JP2012149029A - Hair cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair cosmetic capable of imparting satisfactory slip and manageability to hair after being treated and dried without imparting an oily sensation thereto, and to provide a method for producing the hair cosmetic.SOLUTION: The hair cosmetic includes: a cationized hydroxypropyl cellulose (A); an oil solution (B); and a surfactant (C); wherein the cationized hydroxypropyl cellulose (A) has a main chain derived from an anhydroglucose, and also, the degree of substitution of cationized ethyleneoxy groups is 0.01 to 2.9 moles, the degree of substitution of propyleneoxy groups is 0.1 to 4.0 moles, and the oil solution (B) is one or more kinds of compounds selected from a specified ester compound, a specified dialkyl carbonate compound and a specified dialkyl ether compound. The method for producing the hair cosmetic is provided.

Description

  The present invention relates to a hair cosmetic containing cationized hydroxypropylcellulose and a method for producing the same.

Hair is damaged by chemical treatment with hair color, shampooing, and physical treatment with the heat of a dryer. It is well known that when hair is damaged, negative elements are generated from an aesthetic point of view, such as dryness, poor texture, and loss of gloss. Therefore, a conditioning agent for returning to a smooth feel before processing is widely used.
In the conditioning agent for hair cosmetics, an oil agent such as silicone, ester oil, hydrocarbon oil or the like is blended in order to improve the hairiness of the hair and improve the fingering property and unity. However, when the blending amount of the oil agent is increased, the dryness is improved, but the hair after drying feels sticky, and there is a problem that the touch becomes worse.

In order to improve such a problem, Patent Document 1 discloses a method for producing a cation-modified cellulose derivative such as cationized hydroxypropylcellulose, and describes that it can be used in a compounding agent such as a hair cosmetic. Yes.
Patent Document 2 discloses a hair spray composition containing cationized hydroxypropylcellulose and an alcohol solvent.
Furthermore, cosmetics containing at least one selected from dialkyl ethers, ester oils, hydroxycarboxylic acid esters, etc. (see Patent Document 3), cosmetics containing a specific dialkyl carbonate and an emulsifier (see Patent Document 4), alkoxyl A cosmetic composition (see Patent Document 5) containing an ester of a fluorinated aromatic alcohol and an aliphatic carboxylic acid and a functional component has been proposed.

JP-A-53-90368 JP-A-60-170601 JP 2000-512284 A JP 2000-512285 A JP 2005-506347 A

Conventional hair cosmetics are not sufficiently satisfactory in terms of finger touch, non-stickiness, and good texture after drying.
An object of the present invention is to provide a hair cosmetic that can suppress the sticky feeling of the hair after treatment drying and can impart good fingering property and a feeling of unity, and a method for producing the same.

The present invention provides the following (1) and (2).
(1) The present invention is a hair cosmetic containing cationized hydroxypropylcellulose (A), an oil agent (B), and a surfactant (C),
The cationized hydroxypropylcellulose (A) has a main chain derived from anhydroglucose represented by the following general formula (1), and the substitution degree of the cationized ethyleneoxy group is 0.01 to 2.9 mol. Yes, the degree of substitution of propyleneoxy group is 0.1-4.0 mol,
The oil agent (B) is selected from an ester compound represented by the following general formula (4), a dialkyl carbonate compound represented by the following general formula (5), and a dialkyl ether compound represented by the following general formula (6). Hair cosmetics that are one or more compounds are provided.

(In the formula, R ¹ , R ² and R ³ each independently represent a substituent having a cationized ethyleneoxy group and a propyleneoxy group represented by the following general formula (2), and n is an average of anhydroglucose. The degree of polymerization is 50 to 5000.)

(In the formula, ^one of Y ¹ and Y ² represents a hydrogen atom, the other represents a cationic group represented by the following general formula (3), PO represents a propyleneoxy group, and p represents a general formula (2 ) Represents the number of cationized ethyleneoxy groups (—CH (Y ¹ ) —CH (Y ² ) —O—) contained in the group, q represents the number of propyleneoxy groups (—PO—), and each represents 0 or When both p and q are not 0, the addition order of the cationized ethyleneoxy group and the propyleneoxy group is not limited, and when p and / or q is 2 or more, a block bond or Any of random bonds may be used.)

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, and X ⁻ represents an anionic group.)
_{^{R 7 O- (AO) m -COR}} 8 (4)
(In the formula, R ⁷ represents a carbon hydrogen group having 6 to 20 carbon atoms containing at least one substituted or unsubstituted aromatic ring, and R ⁸ is a linear or branched alkyl group having 1 to 25 carbon atoms. AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and m is a number from 1 to 50. When m is 2 or more, the m AO groups are the same or different. May be good.)
_{^{R 9 O (CH 2 CH 2}} O) r CO (OCH 2 CH 2) s -OR 10 (5)
(In the formula, R ⁹ and R ¹⁰ each represent a linear or branched alkyl group and / or alkenyl group having 6 to 22 carbon atoms, and r and s are each 0 or a number of 1 to 50.)
R ¹¹ —O—R ¹² (6)
(In the formula, R ¹¹ and R ¹² each represent a linear or branched alkyl group and / or alkenyl group having 6 to 22 carbon atoms.)

(2) A hair cosmetic containing a cationized hydroxypropyl cellulose (A), an oil agent (B), and a surfactant (C), wherein the cationized hydroxypropyl cellulose (A) is represented by the general formula (1). And the degree of substitution of the cationized ethyleneoxy group is 0.01 to 2.9 mol, and the degree of substitution of the propyleneoxy group is 0.1 to 4.0. The oil agent (B) is an ester compound represented by the general formula (4), a dialkyl carbonate compound represented by the general formula (5), and a dialkyl ether represented by the general formula (6). It is 1 or more types of compounds chosen from a compound, and the following process (a-1)-(a-3), the following process (b-1)-(b-4), or the following process (c-1)-( hair makeup having c-4) The method of production.
Step (a-1): A step of adding a cationizing agent to the cellulose-containing raw material and carrying out a pulverizer treatment Step (a-2): Adding a base to the pulverizer treated product obtained in step (a-1) The step of obtaining a cationized cellulose by reacting the cellulose-containing raw material with a cationizing agent while carrying out a pulverizer treatment Step (a-3): The cationized cellulose and propylene oxide obtained in Step (a-2) Step of obtaining cationized hydroxypropyl cellulose (A) by reaction Step (b-1): A cellulose-containing raw material containing cellulose having a crystallinity of 10 to 50% is obtained by pulverizing the cellulose-containing raw material. Step Step (b-2): The cellulose-containing raw material obtained in Step (b-1) is 0.6 to 1.5 times mole per mole of anhydroglucose unit constituting the cellulose. Step of obtaining alkali cellulose by adding 20 to 100% by mass of water to the base and cellulose in the cellulose-containing raw material Step (b-3): Alkali cellulose obtained in step (b-2) Step of obtaining hydroxypropylcellulose by reacting with propylene oxide Step (b-4): Cationic hydroxypropylcellulose (A) by reacting hydroxypropylcellulose obtained in step (b-3) with a cationizing agent Step (c-1): Cellulose-containing raw material and a mixture of 0.6 to 1.5 times mole of base per mole of anhydroglucose unit constituting cellulose in the cellulose-containing raw material, The pulverizer is processed under the condition that the water content with respect to the cellulose is 10% by weight or less. Step of obtaining cellulose / base mixed pulverized product of 0 μm Step (c-2): Water is added to the cellulose / base mixed pulverized product obtained in step (c-1), A step of adjusting the water content to 30 to 100% by mass with respect to the cellulose in the cellulose-containing raw material used in the step (c-1) to obtain alkali cellulose Step (c-3): Step (c-2) Step of obtaining hydroxypropyl cellulose by reacting the alkali cellulose obtained in step 1 with propylene oxide Step (c-4): Hydroxypropyl cellulose obtained in step (c-3) and a cationizing agent are reacted to form a cation. For obtaining hydrogenated hydroxypropylcellulose (A)

  ADVANTAGE OF THE INVENTION According to this invention, the hair cosmetics which can suppress the sticky feeling of the hair after process drying, and can provide favorable fingering property and a feeling of unity, and its manufacturing method can be provided.

[Hair cosmetic]
The hair cosmetic composition of the present invention is characterized by containing a specific cationized hydroxypropyl cellulose (A), a specific oil agent (B), and a surfactant (C).
<Cationized hydroxypropyl cellulose (A)>
The hair cosmetic composition of the present invention has a main chain derived from anhydroglucose represented by the following general formula (1) as the component (A), and the substitution degree of the cationized ethyleneoxy group is 0.01 to 2. 9 and cationized hydroxypropylcellulose (hereinafter also referred to as “C-HPC”) having a propyleneoxy group substitution degree of 0.1 to 4.0.

(In the formula, R ¹ , R ² and R ³ each independently represent a substituent having a cationized ethyleneoxy group and a propyleneoxy group represented by the following general formula (2), and n is an average of anhydroglucose. The degree of polymerization is 50 to 5000.)

(In the formula, ^one of Y ¹ and Y ² represents a hydrogen atom, the other represents a cationic group represented by the following general formula (3), PO represents a propyleneoxy group, and p represents a general formula (2 ) Represents the number of cationized ethyleneoxy groups (—CH (Y ¹ ) —CH (Y ² ) —O—), and q represents the number of propyleneoxy groups (—PO—), each of which is 0 or positive. When both p and q are not 0, the order of addition of the cationized ethyleneoxy group and the propyleneoxy group is not limited, and when p and / or q is 2 or more, block bonding or random Any of the bonds may be used.)

（式中、Ｒ⁴、Ｒ⁵及びＲ⁶は、それぞれ独立に炭素数１〜３の直鎖又は分岐鎖のアルキル基を示し、Ｘ^-はアニオン性基を示す。）

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, and X ⁻ represents an anionic group.)

(Main chain derived from anhydroglucose represented by the general formula (1))
In the general formula (1), R ¹ , R ² and R ³ are each independently a substituent represented by the general formula (2), and R ¹ , R ² and R ³ may be the same, May be different. Further, n R ^{1 s} , n R ^{2 s} , and n R ^{3 s} may be the same or different.

Moreover, from the viewpoint of suppressing the sticky feeling of the hair after treatment drying with the hair cosmetic composition of the present invention and improving the fingering property and the feeling of unity, the average degree of polymerization n in the general formula (1) is 50 or more, 100 or more are preferable, 200 or more are more preferable, and 300 or more are still more preferable. Further, from the same viewpoint as above and from the viewpoint of ease of production, the average degree of polymerization n is 5000 or less, preferably 3000 or less, more preferably 2000 or less, and even more preferably 1500 or less. When these viewpoints are combined, the average degree of polymerization n is 50 to 5000, preferably 100 to 3000, more preferably 200 to 2000, and still more preferably 300 to 1500.
In the present invention, the average degree of polymerization refers to a viscosity average degree of polymerization measured by a copper-ammonia method, and is specifically calculated by the method described in Examples.

