silicone oil.

<25> The cleaning composition for skin or hair according to <24>, wherein the silicone oil is dimethylpolysiloxane (dimethicone).

<26> A method for washing hair, wherein the hair is rinsed and dried after washing the hair using the detergent composition according to any one of <1> to <25>.

<27> A method for cleaning the skin, wherein the skin is cleaned with the cleaning composition according to any one of <1> to <25>, and then rinsed and dried.

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: Hydrogen flame ion detector (FID)
Detector temperature: 230 ° C
Driving amount: 1 μL
Carrier gas flow rate: helium 3.0mL / 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.

  When the hydrocarbon group-containing group is an oxypropylene group, pretreatment according to the Zeisel method converts not only the glycerol group but also the oxypropylene group into 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 (mass%) is measured by substituting the obtained content of each substituent into the above 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 measuring 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) Measurement of double bond position of raw material internal olefin The double bond position of the raw material internal olefin was measured by gas chromatography (hereinafter referred to as GC). Specifically, dimethyl disulfide was reacted with an internal olefin to obtain a dithiolated derivative, and then each component was separated by GC. As a result, the double bond position of the internal olefin was determined from each peak area.
In addition, the apparatus and analysis conditions used for the measurement are as follows.
GC device: “HP6890” (made by HEWLETT PACKARD)
Column: “Ultra-Alloy-1HT capillary column” 30 m × 250 μm × 0.15 μm (manufactured by Frontier Laboratories)
Detector: Hydrogen flame ion detector (FID)
Injection temperature: 300 ° C
Detector temperature: 350 ° C
He flow rate: 4.6 mL / min

(6) Measurement of mass ratio of hydroxy body / olefin body of internal olefin sulfonate The mass ratio of hydroxy body / olefin body of internal olefin sulfonate was measured by HPLC-MS. Specifically, the hydroxy body and the olefin body were separated by HPLC, and each was identified by subjecting to MS. As a result, each ratio was determined from the HPLC-MS peak area.
In addition, the apparatus and conditions used for the measurement are as follows.
HPLC apparatus: “Agilent Technology 1100” (manufactured by Agilent Technologies)
Column: “L-column ODS” 4.6 × 150 mm (manufactured by the Chemical Substance Evaluation Research Organization)
Sample preparation: 1000-fold dilution with methanol Eluent A: 10 mM ammonium acetate added water Eluent B: 10 mM ammonium acetate added methanol Gradient: 0 minutes (A / B = 30/70%) → 10 minutes (30/70%) → 55 minutes (0/100%) → 65 minutes (0/100%) → 66 minutes (30/70%) → 75 minutes (30/70%)
MS equipment: “Agilent Technology 1100MS SL (G1946D)”
MS detection: negative ion detection m / z 60-1600, UV 240 nm

(7) Measurement of content of raw material internal olefin in internal olefin sulfonate The content of raw material internal olefin in the internal olefin sulfonate was measured by GC. Specifically, ethanol and petroleum ether were added to the aqueous solution of internal olefin sulfonate, followed by extraction to obtain a raw internal olefin in the petroleum ether phase. As a result, the amount of olefin was quantified from the GC peak area.
In addition, the apparatus and analysis conditions used for the measurement are as follows.
GC device: “Agilent Technology 6850” (manufactured by Agilent Technologies)
Column: “Ultra-Alloy-1HT capillary column” 15 m × 250 μm × 0.15 μm (manufactured by Frontier Laboratories)
Detector: Hydrogen flame ion detector (FID)
Injection temperature: 300 ° C
Detector temperature: 350 ° C
He flow rate: 3.8 mL / min

(8) Measurement of content of inorganic compound in internal olefin sulfonate The content of the inorganic compound in internal olefin sulfonate was measured by potentiometric titration and neutralization titration. The content of Na ₂ SO ₄ was quantified by determining the sulfate radical (SO ₄ ²⁻ ) by potentiometric titration. The content of NaOH was quantified by neutralization titration with dilute hydrochloric acid.