(Substituent represented by the general formula (2))
The substituent represented by the general formula (2) which is R ¹ , R ² and R ³ in the general formula (1) has a cationized ethyleneoxy group and a propyleneoxy group as shown in the following formula (2).

In the general formula (2), ^one of Y ¹ and Y ² is a hydrogen atom, the other is a cationic group represented by the following general formula (3), and PO is a propyleneoxy group.
p represents the number of cationized ethyleneoxy groups (—CH (Y ¹ ) —CH (Y ² ) —O—) contained in the general formula (2), and is 0 or a positive integer. From the viewpoint of ease of production, p is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 0 or 1.
q represents the number of propyleneoxy groups (—PO—) and is 0 or a positive integer. From the viewpoint of ease of production, q is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0 or 1.
When there are a plurality of substituents represented by the general formula (2) in the C-HPC molecule, the values of p and q may be different between the substituents.

The total of p and q is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, more preferably an integer of 1 to 3, from the viewpoint of ease of production. More preferably, it is 1 or 2.
When neither p nor q is 0, the addition order of the cationized ethyleneoxy group and propyleneoxy group is not limited, but from the viewpoint of ease of production, the order described in the general formula (2) may be used. preferable.
Further, when neither p nor q is 0 and p and / or q is 2 or more, either block bonding or random bonding may be used, but from the viewpoint of ease of production, block A bond is preferred.
In n R ¹ , n R ² , and n R ³ , at least one of p in general formula (2) is not 0, and at least one of q in general formula (2) Is not zero.

(Cationic group represented by formula (3))
The cationic group represented by the general formula (3) which is Y ¹ and Y ² in the general formula (2) has a structure represented by the following formula.

In the general formula (3), R ⁴ , R ⁵ and R ⁶ 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, n -A propyl group and an isopropyl group are mentioned. In these, a methyl group or an ethyl group is preferable from a water-soluble viewpoint of C-HPC, and a methyl group is more preferable.
In the general formula (3), X ⁻ represents an anionic group which is a counter ion of an ammonium group. X ⁻ is not particularly limited as long as it is an anionic group. Specific examples thereof include alkyl sulfate ions, sulfate ions, phosphate ions, alkyl carbonate ions, and halide ions. Among these, halide ions are preferable from the viewpoint of ease of production. Examples of halide ions include fluoride ions, chloride ions, bromide ions, and iodide ions. From the viewpoint of the water solubility and chemical stability of C-HPC, chloride ions and bromide ions are preferable. Product ions are more preferred.

In the C-HPC represented by the general formula (1), it is possible to suppress the stickiness after drying of the hair treated with the hair cosmetic composition of the present invention, and to improve the fingering property and the feeling of unity, and the ease of production. In view of the above, the degree of substitution of the cationized ethyleneoxy group is 2.9 or less, preferably 2.5 or less, more preferably 2.0 or less, more preferably 1.5 or less, and further preferably 1.2 or less. preferable. Moreover, from the viewpoint of suppressing the sticky feeling after drying of the hair treated with the hair cosmetic composition of the present invention and improving the fingering property and feeling of unity, it is 0.01 or more, preferably 0.1 or more, and 2 or more is more preferable, 0.3 or more is more preferable, and 0.8 or more is more preferable. Taking these viewpoints together, the degree of substitution of the cationized ethyleneoxy group is 0.01 to 2.9, preferably 0.1 to 2.5, preferably 0.2 to 2.0, 0.3 -1.5 is more preferable, and 0.8-1.2 is still more preferable.
In the present invention, the degree of substitution of the cationized ethyleneoxy group refers to the cationized ethyleneoxy group present in the molecule of C-HPC per mole of anhydroglucose unit (hereinafter also referred to as “AGU”) constituting the cellulose main chain. The average number of moles of a group. The degree of substitution of the cationized ethyleneoxy group is measured by the method described in Examples below.

From the viewpoint of suppressing the stickiness after drying of the hair treated with the hair cosmetic composition of the present invention, improving the fingering property and feeling of unity, and the viewpoint of ease of production, the degree of substitution of the propyleneoxy group is 4. 0 or less, preferably 3.0 or less, more preferably 2.8 or less, more preferably 2.5 or less, and even more preferably 2.0 or less. Further, from the viewpoint of suppressing the sticky feeling after drying of the hair treated with the hair cosmetic composition of the present invention and improving the fingering property and feeling of unity, the degree of substitution of propyleneoxy group is 0.1 or more, 0 .2 or more is preferable, 0.3 or more is more preferable, 0.6 or more is more preferable, and 1.0 or more is more preferable. Taking these viewpoints together, the degree of substitution of the propyleneoxy group is 0.1 to 4.0, preferably 0.2 to 3.0, more preferably 0.3 to 2.8, and 0.6 to 2.5 is more preferable, and 1.0 to 2.0 is still more preferable.
In the present invention, the degree of substitution of propyleneoxy groups means the average number of moles of propyleneoxy groups present in C-HPC molecules per mole of AGU constituting the cellulose main chain. The degree of substitution of the propyleneoxy group is measured by the method described in the examples below.

  From the viewpoint of ease of production, the sum of the degree of substitution of the cationized ethyleneoxy group and the degree of substitution of the propyleneoxy group is preferably 3.2 or less, more preferably 3.0 or less. More preferably, it is preferably 5 or less, and preferably 0.9 or more, and 1.2 or more from the viewpoint of improving the fingering property after drying of the hair treated with the hair cosmetic and the feeling of unity. More preferably, it is 1.5 or more. Summing up these viewpoints, the sum of the substitution degree of the cationized ethyleneoxy group and the substitution degree of the propyleneoxy group is preferably 0.9 to 3.2, more preferably 1.2 to 3.0, and 1.5 -2.5 is more preferable.

  The content of C-HPC is preferably 0.001% by mass or more from the viewpoint of suppressing the stickiness after drying of the hair treated with the hair cosmetic composition of the present invention and improving the feeling of fingering and unity. 0.01 mass% or more is more preferable, 0.05 mass% or more is more preferable, and 0.1 mass% is still more preferable. Further, from the viewpoint of suppressing the sticky feeling after drying of the hair treated with the hair cosmetic composition of the present invention and improving the feeling of fingering and unity, it is preferably 10% by mass or less, more preferably 5% by mass or less. The mass% is more preferable and 0.7 mass% or less is still more preferable. When these viewpoints are combined, the content of C-HPC is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, -0.7 mass% is still more preferable.

[Production of cationized hydroxypropylcellulose (C-HPC)]
The C-HPC of the present invention can be obtained, for example, by the following production methods (1) to (3).
(1) A method in which cellulose, a large amount of water, and a large excess of alkali metal hydroxide are mixed in a slurry state and reacted with a cationizing agent and propylene oxide.
(2) A method in which dimethylacetamide containing lithium chloride is used as a solvent, an amine or an alcoholate catalyst is further added to dissolve cellulose, and a cationizing agent and propylene oxide are reacted.
(3) A method of reacting powdered, pelletized or chip-shaped cellulose, a cationizing agent, and propylene oxide in the presence of a base without using excessive water or a solvent as in (1) and (2) above. .
In the production methods (1) to (3), either the reaction with the cationizing agent or the reaction with propylene oxide may be performed first or simultaneously.
Among these production methods, the production method (3) is preferable from the viewpoint of ease of production. Specific examples of the method for producing C-HPC by the method (3) include (3-1) a method of cationizing and hydroxypropylating a cellulose-containing raw material, and (3-2) alkali-cellulose conversion of the cellulose-containing raw material. And the like, followed by cationization, hydroxypropylation and the like.
Hereinafter, the production method (3) will be specifically described.

[(3-1) Method for Cationization and Hydroxypropylation of Cellulose-Containing Raw Material]
<Cellulose-containing raw material>
Examples of the cellulose-containing raw material for producing C-HPC include (i) a cellulose-containing raw material with reduced crystallinity, such as low crystalline powdered cellulose, and (ii) a cellulose-containing raw material with high crystallinity, such as pulp. Preferably used.
(Cellulose-containing raw material (raw material cellulose))

<(3-1-i) Production of C-HPC using cellulose-containing raw material with reduced crystallinity>
(Production of cellulose-containing raw materials with reduced crystallinity)
Cellulose-containing raw materials with reduced crystallinity, for example, low crystalline powdered cellulose, can be prepared from sheet-like or roll-like pulp with high cellulose purity obtained as a general-purpose raw material. The method for preparing the low-crystalline powdery cellulose is not particularly limited. For example, methods described in JP-A-62-236801, JP-A-2003-64184, JP-A-2004-331918 and the like can be mentioned. Among these, from the viewpoint of improving the productivity of cellulose-containing raw materials having reduced crystallinity, for example, low crystalline powdered cellulose, low crystalline or noncrystalline powdered cellulose obtained by mechanochemical treatment (below) And generically referred to as “low crystalline powdered cellulose”).
Here, the “low crystallinity” of the low crystalline powdered cellulose means a state in which the ratio of the amorphous part is large in the crystal structure of cellulose. Specifically, from the viewpoint of increasing the reactivity with the cationizing agent and propylene oxide, the crystallinity obtained by the following calculation formula (1) is preferably 30% or less, more preferably 20% or less, and further preferably 10% or less. Preferably, it is even more preferable to use completely amorphous cellulose having a crystallinity of approximately 0%.
Crystallinity (%) = [(I _22.6 −I _18.5 ) / I _22.6 ] × 100 (1)
(Wherein, I _22.6 represents the diffraction intensity of the lattice plane of cellulose I type crystal (002 plane) (diffraction angle 2 [Theta] = 22.6 °) in the X-ray diffraction, I _18.5 is amorphous portion (diffraction angle 2 [Theta] = 18.5 °).)

Examples of the method for producing low crystalline powdered cellulose by mechanochemical treatment include a method by treating chip-like pulp obtained by roughly pulverizing sheet pulp with a pulverizer. It is also possible to treat the chip-like pulp with an extruder before the treatment with the pulverizer.
Examples of the extruder used in this method include a single-screw or twin-screw extruder, preferably a twin-screw extruder. From the viewpoint of applying a strong compressive shear force, a so-called kneading is applied to any part of the screw. A thing provided with a disk part is preferred.
Although there is no restriction | limiting in particular as a processing method using an extruder, The method of throwing a chip-form pulp into an extruder and processing continuously is preferable.
As the pulverizer, roll mills such as high-pressure compression roll mills and roll rotating mills; vertical roller mills such as ring roller mills, roller race mills and ball race mills; rolling ball mills, vibration ball mills, vibration rod mills, vibration tube mills, planetary ball mills, Container-driven medium mills such as centrifugal fluidization mills; medium agitation mills such as tower pulverizers, stirring tank mills, flow tank mills, and annular mills; compaction shear mills such as high-speed centrifugal roller mills and ong mills; mortars, Or a stone mill etc. are mentioned. Among these, from the viewpoint of efficiently reducing the crystallinity of cellulose and from the viewpoint of productivity, a container-driven medium mill or a medium stirring mill is preferable, a container-driven medium mill is more preferable, a vibration ball mill, A vibration mill such as a vibration rod mill and a vibration tube mill is more preferable, and a vibration ball mill and a vibration rod mill are more preferable.