(9) Measurement of content of internal olefin sulfonate having sulfonic acid group at 2-position The binding position of the sulfonic acid group of internal olefin sulfonate was measured by GC. Specifically, trimethylsilyldiazomethane was reacted with the obtained internal olefin sulfonate to obtain a methyl ester derivative, and then each component was separated by GC. Using each peak area ratio as a mass ratio, the content of the internal olefin sulfonate having a sulfonic acid group at the 2-position was calculated.
In addition, the apparatus and analysis conditions used for the measurement are as follows.
GC device: “Agilent Technology 6850” (manufactured by Agilent Technologies)
Column: “HP-1 capillary column” 30 m × 320 μm × 0.25 μm (manufactured by Agilent Technologies)
Detector: Hydrogen flame ion detector (FID)
Injection temperature: 300 ° C
Detector temperature: 300 ° C
He flow rate: 1.0 mL / min Oven: 60 ° C. (0 min) → 10 ° C./min→300° C. (10 min)

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.) and 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 the temperature was raised to 70 ° C., a solution obtained 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 to 4, 25 to 26 (Production of CCE (2) to (4), (25) to (26))
CCE (2) -(4) and (25)-(26) 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 5 to 23, 42 (production of CCE (5) to (23), CGC (1))
In Production Example 1, sheet wood pulp as raw material cellulose was changed to Tenfloc BioflocHV +, average polymerization degree 1550, and the cellulose chipping / flocculation step of step (1) was further 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 Co., 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 (5) to (23) 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 24 and 27 to 41 (Production of CCE (24) and (27) to (41))
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 like manufacture example 1 and obtained CCE (24) and (27)-(41).
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 Example A (Production of raw material internal olefin A)
In a flask equipped with a stirrer, 7000 g (28.9 mol) of 1-hexadecanol (Calcoal 6098: Kao Corporation), 700 g of γ-alumina (STREM Chemicals, Inc.) as a solid acid catalyst (10 relative to the raw material alcohol) The reaction was carried out for 3 hours with nitrogen (7000 mL / min) flowing through the system at 280 ° C. with stirring. After the reaction, the alcohol conversion was 100%, and the C16 internal olefin purity was 99.6%. The obtained crude internal olefin was transferred to a distillation flask and distilled at 136 to 160 ° C./4.0 mmHg to obtain an internal olefin having 16 carbon atoms and an olefin purity of 100%. The double bond distribution of the obtained internal olefin was C1 position 1.8 mass%, C2 position 30.4 mass%, C3 position 23.9 mass%, C4 position 16.8 mass%, C5 position 12.0 mass%. %, C6 position 7.4% by mass, C7, position 8 total was 7.8% by mass.

Production Example B (Production of raw material internal olefin B)
In a flask equipped with a stirrer, 7000 g (25.9 mol) of 1-octadecanol (Calcoal 8098: manufactured by Kao Corporation), 700 g of γ-alumina (manufactured by STREM Chemicals, Inc.) as a solid acid catalyst (10 relative to the raw material alcohol) The reaction was carried out for 10 hours while flowing nitrogen (7000 mL / min) through the system at 280 ° C. with stirring. After the reaction, the alcohol conversion was 100%, and the C18 internal olefin purity was 98.2%. The obtained crude internal olefin was transferred to a distillation flask and distilled at an internal temperature of 148 to 158 ° C./0.5 mmHg to obtain an internal olefin having 18 carbon atoms and an olefin purity of 100%. The double bond distribution of the obtained internal olefin was C1 position 0.8 mass%, C2 position 31.3 mass%, C3 position 22.9 mass%, C4 position 15.5 mass%, C5 position 10.8 mass%. %, C6 position 7.2 mass%, C7 position 5.3 mass%, C8, 9th position total was 6.2 mass%.

Production Example C (Production of raw material internal olefin C)
In a flask equipped with a stirrer, 7000 g (28.9 mol) of 1-hexadecanol (Calcoal 6098: Kao Corporation), 700 g of γ-alumina (STREM Chemicals, Inc.) as a solid acid catalyst (10 relative to the raw material alcohol) The reaction was carried out for 5 hours while flowing nitrogen (7000 mL / min) through the system at 280 ° C. with stirring. The alcohol conversion after completion of the reaction was 100%, and the C16 internal olefin purity was 99.7%. The obtained crude internal olefin was transferred to a distillation flask and distilled at 136 to 160 ° C./4.0 mmHg to obtain an internal olefin having 16 carbon atoms and an olefin purity of 100%. The double bond distribution of the obtained internal olefin is as follows: C1-position 0.5 mass%, C2-position 16.5 mass%, C3-position 15.4 mass%, C4-position 16.4 mass%, C5-position 17.2 mass%. %, C6 position 14.2% by mass, and C7, position 8 total was 19.8% by mass.

Production Example D (Production of raw material internal olefin D)
In a flask equipped with a stirrer, 7000 g (25.9 mol) of 1-octadecanol (Calcoal 8098: manufactured by Kao Corporation) and 1050 g of γ-alumina (STREM Chemicals, Inc.) as a solid acid catalyst (15 relative to the raw alcohol) The reaction was carried out for 13 hours while flowing nitrogen (7000 mL / min) through the system at 285 ° C. with stirring. After the reaction, the alcohol conversion was 100%, and the C18 internal olefin purity was 98.5%. The obtained crude internal olefin was transferred to a distillation flask and distilled at 148 to 158 ° C./0.5 mmHg to obtain an 18-carbon internal olefin having an olefin purity of 100%. The double bond distribution of the obtained internal olefin was as follows: C1-position 0.7% by mass, C2-position 16.9% by mass, C3-position 15.9% by mass, C4-position 16.0% by mass, C5-position 14.7% by mass. %, C6 position 11.2 mass%, C7 position 10.2 mass%, C8, and 9th position total was 14.6 mass%.

Production Example E (Production of raw material internal olefin E)
6000 g (35.6 mol) of 1-dodecene (Linearene 12: manufactured by Idemitsu Kosan Co., Ltd.) in a flask equipped with a stirrer, 180 g of β-zeolite (Zeolyst) as a solid acid catalyst (3.0 relative to the raw material 1-dodecene) The reaction was carried out for 12.5 hours while flowing nitrogen (200 mL / min) through the system at 120 ° C. with stirring. After completion of the reaction, the internal isomerization rate of the α-olefin was 98.4%, and the C12 internal olefin purity was 92.1%. The obtained crude internal olefin was transferred to a distillation flask and distilled at 134 to 138 ° C./75.0-78.8 mmHg to obtain a C12 internal olefin having an olefin purity of 100%. The double bond distribution of the obtained internal olefin is as follows: C1-position 0.5% by mass, C2-position 33.1% by mass, C3-position 23.7% by mass, C4-position 21.2% by mass, C5-position 15.0% by mass. %, C6 position was 6.8% by mass.

Production Example 43 (Production of internal olefin sulfonate (1))
Using the thin-film sulfonation reactor (inner diameter 14 mmφ, length 4 m), the SO ₃ concentration of 2.8 vol% sulfur trioxide gas obtained from Production Example A and the outside of the reactor The sulfonation reaction was performed by passing cooling water at 20 ° C. through the jacket. The SO ₃ / internal olefin reaction molar ratio was set to 1.09.
The obtained sulfonated product was added to an alkaline aqueous solution to which sodium hydroxide was added so as to be 1.2 times the theoretical acid value (AV), and neutralized by stirring at 30 ° C. for 1 hour. The neutralized product was hydrolyzed by heating in an autoclave at 160 ° C. for 1 hour to obtain a crude product of 16-carbon sodium olefin sulfonate.
300 g of the obtained crude product was transferred to a separatory funnel, 300 mL of ethanol was added, and 300 mL of petroleum ether was added at one time to extract and remove oil-soluble impurities. At this time, the inorganic compound (main component is sodium nitrate) precipitated at the oil / water interface by addition of ethanol was also separated and removed from the aqueous phase by the oil / water separation operation, and this operation was performed three times. The aqueous phase was evaporated to dryness to obtain sodium olefin sulfonate having 16 carbon atoms (internal olefin sulfonate (1)). Table 3 shows the mass ratio of the hydroxy body / olefin body and the content of the internal olefin sulfonate having a sulfonic acid group at the 2-position. Further, the content of the raw material internal olefin was less than 100 ppm (less than the GC detection lower limit), and the content of the inorganic compound was 1.9% by mass.

Production Example 44 (Production of internal olefin sulfonate (2))
A sodium olefin sulfonate having 18 carbon atoms (internal olefin sulfonate (2)) was obtained under the same conditions as in Production Example 43 except that the internal olefin having 18 carbon atoms obtained in Production Example B was used. . Table 3 shows the mass ratio of the hydroxy body / olefin body and the content of the internal olefin sulfonate having a sulfonic acid group at the 2-position. The content of the raw material internal olefin was less than 100 ppm (less than the GC detection lower limit), and the content of the inorganic compound was 0.9% by mass.