The processing method may be either a batch type or a continuous type.
The filling ratio of the medium such as balls and rods varies depending on the type of pulverizer, but is preferably 10 to 97%, more preferably 15 to 95%. When the filling rate is within this range, the contact frequency between the raw pulp and the medium 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 medium relative to the volume of the stirring unit of the pulverizer.
In the case of a ball mill, the material of the ball used as the medium is not particularly limited, and examples thereof include iron, stainless steel, alumina, zirconia and the like. The outer diameter of the ball is preferably 0.1 to 100 mm, more preferably 1 to 50 mm, from the viewpoint of efficiently reducing the crystallinity of cellulose.
Further, from the viewpoint of efficiently reducing the crystallinity of cellulose, the processing time of the pulverizer is preferably 5 minutes to 72 hours, more preferably 10 minutes to 30 hours. In the pulverizer treatment, the treatment is preferably performed at a temperature of preferably 250 ° C. or lower, more preferably 5 to 200 ° C. from the viewpoint of minimizing denaturation and deterioration due to generated heat.

The rod used as the medium of the pulverizer is a rod-shaped medium, and a rod having a cross section of a polygon such as a quadrangle or a hexagon, a circle, or an ellipse can be used.
The outer diameter of the rod is preferably in the range of 0.5 to 200 mm, more preferably 1 to 100 mm, and still more preferably 5 to 50 mm. The length of the rod is not particularly limited as long as it is shorter than the length of the crusher container. If the size of the rod is in the above range, desired pulverization force can be obtained and cellulose can be efficiently crystallized low.
The treatment time and treatment temperature of the vibration mill filled with the rod are not particularly limited.

According to the above method, the molecular weight can be controlled, and powder cellulose having a high degree of polymerization and low crystallinity, which is generally difficult to obtain, can be easily prepared. The average degree of polymerization of the low crystalline powdered cellulose is preferably 50 to 5000, more preferably 100 to 30000, more preferably 200 to 2000, and still more preferably 300 to 1500.
The average particle size of the low crystalline powder cellulose is not particularly limited as long as it can maintain a good fluidity as a powder, but is preferably 300 μm or less, more preferably 150 μm or less, and even more preferably 50 μm or less. Moreover, from a viewpoint of the handleability improvement of powdered cellulose, 20 micrometers or more are preferable and 25 micrometers or more are more preferable. In order to avoid the inclusion of a minute amount of coarse particles due to aggregation or the like, it is preferable to use an under-sieved product using a sieve having an opening of about 300 to 1000 μm as necessary for the reaction.

(Cationization of cellulose-containing raw materials with reduced crystallinity)
A glycidyl trialkylammonium salt is reacted with a cellulose-containing raw material having reduced crystallinity obtained as described above, for example, low crystalline powdered cellulose in the presence of a base to cationize to produce cationized cellulose.
Examples of the glycidyltrialkylammonium salt used as the cationizing agent include glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyltrimethylammonium bromide, glycidyltriethylammonium bromide, and the like. From the viewpoint of availability, glycidyltrimethylammonium chloride is preferable. .
The addition amount of glycidyl trialkylammonium salt is 0.01 to 8.5 times mol of AGU 1 mol of cellulose from the viewpoint of improving the fingering property and feeling of unity after drying of hair treated with hair cosmetics. Is preferable, 0.1-7 times mole is more preferable, 0.2-5.5 times mole is more preferable, 0.5-4.5 times mole is still more preferable.
Examples of the base to be present at the time of cationization include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. From the viewpoint of availability, versatility, and economy, sodium hydroxide, water Barium oxide is more preferred.
The amount of base added varies depending on the type of cellulose and the like, but from the viewpoint of efficiently reacting cellulose and a cationizing agent, the amount is preferably 0.05 to 1.0 times moles of 1 mole of AGU of cellulose. 06-1.0 times mol is more preferable, 0.07-0.7 times mol is still more preferable, 0.1-0.3 times mol is still more preferable.
The water content in the reaction system is preferably 100% by mass or less based on the cellulose used as a raw material. If the moisture content with respect to cellulose is within this range, the cellulose can be reacted in a fluid powder state without excessive aggregation. In this respect, 80% by mass or less is more preferable, and 5 to 50% by mass is even more preferable.
The reaction temperature is usually 10 to 85 ° C, preferably 15 to 80 ° C.

(Hydroxypropylation of cationized cellulose)
C-HPC can be produced by reacting the cationized cellulose obtained as described above with propylene oxide for hydroxypropylation.
Here, the amount of propylene oxide used is 0.01 to 1 mol per mole of AGU in the cellulose molecule from the viewpoint of suppressing the sticky feeling after drying of the hair treated with the hair cosmetic and improving the touchability and the feeling of unity. 8.5 times mole is preferable, 0.1-5.0 times mole is more preferable, and 1.0-3.0 times mole is still more preferable.

A base or an acid can be used as a catalyst for hydroxypropylation. Examples of the base catalyst 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, triethylamine and triethylenediamine. Secondary amines. Examples of the acid catalyst include Lewis acid catalysts such as lanthanide triflate.
In these, a base catalyst is preferable from a viewpoint of suppressing the fall of the polymerization degree of the cellulose in a cellulose containing raw material, An alkali metal hydroxide is more preferable, Sodium hydroxide and potassium hydroxide are still more preferable. These catalysts can be used alone or in combination of two or more.
The amount of the catalyst used is not particularly limited, but is usually preferably 0.05 to 1.0 times mole, more preferably 0.07 to 0.7 times mole, more preferably 0.1 to 0.1 times mole per mole of AGU in the cellulose molecule. 0.3 times mole is more preferable.
When the cationization step is performed first, the base used in the cationization step can be used as it is as a catalyst in hydroxypropylation, and a new catalyst need not be added in the hydroxypropylation step.

There are no particular restrictions on the method of adding propylene oxide. For example, (a) a method in which propylene oxide is added dropwise after adding a catalyst to cationized cellulose, (b) propylene oxide is added to cationized cellulose all at once, and then a catalyst is added. Although the method of adding and reacting gradually is mentioned, Method (a) is more preferable.
The water content in the reaction system is preferably 100% by mass or less based on the cellulose used as a raw material. If the water content with respect to cellulose is within this range, the cationized cellulose can be reacted in a fluid powder state without excessive aggregation. In this respect, 80% by mass or less is preferable, and 5 to 50% by mass is more preferable.
In the present invention, it is preferable to react the cationized cellulose, the catalyst and propylene oxide in a fluid powder state. However, the cationized cellulose powder and the catalyst are preliminarily mixed with a mixer, a shaker, or a mixing mill. For example, propylene oxide may be added and reacted after uniformly mixing and dispersing as required.

The reaction temperature for hydroxypropylation is preferably 0 to 150 ° C., but is preferably 10 to 100 ° C., more preferably 20 to 80 ° C., from the viewpoint of avoiding polymerization of propylene oxides and abrupt reaction. Is more preferable. The reaction can be carried out at normal pressure.
Moreover, it is preferable to carry out in inert gas atmosphere, such as nitrogen, from a viewpoint of avoiding the fall of the molecular weight by cleavage of the cellulose chain during reaction.
After completion of the reaction, C-HPC used in the present invention can be obtained by removing unreacted propylene oxide, followed by neutralization treatment, purification treatment, etc., if necessary, followed by drying.
The neutralization treatment can be performed by a conventional method. For example, when a base catalyst is used as the catalyst, it can be carried out by adding a liquid acid such as acetic acid, a mixed solution of an acid and an inert organic solvent, or an aqueous acid solution. The type of the acid is not particularly limited, and may be appropriately selected in consideration of the corrosion of the apparatus. The purification treatment can be performed by washing with a solvent such as water-containing isopropanol or water-containing acetone solvent and / or water or a dialysis membrane.
The order of the reaction of cationization and hydroxypropylation in the above <(3-1-i) production of C-HPC using cellulose-containing raw material with reduced crystallinity> is the hydroxypropylation of cellulose in the cellulose-containing raw material. After performing, cationization may be performed or may be performed simultaneously.
From the viewpoint of controlling the degree of substitution of the cationized ethyleneoxy group and propyleneoxy group, it is preferable to perform hydroxypropylation after cationization of the cellulose in the cellulose-containing raw material.
Further, for the purpose of increasing the degree of substitution of the cationized ethyleneoxy group, a cationization reaction or a hydroxypropylation reaction may be performed and then a cationization reaction may be performed.
In the cationization reaction step and the hydroxypropylation reaction step in the above <(3-1-i) production of C-HPC using cellulose-containing raw material with reduced crystallinity>, the cellulose skeleton that becomes the main chain is cleaved. Therefore, the average degree of polymerization of C-HPC obtained can be approximated by the average degree of polymerization of powdered cellulose after the low crystallization treatment.

<(3-1-ii) Production of C-HPC using cellulose-containing raw material with high crystallinity>
(Cationization of highly crystalline cellulose-containing raw materials)
Cellulose-containing raw materials with reduced crystallinity as described above, such as cellulose-containing raw materials with high crystallinity, such as pulp (hereinafter referred to as cellulose-containing raw materials) Is a pulp), it is preferable to perform low crystallization at the time of cationization in order to improve the reactivity of the cellulose-containing raw material.
Specifically, a cationizing agent is added to a cellulose-containing raw material and low crystallization is performed by a pulverizer treatment, and then a cellulose is added to the cellulose-containing raw material and the cationizing agent while low crystallization is performed by a pulverizer treatment. A cellulose-containing raw material and a cationizing agent are added while performing a reaction, or adding a base to the cellulose-containing raw material and performing low crystallization by a pulverizer treatment, and then adding a cationizing agent and performing low crystallization by a pulverizer treatment By performing the reaction, cationized cellulose can be obtained. In addition, from the viewpoint of obtaining C-HPC having a high degree of substitution of a cationized ethyleneoxy group, a cationizing agent is added to the cellulose-containing raw material to perform a pulverizer treatment, and then a base is added to perform a pulverizer treatment. Further, it is preferable to add a cationizing agent and perform the pulverizer treatment. The addition of the base and the subsequent addition of the cationizing agent may be performed in multiple stages.
From the viewpoint of water solubility of C-HPC obtained through this cationization, in the cationization of cellulose, first, a cationizing agent is added to the cellulose-containing raw material, and low crystallization is performed by a pulverizer treatment. Thereafter, it is preferable to react the cellulose-containing raw material with the cationizing agent while adding a base and performing low crystallization by a pulverizer treatment.

  Highly crystalline cellulose-containing raw materials include various types of wood chips; wood pulp made from wood, pulps such as cotton linter pulp obtained from fibers around cotton seeds; newspapers, cardboard, magazines, fine paper Paper stems such as rice straw, corn stalks and other plant stems and leaves; plant husks such as rice husks, palm husks, coconut husks, etc. From the viewpoint of high cellulose purity and C-HPC productivity Wood pulp is preferred.