Production Example 45 (Production of internal olefin sulfonate (3))
A sodium olefin sulfonate having 16 carbon atoms (internal olefin sulfonate (3)) was obtained under the same conditions as in Production Example 43 except that the internal olefin having 16 carbon atoms obtained in Production Example C was used. . Table 3 shows the mass ratio of the hydroxy body / olefin body and the content of the internal olefin sulfonate having a sulfonic acid group at the 2-position. Further, the content of the raw material internal olefin was less than 100 ppm (less than the GC detection lower limit), and the content of the inorganic compound was 1.3% by mass.

Production Example 46 (Production of internal olefin sulfonate (4))
Except for using the internal olefin having 18 carbon atoms obtained in Production Example D, sodium olefin sulfonate having 18 carbon atoms (internal olefin sulfonate (4)) was obtained under the same conditions as in Production Example 43. . Table 3 shows the mass ratio of the hydroxy body / olefin body and the content of the internal olefin sulfonate having a sulfonic acid group at the 2-position. Further, the content of the raw material internal olefin was less than 100 ppm (less than the GC detection lower limit), and the content of the inorganic compound was 1.7% by mass.

Production Example 47 (Production of internal olefin sulfonate (5))
Sodium olefin sulfonate having 12 carbon atoms (internal olefin sulfonate (5)) was obtained under the same conditions as in Production Example 43 except that the internal olefin having 12 carbon atoms obtained in Production Example E was used. . Table 3 shows the mass ratio of the hydroxy body / olefin body and the content of the internal olefin sulfonate having a sulfonic acid group at the 2-position. Further, the content of the raw material internal olefin was less than 100 ppm (less than the GC detection lower limit), and the content of the inorganic compound was 0.2% by mass.

[Composition and evaluation of cleaning composition for hair]
Examples 1 to 102 (production and evaluation of shampoo)
Using CCE (1) to (32) as components (A), shampoos having compositions shown in Tables 4 to 12 were prepared by a conventional method.
Specifically, the component (A) was dissolved or uniformly dispersed in water, an appropriate amount of water and the surfactant (B) were taken in a beaker, heated to 60 ° C., uniformly mixed, and cooled to 50 ° C. Oil agent (C) was added there, and it cooled to 40 degreeC after homogeneous mixing. The pearlizing agent was added thereto, stirred and emulsified for 30 minutes, and cooled. Finally, the water evaporated by heating was replenished, and the pH was measured. The pH was adjusted to 5 with a pH adjuster (50% aqueous citric acid solution).
For Examples 62 to 93, component (A) was dissolved or uniformly dispersed in water, an appropriate amount of water and surfactant (B) were taken in a beaker, heated to 60 ° C. and uniformly mixed, and oil agent (C ) Was added, mixed uniformly, and cooled to 40 ° C. A pearlizing agent was added thereto, stirred and emulsified for 30 minutes, and cooled. Finally, the water evaporated by heating was replenished, and the pH was measured. The pH was adjusted to 5 with a pH adjuster (50% aqueous citric acid solution).

The hair bundle was washed with a plain shampoo shown below and sufficiently moistened with warm water of 35 to 40 ° C., and then 0.5 g of the shampoo of Examples 1 to 102 was applied and washed for 1 minute. Thereafter, it was rinsed with warm water for 30 seconds, moisture was removed with a towel, a hair bundle was prepared with a comb, and further dried with warm air from a dryer, and a hair bundle was prepared with a comb for finishing to obtain an evaluation tress.
Five panelists evaluated the fingering property at the time of hair washing, the slipperiness at the time of rinsing, the persistence of the slipperiness, the moist feeling after drying, and the uniformity according to the following evaluation criteria and evaluation methods. The evaluation results are shown in Tables 4-12. The uniformity after drying indicates that the touch is uniform from the root of the hair bundle to the hair tip.
If Comparative Example 1 is the reference score 3, and the average score of the five panelists is 3.4 or more, it can be said that the evaluation clearly has excellent performance.