The shape of the pulp used as the cellulose-containing raw material is not particularly limited as long as the introduction into the production apparatus is not hindered, but from the viewpoint of operation, a pellet form obtained by cutting or coarsely pulverizing sheet-like pulp or sheet-like pulp or It is preferable to use chip-like pulp or powdered cellulose obtained by pulverization.
There is no limitation on the crystallinity of the pulp used as the cellulose-containing raw material. However, in general, the cellulose crystallinity-reducing treatment is accompanied by a decrease in the molecular weight associated with the breaking of the cellulose chain, so that the cellulose in the cellulose-containing raw material having a low crystallinity has a low molecular weight. Therefore, it is preferable to use cellulose having high crystallinity from the viewpoint of obtaining high molecular weight C-HPC. On the other hand, it is difficult to obtain cellulose having a crystallinity of 95% or higher according to the calculation formula (1). Therefore, from the viewpoint of the degree of polymerization and easy availability, the crystallinity of the cellulose in the cellulose-containing raw material is preferably 10 to 95%, more preferably 30 to 90%, and more preferably 60 to 90%. 80% is more preferable.
Although the average degree of polymerization of cellulose in the cellulose-containing raw material is not limited, it is preferable to use cellulose having a higher degree of polymerization from the viewpoint of obtaining high molecular weight C-HPC. From this viewpoint, the average degree of polymerization of cellulose in the cellulose-containing raw material is preferably 50 to 5000, and more preferably 100 to 2000.

Preferred embodiments such as the kind and amount of the cationizing agent, the kind of base, the kind of pulverizer, the low crystallization method and the conditions, except for the processing time of the pulverizer for low crystallization and the amount of base, (3-1- (i) This is the same as that described in the section “Production of C-HPC Using Cellulose-Containing Raw Material with Reduced Crystallinity >>.
The processing time of the pulverizer for low crystallization is preferably 1 minute to 5 hours, preferably 2 minutes to 3 hours from the viewpoint of efficiently reducing the crystallinity of cellulose and suppressing the decrease in the polymerization degree. More preferred is 5 minutes to 2 hours.
The amount of the base is preferably 0.05 to 1.5 times mol, preferably 0.07 to 1.0 times mol per mol of AGU of cellulose in the cellulose-containing raw material, from the viewpoint of efficiently reacting cellulose and cationizing agent. Is more preferable, and 0.1-0.6 times mole is still more preferable.
Cationization proceeds at the time of low crystallization after the addition of a cationizing agent and a base, but when the progress of the reaction is insufficient, aging is preferably performed at 10 to 100 ° C, more preferably at 30 to 80 ° C. Thus, the reaction can proceed.
Even if the cationization reaction proceeds sufficiently, a cationized cellulose having a high degree of substitution of the cationized ethyleneoxy group can be obtained by further adding glycidyltrialkylammonium salt and aging. .
In the case of cationization of the above-mentioned low crystalline powdered cellulose, except that the moisture content at the time of ripening, and the preferred embodiment thereof, use a cellulose-containing raw material having a high degree of crystallinity instead of the low crystalline powdered cellulose It is the same.
Moreover, it is preferable to carry out in inert gas atmosphere, such as nitrogen, from a viewpoint of avoiding the fall of the molecular weight by cleavage of the cellulose chain during reaction.

(Hydroxypropylation of cationized cellulose)
<(3-1-ii) Production of C-HPC using cellulose-containing raw material with high crystallinity: Method a >> Propylene oxide amount used in hydroxypropylation of cationized cellulose, catalyst, reaction conditions, after completion of reaction The treatment and preferred embodiments thereof are the same as those described for hydroxypropylation in <(3-1-i) Production of C-HPC using cellulose-containing raw material with reduced crystallinity>.
The order of the reaction of cationization and hydroxypropylation in the above <(3-1-ii) C-HPC production using cellulose-containing raw material with high crystallinity: Method a> is performed by hydroxypropylating the cellulose-containing raw material. After the cationization, the cellulose-containing raw material may be cationized from the viewpoint of controlling the degree of substitution of the cationized ethyleneoxy group and propyleneoxy group, and then hydroxypropylated. It is preferable to carry out.
Further, from the viewpoint of increasing the degree of substitution of the cationized ethyleneoxy group, a cationization reaction or a hydroxypropylation reaction may be performed, followed by further cationization reaction.

[(3-2) Method of Cationization and Hydroxypropylation after Making Cellulose-Containing Raw Material Alkaline Cellulose]
<Cellulose-containing raw material>
The cellulose-containing raw material for producing C-HPC is the same as [(3-1) Method of cationizing and hydroxypropylating a cellulose-containing raw material] (i) a cellulose-containing raw material with reduced crystallinity, (Ii) A cellulose-containing raw material having high crystallinity is preferably used.

<(3-2-i) Production of C-HPC Using Cellulose-Containing Raw Material with Reduced Crystallinity: Method b>
(Production of cellulose-containing raw materials with reduced crystallinity)
The cellulose-containing raw material with reduced crystallinity is the same as that described in <(3-1-i) Production of C-HPC using cellulose-containing raw material with reduced crystallinity>.
From the viewpoint of improving the productivity of a cellulose-containing raw material having reduced crystallinity, a cellulose-containing raw material having high crystallinity, for example, a material obtained by pulverizing wood pulp is preferable.
The crystallinity of the cellulose-containing raw material with reduced crystallinity is 10 to 10 from the viewpoint of increasing the reactivity between alkali cellulose, a cationizing agent and propylene oxide, which will be described later, and the degree of polymerization of the cellulose-containing raw material. 50% is preferable, 10 to 40% is more preferable, and 10 to 30% is still more preferable.

(Alkaline cellulose conversion of cellulose-containing raw materials with reduced crystallinity)
Alkali cellulose can be obtained by mixing a cellulose-containing raw material having reduced crystallinity, a base and water.
Bases include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, and tertiary such as trimethylamine, triethylamine and triethylenediamine. Examples include amines. Among these, alkali metal hydroxides or alkaline earth metal hydroxides are preferable, alkali metal hydroxides are more preferable, and sodium hydroxide and potassium hydroxide are still more preferable. These bases can be used alone or in combination of two or more.
The amount of the base is 0 per mol of AGU constituting the cellulose in the cellulose-containing raw material from the viewpoint of improving the yield of the alkali cellulose and enhancing the productivity of the alkali cellulose, the cationizing agent, and propylene oxide described later. .6 to 1.5 mol is preferable, 0.7 to 1.3 mol is more preferable, and 0.8 to 1.2 mol is still more preferable.
The addition amount of water is 20-100 with respect to the cellulose in a cellulose containing raw material from a viewpoint which improves the yield of an alkali cellulose, and the viewpoint which improves the productivity of the alkali cellulose mentioned later and a cationizing agent, and a propylene oxide. It is preferably at least mass%, more preferably from 25 to 70 mass%, still more preferably from 30 to 60 mass%.

The method for mixing the cellulose-containing raw material, base, and water with reduced crystallinity is not particularly limited, but from the viewpoint of improving productivity, a base and water are added to the cellulose-containing raw material with reduced crystallinity. Is preferred. As a method for addition, batch addition or divided addition may be used. Moreover, you may spray and add what mixed the base and water beforehand.
An apparatus for mixing is not particularly limited as long as the apparatus can disperse the base in the cellulose-containing raw material. Examples of the mixer include a ribbon type mixer, a paddle type mixer, a conical planetary screw type mixer, and a kneader. Among these, a horizontal shaft type paddle type mixer is more preferable, and specifically, a Redige mixer which is a horizontal shaft type paddle type mixer having chopper blades is preferable.
It is preferable to age from the viewpoint of improving the production rate of alkali cellulose after mixing the cellulose-containing raw material having reduced crystallinity, a base, and water. The aging temperature is preferably 35 to 90 ° C, more preferably 38 to 80 ° C, and still more preferably 40 to 70 ° C. The aging time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours, and further preferably 1 to 6 hours.
The change from the cellulose-containing raw material to alkali cellulose can be confirmed by X-ray crystal diffraction measurement.

(Hydroxypropylation of alkali cellulose)
Preferred embodiments of the amount of propylene oxide, catalyst type, amount of catalyst, and reaction conditions in hydroxypropylation of alkali cellulose are as follows: <(3-1-i) Production of C-HPC using cellulose-containing raw material with reduced crystallinity > Is the same as described in (Hydroxypropylation).
(Cationization of hydroxypropylcellulose)
Preferred embodiments of cationizing agent species, cationizing agent amount, cationizing agent amount, catalyst amount, catalyst amount and reaction conditions in the cationization of hydroxypropyl cellulose use the above-mentioned <(3-1-i) cellulose-containing raw material with reduced crystallinity. The same as described in (Cationization) in Production of C-HPC>.

<(3-2-ii) Production of C-HPC Using Cellulose-Containing Raw Material with High Crystallinity: Method c>
(Alkaline cellulose conversion of cellulose-containing raw materials)
The cellulose-containing raw material can be pulverized together with a base under conditions where water is not substantially present to obtain a cellulose / base mixed pulverized product, and then mixed with water to obtain alkali cellulose.
The preferred embodiments of the type, shape, crystallinity, and average degree of polymerization of the cellulose-containing raw material are the same as those described in (Cationization of cellulose-containing raw material with high crystallinity) in the method a.
Moreover, the preferable aspect of the kind of basic compound and the quantity of a base is the same as that of the thing as described in the (alkaline celluloseation) in said b method.
From the viewpoint of reducing the amount of water during pulverization, the base is preferably mixed without containing water.
The pulverizer treatment is preferably performed under conditions where water is not substantially present. That is, from the viewpoint of improving productivity such as grinding efficiency and ease of water removal, the water content with respect to the cellulose-containing raw material is preferably 10% by mass or less, more preferably 0.01 to 8% by mass, and more preferably 0.1 to 6%. % By mass is more preferable, and 1% by mass to 5% by mass is even more preferable.

The preferred embodiments of the type of pulverizer and the pulverizing conditions are the above (<3-1-i) C-HPC production using cellulose-containing raw material with reduced crystallinity> (cellulose content with reduced crystallinity). This is the same as that described in (Production of raw materials).
From the viewpoint of improving the production rate of alkali cellulose, from the viewpoint of improving the yield of alkali cellulose, and from the viewpoint of suppressing a decrease in the average degree of polymerization of cellulose, the average particle size of cellulose in the cellulose / base mixed pulverized product is 10 to 10. It is preferable to grind | pulverize until it becomes 150 micrometers, 20-130 micrometers is more preferable, 40-100 micrometers is still more preferable, 50-80 micrometers is still more preferable. The average particle size of cellulose in the cellulose / base mixed pulverized product is measured by the method described in Examples.
From the viewpoint of improving the yield of alkali cellulose, and from the viewpoint of increasing the productivity of alkali cellulose, a cationizing agent, and propylene oxide, which will be described later, the water content of the cellulose / base mixed pulverized product is relative to the cellulose in the cellulose-containing raw material. Thus, water is preferably mixed with the cellulose / base mixed pulverized product so as to be 30 to 100% by mass, more preferably 35 to 70% by mass, and still more preferably 40 to 60% by mass.

(Hydroxypropylation of alkali cellulose)
Preferred embodiments of the amount of propylene oxide, catalyst type, amount of catalyst, and reaction conditions in hydroxypropylation of alkali cellulose are as follows: <(3-1-i) Production of C-HPC using cellulose-containing raw material with reduced crystallinity > Is the same as described in (Hydroxypropylation).
(Cationization of hydroxypropylcellulose)
Preferred embodiments of cationizing agent species, cationizing agent amount, cationizing agent amount, catalyst amount, catalyst amount and reaction conditions in the cationization of hydroxypropyl cellulose use the above-mentioned <(3-1-i) cellulose-containing raw material with reduced crystallinity. The same as described in (Cationization) in Production of C-HPC>.

  The reaction order of hydroxypropylation and cationization in the above b method and c method may be reversed, but from the viewpoint of increasing the substitution degree of the cationized ethyleneoxy group, it is preferable to carry out the hydroxypropylation reaction and the cationization reaction in this order. .

As a method for producing C-HPC used in the present invention, from the viewpoint of improving the fingering property after drying of the hair treated with the hair cosmetic composition of the present invention and the feeling of unity, in the method of (3-1), <(3-1-ii) Production of C-HPC using cellulose-containing raw material with high crystallinity> (Method a below) and Method (3-2) below (Method b and c below) Method) is preferred.
Specifically, from the viewpoint of improving the fingering property after drying of the hair treated with the hair cosmetic composition of the present invention and the feeling of unity, C-HPC comprises the following steps (a-1) to (a-3): Obtained by a method having the following steps, or obtained by a method having the following steps (a-4) and (a-5), obtained by a method having the following steps (b1) to (b4), or What is obtained by the method which has process (c-1)-(c-4) is preferable, and what is obtained by the method which has the following method a: process (a-1)-(a-3), the following method b: Those obtained by the method having the steps (b-1) to (b-4) or those obtained by the method having the following c method: steps (c-1) to (c-4) are more preferable.

Method a:
Step (a-1): A step of adding a cationizing agent to the cellulose-containing raw material and carrying out a pulverizer treatment Step (a-2): Adding a base to the pulverizer treated product obtained in step (a-1) The step of obtaining a cationized cellulose by reacting the cellulose-containing raw material with a cationizing agent while carrying out a pulverizer treatment Step (a-3): The cationized cellulose and propylene oxide obtained in Step (a-2) Process for obtaining cationized hydroxypropylcellulose (A) by reaction

Step (a-4): A base is added to the cellulose-containing raw material and low crystallization is performed by a pulverizer treatment, and then a cationizing agent is added and the crystallization is performed by a pulverizer treatment while the cellulose-containing raw material is cationized. Step of obtaining a cationized cellulose by reacting an agent Step (a-5): A step of obtaining cationized hydroxypropylcellulose by reacting the cationized cellulose obtained in step (a-4) with propylene oxide.

Method b:
Step (b-1): A step of obtaining a cellulose-containing raw material containing cellulose having a crystallinity of 10 to 50% by pulverizing the cellulose-containing raw material Step (b-2): Step (b-1) To the cellulose-containing raw material obtained in step 1 to 0.6 to 1.5-fold moles of base per mole of AGU constituting the cellulose, and 20 to 100% by mass of water to the cellulose in the cellulose-containing raw material. Step of adding and obtaining alkali cellulose Step (b-3): Step of obtaining hydroxypropyl cellulose by reacting the alkali cellulose obtained in step (b-2) with propylene oxide Step (b-4): Step ( a step of reacting the hydroxypropylcellulose obtained in b-3) with a cationizing agent to obtain cationized hydroxypropylcellulose (A)

Method c:
Step (c-1): A cellulose-containing raw material and a mixture of 0.6 to 1.5-fold moles of base per mole of AGU constituting the cellulose in the cellulose-containing raw material have a water content with respect to cellulose in the cellulose-containing raw material. A step of obtaining a cellulose / base mixed pulverized product having a mean cellulose particle size of 10 to 150 μm by subjecting to a pulverizer under a condition of 10% by weight or less. Step (c-2): obtained in step (c-1) Water is added to the cellulose / base mixed pulverized product, and the water content in the cellulose / base mixed pulverized product is adjusted to 30 to 100% by mass with respect to the cellulose in the cellulose-containing raw material used in step (c-1). Step of obtaining alkali cellulose Step (c-3): The alkali cellulose obtained in step (c-2) is reacted with propylene oxide to produce hydroxypropyl cellulose. Step (c-4): Step of obtaining cationized hydroxypropylcellulose (A) by reacting the hydroxypropylcellulose obtained in step (c-3) with a cationizing agent.

<Oil agent (B)>
The hair cosmetic composition of the present invention comprises, as an oil agent (B), an ester compound represented by the general formula (4), a dialkyl carbonate compound represented by the general formula (5), and a dialkyl represented by the general formula (6). Contains one or more compounds selected from ether compounds.
(Ester compound represented by the general formula (4))
The ester compound represented by the following general formula (4) is an ester compound obtained by an esterification reaction of an aromatic alcohol alkylene oxide adduct and an aliphatic carboxylic acid.
_{^{R 7 O- (AO) m -COR}} 8 (4)
(In the formula, R ⁷ represents a carbon hydrogen group having 6 to 20 carbon atoms containing at least one substituted or unsubstituted aromatic ring, and R ⁸ is a linear or branched alkyl group having 1 to 25 carbon atoms. AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and m is a number from 1 to 50. When m is 2 or more, the m AO groups are the same or different. May be good.)
R ^{7 in the} general formula (4) is an aromatic group having 6 to 12 carbon atoms from the viewpoint of suppressing the stickiness after drying of the hair treated with the hair cosmetic composition of the present invention and improving the feeling of fingering and unity. A hydrocarbon group is preferred, an aromatic hydrocarbon group having 6 to 10 carbon atoms is more preferred, and a benzyl group is still more preferred.
R ⁸ is preferably an alkyl group having 7 to 21 carbon atoms, more preferably an alkyl group having 11 to 15 carbon atoms, from the same viewpoint as described above.
From the same viewpoint as described above, the AO group is preferably a propyleneoxy group, m is preferably 1 to 10, and more preferably 1 to 5.
Preferred examples of the ester compound represented by the general formula (4) include propylene oxide 3 mol adduct of benzyl alcohol and myristic acid ester (trade name: Kurodamol STS, manufactured by Croda), 3 mol of propylene oxide of benzyl alcohol. Examples include adducts and esters of 2-ethylhexylic acid (manufactured by Croda, trade name: Kurodamol SFX).

(Dialkyl carbonate compound represented by the general formula (5))
^{_{R 9 O (CH 2 CH 2}} O) r CO (OCH 2 CH 2) s -OR 10 (5)
(In the formula, R ⁹ and R ¹⁰ each represent a linear or branched alkyl group and / or alkenyl group having 6 to 22 carbon atoms, and r and s are each 0 or a number of 1 to 50.)
In the compound represented by the general formula (5), R ⁹ and R ¹⁰ are from the viewpoint of suppressing the sticky feeling after drying of the hair treated with the hair cosmetic composition of the present invention and improving the feeling of fingering and unity. An alkyl group having 6 to 18 carbon atoms is preferable, and an alkyl group having 8 to 12 carbon atoms is more preferable.
From the same viewpoint as described above, r and s are preferably 0 or a number of 1 to 5, and more preferably 0.
Preferable examples of the dialkyl carbonate compound represented by the general formula (5) include dioctyl carbonate (trade name: cethiol CC, manufactured by Cognis).

(Dialkyl ether compound represented by the following general formula (6))
R ¹¹ —O—R ¹² (6)
(In the formula, R ¹¹ and R ¹² each represent a linear or branched alkyl group and / or alkenyl group having 6 to 22 carbon atoms.)
In the dialkyl ether compound represented by the general formula (6), R ¹¹ and R ¹² suppress the stickiness after drying of the hair treated with the hair cosmetic composition of the present invention, and improve the fingering property and the feeling of unity. From the viewpoint, an alkyl group having 6 to 18 carbon atoms is preferable, and an alkyl group having 8 to 12 carbon atoms is more preferable.
Preferable examples of the dialkyl ether compound represented by the general formula (6) include dioctyl ether (trade name: cethiol OE, manufactured by Cognis).
The compounds represented by the general formulas (4) to (6) can be used alone or in combination of two or more.

The hair cosmetic composition of the present invention may contain an oil agent (hereinafter referred to as “other oil agent”) other than the oil agent (B), which has a solubility in 100 g of water at 20 ° C. of 0 to 0. 1 g of oil is preferable, and it is an oily component that is usually used in pharmaceuticals, quasi-drugs, cosmetics, toiletries, miscellaneous goods, etc. Any water-insoluble oil agent can be used.
Specific examples of other oil agents include (i) ester oils, (ii) silicone oils, (iii) ether oils, (iv) hydrocarbon oils, (v) having a solubility in 100 g of water at 20 ° C. of 0 to 1 g. ) Higher alcohol, and (vi) carboxylic acid having a hydrocarbon group having 17 to 23 carbon atoms which may be substituted by a hydroxyl group.
Among these, when the hair cosmetic composition of the present invention is used in a conditioner, hair rinse, treatment, etc., from the viewpoint of improving the feeling of fingering and unity after drying of the hair treated with the hair cosmetic composition of the present invention (v ) Higher alcohols are preferred, and higher alcohols having a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, preferably 8 to 20 carbon atoms, more preferably 12 to 18 carbon atoms are preferred.
Specific examples of higher alcohols include 2-ethylhexyl alcohol, octyl alcohol, decyl alcohol, isodecyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, ico Sil alcohol, behenyl alcohol, etc. are mentioned.

The content of the oil agent (B) is 0.01% by mass in the hair cosmetic composition from the viewpoint of suppressing the stickiness after drying of the hair treated with the hair cosmetic composition of the present invention and improving the feeling of fingering and unity. % Or more is preferable, 0.05 mass% or more is more preferable, and 0.1 mass% is still more preferable. Further, from the viewpoint of suppressing the stickiness after drying of the hair treated with the hair cosmetic composition of the present invention and improving the fingering property, it is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less. Is more preferable. If these viewpoints are put together, 0.01-20 mass% is preferable in hair cosmetics, as for content of an oil agent (B), 0.05-15 mass% is more preferable, and 0.1-10 mass% is 0.1-10 mass%. Further preferred.
Further, the mass ratio of the oil agent (B) to the C-HPC (A) [oil agent (B) / C-HPC (A)] suppresses the stickiness after drying of the hair treated with the hair cosmetic composition of the present invention. From the viewpoint of improving the fingering property, 0.05 to 1500 is preferable, 0.05 to 1000 is more preferable, and 0.05 to 500 is still more preferable.