(Plain shampoo composition)
(Ingredient) (%)
Polyoxyethylene lauryl ether sulfate Na 11.3
(Kao Corporation: 42.0% as Emar E-27C (effective 27%))
Palm oil fatty acid N-methylethanolamide 3.0
(Kao Corporation: Aminone C-11S)
Citric acid 0.2
Methylparaben 0.3
Purified water balance
Total 100.0

(Manufacture of plain shampoo)
Each component was taken in a beaker, heated to 80 ° C., mixed, and after confirming that it was uniformly dissolved, it was cooled to obtain a plain shampoo.

(Evaluation criteria and evaluation method)
・ Fingering at the time of washing 5: Fingering is very good 4: Fingering is good 3: Fingering is normal (based on fingering of Comparative Example 1)
2: Poor fingering 1: Poor fingering / sliding during rinsing 5: Very good sliding 4: Good sliding 3: Normal sliding (based on the sliding property of Comparative Example 1)
2: Slip is poor 1: Slip is very bad and slipperiness is sustained 5: Sustainability is very strong 4: Sustainability is strong 3: Normal (based on the sustainability of Comparative Example 1)
2: The feeling of persistence is weak 1: The feeling of persistence is very weak ・ Moist feeling after drying 5: Very moist feeling is strong 4: Moist feeling is strong 3: Normal (based on the moist feeling of Comparative Example 1)
2: Moist feeling is weak 1: Moist feeling is very weak ・ Uniformity after drying 5: Very high uniformity 4: High uniformity 3: Normal (based on uniformity in Comparative Example 1)
2: Hair ends are crushed 1: Hair ends are crushed

Comparative Examples 1-3 (manufacture and evaluation of shampoo)
Shampoos using various polymers shown in Table 4 instead of the component (A) in Example 1 were prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The shampoos of Comparative Examples 1 to 3 were similarly adjusted to pH 5.
Table 4 shows the results of evaluating the shampoos of Comparative Examples 1 to 3.

  From Tables 4 to 12, the shampoos of Examples 1 to 102 are excellent in imparting fingering property during hair washing, slipperiness during rinsing, a long-lasting slipperiness, a moist feeling after drying, and uniformity. It turns out to be a shampoo.

[Evaluation of Dimethicone Residue of Hair Cleaner Composition]
Examples 103 to 108 (Dimethicone residue evaluation of shampoo)
A shampoo having the composition shown in Table 12 was prepared in the same manner as in Example 1 using CCE (24), (27), (28), (29), (31), and (32) as component (A). .
The hair bundle 1g “BS-BA” (manufactured by Beaulux Co., Ltd .: 10 cm) was washed with the plain shampoo shown above, sufficiently moistened with warm water of 35-40 ° C., and then the shampoo 0 of Examples 103-108 .1 g was applied and washed for 1 minute. Thereafter, it was rinsed with warm water for 30 seconds, moisture was removed with a towel, a hair bundle was prepared with a comb, and further dried with warm air from a dryer to obtain an evaluation tress. The tress was immersed in 10 mL of chloroform for 10 minutes and stirred to extract dimethicone adsorbed on the tress. This extraction operation was performed three times, the extract was collected, and the solvent was distilled off. Heavy chloroform was added to the residue and dissolved, and dimethicone was quantified by ¹ H-NMR. The results are shown in Table 13.

Examples 109 to 121, Comparative Example 4 (Dimethicone residue evaluation of shampoo)
For Examples 109 to 121, CCEs (27) to (29) and (32) to (41) were used as the component (A), and shampoos having the compositions shown in Table 14 were prepared in the same manner as Example 1. Evaluation was performed in the same manner as in Example 103.
For Comparative Example 4, a shampoo using the polymer shown in Table 14 instead of the component (A) of Example 109 was prepared in the same manner as in Example 109 and evaluated in the same manner as in Example 103.
Table 14 shows the results of evaluating the shampoos of Examples 109 to 121 and Comparative Example 4.

  From Table 13, it can be seen that a sample with a high cationic charge density is excellent in dimethicone persistence. Moreover, it can be seen from Table 14 that the shampoos of Examples 109 to 121 are superior to the shampoo of Comparative Example 4 in that the residual amount of dimethicone is excellent although the amount of the polymer added is small.