(Application to shampoo)
When the hair cosmetic composition of the present invention is used for shampoos and the like, from the same viewpoint as described above, the content of the oil agent (B) is preferably 0.1 to 10 mass% in the hair cosmetic composition, and 0.5 to 8 mass%. % Is more preferable, and 3-6 mass% is still more preferable.
When the oil agent (B) and other oil agent are used in combination, the content of the other oil agent is selected from the viewpoint of improving the fingering property after drying of the hair treated with the hair cosmetic material of the present invention and the feeling of unity. Among these, 0.1% by mass or more is preferable, 0.3% by mass or more is more preferable, and 0.5% by mass or more is more preferable. In addition, from the viewpoint of suppressing the stickiness of the hair after treatment drying with the hair cosmetic of the present invention and improving the fingering property, the content of the other oil agent is preferably 10% by mass or less in the hair cosmetic, 8 mass% or less is more preferable, and 5 mass% or less is still more preferable. Taking these viewpoints together, the content of the other oil agent is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, and further preferably 0.5 to 5% by mass in the hair cosmetic composition. preferable. Furthermore, as another oil agent, it is still more preferable to contain 0.5-5 mass% of silicone oil.

When the hair cosmetic composition of the present invention is used for shampoos, etc., the total content of the oil agent (B) and other oil preparations improves the fingering property and unity feeling after drying of the hair treated with the hair cosmetic composition of the present invention. From the viewpoint, in the hair cosmetic composition, 0.2% by mass or more is preferable, 0.5% by mass or more is more preferable, and 1% by mass or more is further preferable. Further, from the viewpoint of suppressing the sticky feeling of the hair after treatment drying with the hair cosmetic of the present invention and improving the fingering property, 10% by mass or less is preferable, and 8% by mass or less is more preferable. 6 mass% or less is still more preferable. If these viewpoints are put together, 0.2-10 mass% is preferable in hair cosmetics, and, as for the total content of an oil agent (B) and another oil agent, 0.5-8 mass% is more preferable, 1-6 More preferred is mass%.
Further, the mass ratio of the oil agent (B) to the C-HPC (A) [oil agent (B) / C-HPC (A)] suppresses the stickiness after drying of the hair treated with the hair cosmetic composition of the present invention. From the viewpoint of improving the fingering property, 0.05 to 150 is preferable, 0.1 to 50 is more preferable, 0.5 to 25 is more preferable, and 1.5 to 12 is still more preferable.

(Application to conditioner, hair rinse, treatment)
When the hair cosmetic composition of the present invention is used in a conditioner, hair rinse, treatment or the like, the content of the oil agent (B) suppresses the stickiness after drying of the hair treated with the hair cosmetic composition of the present invention, From the viewpoint of improving the sense of unity, the content in hair cosmetics is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.8% by mass or more. Further, from the viewpoint of suppressing the sticky feeling after drying of the hair treated with the hair cosmetic of the present invention, the content in the hair cosmetic is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 2% by mass or less. preferable. When these viewpoints are put together, the content of the oil agent (B) is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and 0.8 to 2% by mass in the hair cosmetic composition. Further preferred.
When other oil agent is used in combination, the content of the other oil agent is 1% by mass in the hair cosmetic composition from the viewpoint of improving the fingering property after drying the hair treated with the hair cosmetic composition of the present invention and the feeling of unity. The above is preferable, 2 mass% or more is more preferable, and 3 mass% or more is still more preferable. Further, from the viewpoint of suppressing the sticky feeling of the hair after treatment drying with the hair cosmetic of the present invention and improving the fingering property, 10% by mass or less is preferable, and 8% by mass or less is more preferable. 5 mass% or less is still more preferable. When these viewpoints are put together, the content of the other oil agent is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably 3 to 5% by mass in the hair cosmetic composition.
Furthermore, it is more preferable to contain 3-5 mass% of higher alcohols as other oil agents.

When the hair cosmetic composition of the present invention is used in a conditioner, hair rinse, treatment, etc., the total content of the oil agent (B) and other oil preparations is determined as follows: From a viewpoint of improving a feeling, 1 mass% or more is preferable in hair cosmetics, 2 mass% or more is more preferable, and 4 mass% or more is still more preferable. Further, from the viewpoint of suppressing the sticky feeling of the hair after treatment drying with the hair cosmetic of the present invention, the hair cosmetic preferably has 20% by mass or less, more preferably 10% by mass or less, and still more preferably 6% by mass or less. . If these viewpoints are put together, 1-20 mass% is preferable in hair cosmetics, and, as for the total content of oil agent (B) and other oil agents, 2-10 mass% is more preferable, and 4-6 mass% is still more. preferable.
The mass ratio of oil agent (B) to C-HPC (A) [oil agent (B) / C-HPC (A)] suppresses the stickiness after drying of the hair treated with the hair cosmetic composition of the present invention. From the viewpoint of improving the passability and unity, 0.1 to 150 is preferable, 0.5 to 50 is more preferable, 1.5 to 25 is more preferable, and 3 to 12 is still more preferable.

<Surfactant (C)>
As the surfactant (C) used in the present invention, any surfactant can be used as long as it is usually used in pharmaceuticals, quasi drugs, cosmetics, toiletries, miscellaneous goods and the like.
Specific examples include anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants, which improve the feeling of unity after drying hair treated with hair cosmetics. From the viewpoint, it is preferable to use an ionic surfactant such as an anionic surfactant, an amphoteric surfactant, and a cationic surfactant.

When the hair cosmetic composition of the present invention is used as a hair shampoo or the like, it is selected from an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant from the viewpoints of detergency, foamability and foam quality. It is preferable to use one or more of these.
In addition, when the hair cosmetic composition of the present invention is used as a hair treatment, hair rinse, hair conditioner, hair cream or the like, a cation is used from the viewpoint of improving the fingering property and unity feeling after drying of the hair treated with the hair cosmetic composition. It is preferable to use a cationic surfactant and / or a nonionic surfactant, and it is more preferable to use a cationic surfactant.

(Anionic surfactant)
As the anionic surfactant, those of sulfate ester, sulfonate, carboxylate, phosphate ester and amino acid salt are preferable.
Specifically, sulfates such as alkyl sulfates, alkenyl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, polyoxyalkylene alkyl phenyl ether sulfates; sulfosuccinic acid alkyl ester salts, poly Oxyalkylenesulfosuccinic acid alkyl ester salts, alkane sulfonates, acyl isethionates, acyl methyl taurates and other sulfonates; C 8-16 higher fatty acid salts, carboxylates such as polyoxyalkylene alkyl ether acetates Phosphoric acid ester salts such as alkyl phosphates and polyoxyalkylene alkyl ether phosphates; and amino acid salts such as acyl glutamates, alanine derivatives, glycine derivatives, and arginine derivatives.
Anionic surfactants are hydrophobic from the viewpoints of cleansing properties, foaming properties and foam quality of hair cosmetics, and improving the feel of hair after treatment with hair cosmetics and the feeling of unity. The moiety preferably has an alkyl group or alkenyl group having 8 to 20 carbon atoms, and more preferably has an alkyl group or alkenyl group having 10 to 16 carbon atoms.
Among these, alkyl sulfates such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate (sodium laureth-2 sulfate), higher fatty acid salts such as potassium laurate, polyoxyethylene Polyoxyethylene alkyl ether acetates such as sodium lauryl ether acetate (laureth-4.5 sodium acetate), sulfosuccinic acid alkyl ester salts such as sodium laureth-2 sulfosuccinate, sodium N-acyl-L-glutamate (sodium cocoyl glutamate) Acyl glutamates such as are preferred.

(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, Examples include polyethylene glycol types such as oxyalkylene (cured) castor oil, polyhydric alcohol types such as sucrose fatty acid ester, polyglycerin alkyl ether, polyglycerin fatty acid ester, alkylglycoside, and fatty acid alkanolamide.
From the viewpoint of improving the washability of the hair cosmetic and the amount of foam at the time of washing, the viewpoint of foam quality, and the fingering property after drying of the hair treated with the hair cosmetic, the non-ionic surfactant is improved. It is preferable to have an alkyl group or an alkenyl group having 8 to 20 carbon atoms as the hydrophobic site.
Among these, alkyl glucosides having 8 to 18 carbon atoms, preferably 8 to 12 carbon atoms such as decyl glucoside, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene cetostearyl ether, coconut oil fatty acid mono Fatty acid monoalkanolamides such as ethanolamide and coconut oil fatty acid N-methylmonoethanolamide are 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, imidazoline-based betaine from the viewpoint of improving the cleanability of the hair cosmetic and the amount of foam at the time of washing, the foam quality, and the fingering property after drying of the hair treated with the hair cosmetic and the feeling of unity , Sulfobetaine, fatty acid amidopropyl betaine, and the like are preferable. Specifically, coconut oil fatty acid amidopropyl betaine, laurylcarbomethoxymethylhydroxyimidazolium betaine, laurylhydroxysulfobetaine, and the like are preferable.

(Cationic surfactant)
The cationic surfactant includes a mineral amine or organic acid salt of a tertiary amine represented by the following general formula (7), and a quaternary ammonium salt type surfactant represented by the following general formula (8). Is mentioned.

(In the formula, R ¹³ represents a linear or branched alkyl group or alkenyl group having 6 to 28 carbon atoms which may be interrupted by an amide group, an ester group or an ether group, and R ¹⁴ represents an amide group, A linear or branched alkyl group having 1 to 28 carbon atoms, an alkenyl group or an alkanol group which may be interrupted by an ester group or an ether group, and R ¹⁵ is a linear or branched chain having 1 to 3 carbon atoms. Represents an alkyl group or an alkanol group.)
In the general formula (7), the carbon number of R ¹³ is preferably 12 to 28, and preferably 14 to 25, from the viewpoint of improving the fingering property after drying of the hair treated with the hair cosmetic composition of the present invention and the feeling of unity. More preferably, 16-25 is still more preferable. From the same viewpoint, R ¹⁴ preferably has 12 to 28, more preferably 14 to 25, and still more preferably 16 to 25, or a methyl group, an ethyl group, or a hydroxylethyl group. From the same viewpoint, R ¹⁵ is preferably a methyl group, an ethyl group, or a hydroxylethyl group.
The mineral acid or organic acid that forms a salt with the tertiary amine represented by the general formula (7) is not particularly limited, but from the viewpoint of dispersion stability of the surfactant, hydrogen halide, sulfuric acid, acetic acid, citric acid, Lactic acid glutamic acid and alkyl sulfuric acid having 1 to 3 carbon atoms are preferred, and hydrogen halide is preferred from the viewpoint of chemical stability.