Example 122 (body shampoo)
A body shampoo having the following composition was produced by a conventional method.
Both hands were wetted, 0.5 mL of the obtained body shampoo was applied to both hands, foamed, then both hands were rinsed in running water for 10 seconds, water drops were wiped off with a towel, and the skin feel after drying was evaluated.
As a result, the skin washed and dried with this body shampoo had an excellent moisturizing feeling.

(Ingredient) (%)
Sodium polyoxyethylene alkyl ether sulfate * 1 6.2
Sodium cocoyl isethionate * 2 5.8
Palm oil fatty acid amidopropyl betaine * 3 3.7
Glycerin 3.2
Lauric acid 4.0
Myristic acid 0.5
Palmitic acid 1.5
Stearic acid 1.5
Sunflower oil 13.2
CCE (26) 0.2
Potassium hydroxide (amount to be adjusted to pH 7.3) appropriate amount perfume, preservative appropriate amount
Purified water balance
Total 100.0

* 1: Made by Kao Corporation: EMAL 270J (active ingredient 70%)
(The above composition is converted to sodium polyoxyethylene alkyl ether sulfate)
* 2: NOF Corporation: Diapon CI (active ingredient 100%)
* 3: Kao Corporation: Anhitoal 55AB (30% active ingredient)
(The above composition is converted to palm oil fatty acid amidopropyl betaine)

Example 123 (face wash)
A face wash having the following composition was produced and evaluated in the same manner as in Example 122. As a result, the skin washed and dried with this face wash had an excellent moisturizing feeling.

(Ingredient) (%)
Cocoylglycine sodium * 1 9.4
Sodium cocoamphoacetate * 2 2.5
Coconut oil fatty acid amidopropyl betaine * 3 1.7
Lauric acid 2.0
Glycerin 6.0
Vaseline 9.0
CCE (26) 0.3
Fragrance, preservatives appropriate amount pH adjuster (amount to adjust to pH 7.0) appropriate amount
Purified water balance
Total 100.0

* 1: Ajinomoto Co., Inc. Amilite GCS-11 (100% active ingredient)
* 2: Nikko Chemicals Corporation: NIKKOL AM-101 (active ingredient 40%)
(The above composition is in terms of sodium cocoamphoacetate)
* 3: Kao Corporation: Anhitoal 55AB (30% active ingredient)
(The above composition is converted to palm oil fatty acid amidopropyl betaine)

Example 124 (face wash)
A face wash having the following composition was produced and evaluated in the same manner as in Example 122. As a result, the skin washed and dried with this face wash had an excellent moisturizing feeling.

(Ingredient) (%)
Cocoyl methyl taurine sodium * 1 1.4
Lauric acid 28.2
Myristic acid 2.8
Palmitic acid 3.1
PEG-32 * 2 2.0
Glycerin 16.0
Vaseline 5.0
CCE (26) 0.3
Fragrance, preservatives appropriate amount pH adjuster (amount adjusted to pH 9.0) appropriate amount
Purified water balance
Total 100.0

* 1: Nikko Chemicals Co., Ltd .: NIKKOL CMT-30 (30% active ingredient)
(The above composition is cocoyl methyl taurine sodium equivalent)
* 2: NOF Corporation: PEG # 1500

Examples 125 to 132 (production and evaluation of shampoo)
Using CCE (20) as component (A), a shampoo having the composition shown in Table 15 was prepared in the same manner as in Example 1.
The hair bundle was washed with the aforementioned plain shampoo and sufficiently moistened with warm water of 35 to 40 ° C., and then 0.5 g of the shampoo of Examples 125 to 132 was applied and washed for 1 minute. Thereafter, it was rinsed with warm water for 30 seconds, moisture was removed with a towel, a hair bundle was prepared with a comb, and further dried with warm air from a dryer, and a hair bundle was prepared with a comb for finishing to obtain an evaluation tress.
Five panelists evaluated the fingering property at the time of hair washing, the slipperiness at the time of rinsing, the persistence of the slipperiness, the moist feeling after drying, and the uniformity according to the following evaluation criteria and evaluation methods. The evaluation results are shown in Table 15.
If Comparative Example 5 is set to a reference score of 3 and the average score of five panelists is 3.4 or more, it can be said that the evaluation clearly has excellent performance.