(Wherein R ¹⁶ represents a linear or branched alkyl group or alkenyl group having 6 to 28 carbon atoms which may be interrupted by an amide group, an ester group or an ether group, and R ¹⁷ represents an amide group, A linear or branched alkyl group, an alkenyl group or an alkanol group having 1 to 28 carbon atoms which may be interrupted by an ester group or an ether group, and R ¹⁸ and R ¹⁹ are linear chains having 1 to 3 carbon atoms. Alternatively, it represents a branched alkyl group, and Z ⁻ represents an anionic group which is a counter ion of an ammonium salt.)
In the general formula (8), a preferable embodiment of R ¹⁶ is preferably R ¹³ in the general formula (7) from the viewpoint of improving the fingering property and the feeling of unity after drying of the hair treated with the hair cosmetic composition of the present invention. Same as embodiment. From the same viewpoint, the preferred embodiment of R ¹⁷ is the same as the preferred embodiment of R ¹⁴ in the general formula (7). From the same viewpoint, R ¹⁸ and R ¹⁹ are preferably a methyl group or an ethyl group.
Z ⁻ is not particularly limited as long as it is an anionic group. Specific examples thereof include alkyl sulfate ions, sulfate ions, phosphate ions, alkyl carboxylates, and halide ions. Among these, halide ions are preferable from the viewpoints of ease of production and availability. Halide ions include fluoride ions, chloride ions, bromide ions, and iodide ions. From the viewpoint of chemical stability, chloride ions and bromide ions are preferable, and chloride ions are more preferable.

  Examples of the cationic surfactants represented by the general formulas (7) and (8) include mono long-chain alkyltrimethylammonium chloride, dilong-chain alkyldimethylammonium chloride, and long-chain tertiary amine salts. Specifically, mono-chain alkyltrimethylammonium chloride such as stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearoxypropyltrimethylammonium chloride; distearyldimethylammonium chloride, diisostearyldimethylammonium chloride, etc. Di long chain alkyldimethylammonium chloride; mono long chain dimethylamine such as stearyl dimethylamine, behenyl dimethylamine, octadecyloxypropyl dimethylamine, stearamide ethyl diethylamine, stearamide propyl dimethylamine, behenamide propyl dimethylamine, mono long Hair treated with the hair cosmetic of the present invention, including glutamic acid, hydrochloric acid, citric acid, or lactate of chain diethylamine From the viewpoint of improving the fingering property and unity after drying, behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearoxypropyltrimethylammonium chloride, stearyldimethylamine, stearamidepropyldimethylamine, and behenamidopropyldimethylamine are preferable. .

The content of the surfactant (C) used in the present invention suppresses the stickiness after drying of the hair treated with the hair cosmetic, and improves the fingering property and the feeling of unity. 50 mass% or less is preferable, 40 mass% or less is more preferable, 30 mass% or less is more preferable, and 25 mass% or less is still more preferable. In addition, from the viewpoint of suppressing the stickiness after drying of hair treated with hair cosmetics and improving the fingering property and feeling of unity, 0.01% by mass or more is preferable, 0.05% by mass or more is more preferable, 0.1 mass% or more is more preferable, and 0.5 mass% or more is still more preferable. If these viewpoints are put together, 0.01-50 mass% is preferable in hair cosmetics, and, as for content of surfactant (C), 0.05-40 mass% is more preferable, 0.1-30 mass % Is more preferable, and 0.5 to 20% by mass is still more preferable.
The mass ratio of the surfactant (C) to the C-HPC (A) [surfactant (C) / C-HPC (A)] is the stickiness after drying of the hair treated with the hair cosmetic of the present invention. From the viewpoint of suppressing the feeling and improving the fingering property, 0.1 to 2000 is preferable, and 1 to 1000 is more preferable.

(Application to shampoo)
When using the hair cosmetics of this invention for a shampoo etc., 3-18 mass% is preferable from a viewpoint similar to the above, and, as for content of surfactant (C), 8-15 mass% is more preferable.
The mass ratio of the surfactant (C) to the C-HPC (A) [surfactant (C) / C-HPC (A)] gives a sticky feeling after drying of the hair treated with the hair cosmetic of the present invention. From a viewpoint of suppressing and improving finger-penetration property, 5-1000 are preferable, 10-300 are more preferable, and 15-150 are still more preferable.

(Application to conditioner, hair rinse, treatment)
When the hair cosmetic composition of the present invention is used in a conditioner, hair rinse, treatment or the like, the content of the surfactant (C) is preferably from 0.8 to 5% by mass from the same viewpoint as described above, and from 1.0 to 3 0.0 mass% is more preferable.
The mass ratio of the surfactant (C) to the C-HPC (A) [surfactant (C) / C-HPC (A)] gives a sticky feeling after drying of the hair treated with the hair cosmetic of the present invention. 1-200 are preferable from a viewpoint of suppressing and improving finger-penetrating property, 2-50 are more preferable, and 4-20 are still more preferable.

<Other ingredients>
In the hair cosmetic composition of the present invention, in addition to the C-HPC (A), the oil agent containing the oil agent (B), and the surfactant (C), the hair cosmetic composition may contain other components used as normal cosmetic raw materials. it can. Such optional components include feel improvers, thickeners, surfactants, fragrances, UV absorbers, visible light absorbers, chelating agents, antioxidants, colorants, preservatives, pH adjusters, viscosity adjusters. Agents, pearlescent agents, wetting agents and the like.

[Method for producing hair cosmetics]
The method for producing a hair cosmetic of the present invention is a method for producing a hair cosmetic containing a cationized hydroxypropylcellulose (A), an oil (B), and a surfactant (C). (A) has a main chain derived from anhydroglucose represented by the general formula (1), and the degree of substitution of the cationized ethyleneoxy group is 0.01 to 2.9 mol, and a propyleneoxy group The degree of substitution is 0.1 to 4.0 mol, and the oil agent (B) is an ester compound represented by the general formula (4), a dialkyl carbonate compound represented by the general formula (5), and the above It is one or more compounds selected from dialkyl ether compounds represented by the general formula (6), and the steps (a-1) to (a-3) and the steps (a-4) to (a-5). , The step (b-1 Having ~ a (b-4), or the step (c-1) ~ (c-4).
The production method of the present invention includes the steps (a-1) to (a-3) and the steps described above from the viewpoint of improving the fingering property after drying of the hair treated with the hair cosmetic composition of the present invention and the feeling of unity. It is preferable to have (b-1) to (b-4) or the steps (c-1) to (c-4), and from the viewpoint of suppressing a decrease in the molecular weight of C-HPC, the step (b- It is more preferable to have 1)-(b-4) or the said process (c-1)-(c-4).

  In the following Examples and Comparative Examples, “parts” means “parts by mass” and “%” means “% by mass” unless otherwise specified. Moreover, the measuring method of various physical properties is as follows.

(1) Measurement of moisture content of pulp and powdered cellulose The moisture content of pulp and powdered cellulose was measured using an infrared moisture meter ("FD-610", manufactured by Kett Scientific Laboratory). The point at which the weight change rate for 30 seconds was 0.1% or less at a measurement temperature of 120 ° C. was defined as the end point of measurement.
(2) Calculation of crystallinity of pulp and powdered cellulose From the peak intensity of the diffraction spectrum measured under the following conditions using “Rigaku RINT 2500VC X-RAY diffractometer” manufactured by Rigaku Corporation, the calculation formula (1) is obtained. Based on the calculation.
X-ray source: Cu / Kα-radiation, tube voltage: 40 kV, tube current: 120 mA
Measurement range: 2θ = 5-45 °
Measurement sample: Prepared by compressing pellets with an area of 320 mm2 x thickness of 1 mm X-ray scanning speed: 10 ° / min
When the obtained crystallinity had a negative value, the crystallinity was 0%.
(3) Measurement of average particle size of cellulose in powdered cellulose and cellulose / base mixed pulverized product The average particle size of powdered cellulose is a laser diffraction / scattering type particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.). It measured using. As a measurement sample, 0.1 g of powdered cellulose was added to 5 mL of water, and a sample dispersion treated with ultrasonic waves for 1 minute was used. The volume-based median diameter was measured at a temperature of 25 ° C., and this was defined as the average particle diameter.
The average particle size of cellulose in the cellulose / base mixed pulverized product is adjusted to a concentration so that the transmittance is in the range of 70-95% in addition to ethanol in the cellulose / base mixed pulverized product using the same measuring device. Then, a sample dispersion in which NaOH was dissolved by ultrasonic treatment for 1 minute was used.

(4) Calculation of substitution degree of C-HPC After purifying the C-HPC obtained in the production example with a dialysis membrane (fraction molecular weight 1000), the aqueous solution was lyophilized to obtain purified C-HPC. The chlorine content (%) of the obtained purified C-HPC was measured by elemental analysis, and the number of cationic groups contained in C-HPC and the number of counter ions as chloride ions were approximated. From the following formula (2), the amount of cationized ethyleneoxy group (—CH (Y ¹ ) —CH (Y ² ) O—) contained in the C-HPC unit mass (a (mol / g)) Asked.
a (mol / g) = chlorine content determined from elemental analysis (%) / (35.5 × 100) (2)
The hydroxypropoxy group content (%) was measured according to “Analytical method of hydroxypropyl cellulose” described in the Japanese Pharmacopoeia, except that the object of analysis was not purified hydroxypropyl cellulose but purified C-HPC. From the following formula (3), the hydroxypropoxy group content [formula (OC ₃ H ₆ OH = 75.09)] (b (mol / g)) was determined.
b (mol / g) = hydroxypropoxy group content (%) determined from gas chromatography analysis / (75.09 × 100) (3)
The substitution degree (k) of the cationized ethyleneoxy group and the substitution degree (m) of the propyleneoxy group were calculated from the obtained a and b and the following formulas (4) and (5).
a = k / (162 + k × K + m × 58) (4)
b = m / (162 + k × K + m × 58) (5)
[Wherein, k and K represent the degree of substitution of the cationized ethyleneoxy group and the formula weight, respectively, and m represents the degree of substitution of the propyleneoxy group. ]

(5) Measurement of average degree of polymerization (copper ammonia method)
(5-1) Measurement of viscosity average degree of polymerization of pulp and powdered cellulose (i) Preparation of measuring solution Add 0.5 g of cuprous chloride and 20-30 mL of 25% aqueous ammonia to a measuring flask (100 mL), and completely After dissolution, 1.0 g of cupric hydroxide and 25% aqueous ammonia were added to make the amount up to one dimension before the marked line. This was stirred for 30-40 minutes to completely dissolve. Thereafter, precisely weighed cellulose was added to fill the ammonia water up to the marked line. It sealed so that air might not enter, and it stirred and melt | dissolved with the magnetic stirrer for 12 hours, and prepared the solution for a measurement. The amount of cellulose to be added was changed in the range of 20 to 500 mg to prepare measurement solutions having different concentrations.
(Ii) Measurement of viscosity average degree of polymerization After the above (i) obtained measurement solution (copper ammonia solution) was put into an Ubbelohde viscometer and left standing in a thermostatic bath (20 ± 0.1 ° C.) for 1 hour, The flow rate of the liquid was measured. From the flow time (t (second)) of the copper ammonia solution having various cellulose concentrations (g / dL) and the flow time (t ₀ (second)) of the copper ammonia solution without addition of cellulose, the relative viscosity η _r is calculated by the following equation. Asked.
η _r = t / t ₀
Next, the reduced viscosity (η _sp / c) at each concentration was determined by the following formula.
η _sp / c = (η _r −1) / c
(C: Cellulose concentration (g / dL)
Further, the intrinsic viscosity [η] (dL / g) was obtained by extrapolating the reduced viscosity to c = 0, and the viscosity average degree of polymerization (DP) was obtained by the following formula.
DP = 2000 × [η]