(Evaluation criteria and evaluation method)
・ Fingering at cleaning 5: Very good by fingering 4: Good by fingering 3: Normal by fingering (based on fingering of Comparative Example 5)
2: Bad fingering 1: Very bad fingering ・ Sliding property when rinsing 5: Very good sliding 4: Good sliding 3: Normal sliding (based on the sliding property of Comparative Example 5)
2: Slip is poor 1: Slip is very bad / Slippery sustainability 5: Sustainability is very strong 4: Sustainability is strong 3: Normal (based on the sustainability of Comparative Example 5)
2: The feeling of persistence is weak 1: The feeling of persistence is very weak ・ Moist feeling after drying 5: Very moist feeling is strong 4: Moist feeling is strong 3: Normal (based on the moist feeling of Comparative Example 5)
2: Moist feeling is weak 1: Moist feeling is very weak ・ Uniformity after drying 5: Very high uniformity 4: High uniformity 3: Normal (based on uniformity in Comparative Example 5)
2: Hair ends are crushed 1: Hair ends are crushed

Comparative Example 5 (Production and evaluation of shampoo)
Instead of the component (A) of Example 1, a shampoo having the composition shown in Comparative Example 5 of Table 15 was prepared in the same manner as in Example 1, and evaluated in the same manner as described above. The pH of the shampoo of Comparative Example 5 was also adjusted to 5.

  The cleaning composition of the present invention, when used in a hair cleaning product such as a hair shampoo, is excellent for finger washing during hair cleaning, excellent slipperiness during rinsing after treatment of hair, and its long-lasting feeling, and drying. An excellent moist feeling and uniformity can be imparted later, and an excellent moisturizing feeling after drying can be imparted when used in a skin cleanser such as a body shampoo or facial cleanser.

Claims (13)

A detergent composition for skin or hair containing a cationic group-containing cellulose ether (A), a surfactant (B), and an oil agent (C), wherein the cationic group-containing cellulose ether (A) is: Having a main chain derived from anhydroglucose represented by the general formula (1), wherein the degree of substitution of the cationized oxyalkylene group per anhydroglucose unit is 0.01 or more and 1.0 or less, The degree of substitution of the group containing a hydrocarbon group having 3 to 18 carbon atoms and having a substitution degree of 0.5 to 5.0 and represented by the following general formulas (6) to (8) is 0. A cleaning composition for skin or hair which is 0001 or more and 0.2 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 cleaning composition for skin or hair 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 skin or hair cleaning 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 skin or hair cleaning composition according to any one of claims 1 to 3, wherein the hydrocarbon group has 3 to 7 carbon atoms.   The degree of substitution of the cationized oxyalkylene group per anhydroglucose unit of the cationic group-containing cellulose ether (A) is 0.09 or more and 0.35 or less, and the degree of substitution of the glycerol group is 1.0 or more and 3.8 or less. And the degree of substitution of the group containing a hydrocarbon group having 3 to 18 carbon atoms is 0.01 or more and 0.06 or less, according to claim 1. Composition.   The degree of substitution of the cationized oxyalkylene group per anhydroglucose unit of the cationic group-containing cellulose ether (A) is 0.40 or more and 0.90 or less, and the degree of substitution of the glycerol group is 0.6 or more and 3.0 or less. And the degree of substitution of the group containing a hydrocarbon group having 3 to 18 carbon atoms is 0.01 or more and 0.06 or less, according to claim 1. Composition.   The detergent composition for skin or hair according to any one of claims 1 to 6, wherein the mass ratio of the cationic group-containing cellulose ether (A) to the surfactant (B) is 0.0002 or more and 10 or less.   The detergent composition for skin or hair according to any one of claims 1 to 7, wherein the content of the surfactant (B) is 1% by mass or more and 80% by mass or less.   The skin or hair cleaning composition according to any one of claims 1 to 8, wherein the content of the oil agent (C) is 0.01% by mass or more and 30% by mass or less.   The oil agent (C) is one or more 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 hydroxyl groups. The cleaning composition for skin or hair according to any one of claims 1 to 9.   The cleansing composition for skin or hair according to any one of claims 1 to 10, wherein the oil (C) contains silicone oil.   A method for washing hair, wherein the hair is rinsed and dried after washing the hair using the detergent composition according to any one of claims 1 to 11.   A method for cleaning the skin, wherein the skin is cleaned using the cleaning composition according to any one of claims 1 to 11, and then rinsed and dried.