(5-2) Measurement of viscosity average degree of polymerization of C-HPC (iii) Preparation of measurement solution Except for the point of using precisely weighed C-HPC instead of precisely weighed cellulose, A measurement solution was prepared in the same manner as the preparation.
(Iv) Measurement of viscosity average degree of polymerization The measurement was performed in the same manner as the measurement of the viscosity average degree of polymerization in (ii) above, except that a cellulose equivalent concentration (g / dL) was used as the concentration of the measurement solution.
Here, the cellulose equivalent concentration (c _cell ) refers to the mass (g) of the cellulose skeleton part contained in 1 dL of the measurement solution, and is defined by the following formula (6).
c _cell = u × 162 / (162 + k × K + m × 58) (6)
[In the formula, u represents the mass (g) of the precisely weighed C-HPC used at the time of preparing the measurement solution, and k, K, and m represent the same meanings as the above-described formulas (4) and (5), . ]

Production Example 1 [Production of C-HPC (1)]
(1) Chip-forming process Sheet-like wood pulp [Biofloc HV +, manufactured by Tenbeck Co., Ltd., average polymerization degree 1770, crystallinity 74%, moisture content 7.0%] sheet pelletizer ("SGG-220" manufactured by Horai Co., Ltd.) To form a 3-5 mm square chip.
(2) Cationization step (1)
To 100 g of the chip-like pulp obtained in (1) above, 23.4 g of an aqueous glycidyltrimethylammonium chloride solution (manufactured by Sakamoto Pharmaceutical Co., Ltd., water content 20%, purity 90% or more) (hereinafter referred to as “GMAC”) [Amount equivalent to 0.2 mole per mole of AGU] was mixed in a mortar, and then a batch-type vibration mill ("MB-1" manufactured by Chuo Kako Co., Ltd .: total volume 3.5 L, as a rod, φ30 mm, length 218 mm, The rods were put into 13 rods made of SUS304 having a circular cross-sectional shape and a filling rate of 57%. A pulverization treatment (frequency 20 Hz, amplitude 8 mm, temperature 30 to 70 ° C.) was performed for 30 minutes to obtain a powdery mixture of cellulose and GMAC.
To the obtained powdery mixture, 20 g of a 24.7% aqueous sodium hydroxide solution (0.2 mol equivalent per mol of AGU) was mixed in a mortar, and then charged into the batch type vibration mill. A pulverization process was performed for 60 minutes under the same conditions to obtain 151 g of cationized cellulose (i).
(3) Cationization step (2)
After adding 31.3 g of GMAC (equivalent to 0.32 mol per mol of AGU) to 128 g of the cationized cellulose (i) obtained in the above (2) and mixing in a mortar, the resulting mixture was added to the reflux tube. Was added to a 1 L kneader (manufactured by Irie Shokai Co., Ltd., PNV-1 type) and aged for 5 hours while stirring at 50 rpm in a nitrogen atmosphere at 50 ° C. to obtain cationized cellulose (ii).
(4) Hydroxypropylation step A kneader containing 152.6 g (unneutralized / unpurified product) of cationized cellulose (ii) obtained after aging was heated to 70 ° C., and 72.5 g of propylene oxide (AGU 1 An amount equivalent to 2.5 moles per mole, manufactured by Kanto Chemical Co., Ltd., a special grade reagent) was added dropwise with stirring, and the reaction was carried out for 20 hours until propylene oxide was consumed and refluxing stopped.

The reaction completed mixture was taken out from the kneader to obtain 210.6 g of light brown crude C-HPC powder. 10.0 g of this crude C-HPC powder was collected and neutralized with acetic acid. In order to determine the degree of substitution of propyleneoxy groups and cationized ethyleneoxy groups, the neutralized product was purified by a dialysis membrane (fractional molecular weight 1000), and then the aqueous solution was lyophilized to obtain purified C-HPC (1). .
From the elemental analysis of the obtained purified C-HPC (1), the chlorine content was 3.4%. Further, the hydroxypropoxy group content according to the aforementioned “Analytical Method for Hydroxypropyl Cellulose” was 43.3%. The degree of substitution of the cationized ethyleneoxy group and the degree of substitution of the propyleneoxy group were 0.30 and 1.8, respectively. The average degree of polymerization of purified C-HPC (1) was 739. The results are shown in Table 1.

Production Example 2 [Production of C-HPC (2)]
The same procedure as in Production Example 1 was conducted except that the cationization step (1) was changed to the conditions shown in Table 1, the cationization step (2) was not performed, and the hydroxypropylation step was changed to the conditions shown in Table 1. The results of the obtained purified C-HPC (2) are shown in Table 1.
Production Example 3 [Production of C-HPC (3)]
The same procedure as in Production Example 1 was conducted except that the cationization step (1), the cationization step (2), and the hydroxypropylation step were changed to the conditions shown in Table 1. The results of the obtained purified C-HPC (3) are shown in Table 1.
Production Example 4 [Production of C-HPC (4)]
The same procedure as in Production Example 1 was conducted except that the cationization step (1) was changed to the conditions shown in Table 1, the cationization step (2) was not performed, and the hydroxypropylation step was changed to the conditions shown in Table 1. The results of the obtained purified C-HPC (4) are shown in Table 1.
Production Example 5 [Production of C-HPC (5)]
The same procedure as in Production Example 1 was conducted except that the cationization step (1), the cationization step (2), and the hydroxypropylation step were changed to the conditions shown in Table 1. The results of the obtained purified C-HPC (5) are shown in Table 1.

Production Example 6 [Production of C-HPC (6)]
(1) Chip-forming step A sheet-like wood pulp (Biofloc HV10, average polymerization degree 1508, crystallinity degree 74%, moisture content 7.0%, manufactured by Tenbeck Co., Ltd.) is used as cellulose. -220 ") to form chips of 3 to 5 mm square.
(2) Cationization step (1)
GMAC559g (corresponding to 0.52 mol per mol of AGU) and 24 g of ion-exchanged water are added to 989 g of chip-shaped pulp obtained in (1) above (moisture content of 7.0%) and mixed in a plastic bag. After that, a batch-type vibration mill (“FV-10” manufactured by Chuo Kako Co., Ltd., total container capacity: 35 L, as a rod, φ30 mm, length 510 mm, 63 SUS304 rods with a circular cross-section, filling rate 64% ). The mixture was pulverized for 12 minutes (frequency 20 Hz, amplitude 8 mm, temperature 10 to 40 ° C.) to obtain a powdery mixture of cellulose and GMAC.
Further, 136.2 g of granular sodium hydroxide (effective content 100%) (corresponding to 0.60 mol per mol of AGU) was charged into the vibration mill. The pulverization process was again performed for 112 minutes, and the cationized cellulose was obtained.
(3) Hydroxypropylation step 95.0 g of the cationized cellulose obtained in (2) above was charged into a kneader equipped with the reflux tube used in Production Example 1, the kneader was heated to 70 ° C, and propylene oxide 35. 4 g (2.0 mol equivalent per 1 mol of AGU) was added dropwise with stirring, and the reaction was carried out for 7 hours until propylene oxide was consumed and refluxing stopped. The reaction-terminated mixture was taken out of the kneader to obtain 120.6 g of light brown crude C-HPC powder.
(4) Cationization step (2)
After adding 16.2 g of GMAC (equivalent to 3.5 mol per 1 mol of AGU) to 10.6 g of the crude C-HPC powder obtained in (3) above, mixing in a mortar, followed by 50 ° C in a thermostatic bath For 24 hours. The obtained crude C-HPC was dispersed using 100 g of a mixed solvent of water: ethanol: isopropyl alcohol = 5: 45: 50 (weight ratio), neutralized by adding acetic acid, and purified by precipitation. The precipitate was collected by filtration and dried in a dryer at 60 ° C. under reduced pressure overnight to obtain a light brown lump-like crude C-HPC (6).
In order to determine the degree of substitution of propyleneoxy group and cationized ethyleneoxy group, the product was purified by a dialysis membrane (fractionated molecular weight 1000), and then the aqueous solution was lyophilized to obtain purified C-HPC (6).
From the elemental analysis of the obtained purified C-HPC (6), the chlorine content was 9.1%. The hydroxypropoxy group content was 25.1%. The substitution degrees of the cationized ethyleneoxy group and propyleneoxy group were calculated as 1.00 and 1.3, respectively. The average degree of polymerization of purified C-HPC (6) was 464. The results are shown in Table 2.

Production Example 7 [Production of C-HPC (7)]
The same procedure as in Production Example 6 was conducted except that the raw material pulp was changed to the raw material pulp shown in Table 2 and the cationization step (1), hydroxypropylation step, and cationization step (2) were changed to the amounts shown in Table 2. . The results of the obtained purified C-HPC (7) are shown in Table 2.

Production Example 8 [Production of C-HPC (8)]
(1) Manufacturing process of low crystalline powder cellulose Sheet-like wood pulp (Biofloc HV + manufactured by Tenbeck Co., Ltd., average polymerization degree 1770, crystallinity 74%, water content 7.0%) was shredded (manufactured by Meiko Shokai Co., Ltd., “ MSX2000-IVP440F ") to form chips of 3 to 5 mm square. Then, the drying process was performed under reduced pressure at 50 ° C. for 12 hours to obtain a chip-like dried pulp (water content 0.4%).
Next, 100 g of the obtained chip-shaped dry pulp was put into the batch type vibration mill used in Production Example 1. A pulverization process is performed for 35 minutes at a frequency of 20 Hz, a total amplitude of 8 mm, and a temperature of 30 to 70 ° C. Obtained.
(2) Cationization step To 100 g of the powdered cellulose obtained in (1) above, 46.9 g of GMAC (0.4 mol equivalent per 1 mol of AGU) was added and mixed in a mortar. Thereafter, 5.14 g of a 48% sodium hydroxide aqueous solution (equivalent to 0.1 mol per mol of AGU) and 18 g of ion-exchanged water were added and mixed. The kneader used in Production Example 1 was charged with the obtained mixture and stirred at 50 ° C. for 4 hours to obtain 170 g of cationized cellulose.
(3) Hydroxypropylation step 170 g of the cationized cellulose obtained in (2) above was heated to 70 ° C., and while stirring, 4.7 g of 48% aqueous sodium hydroxide solution (corresponding to 0.1 mol per mol of AGU) 16.4 g of ion exchange water. Furthermore, 101 g of propylene oxide (equivalent to 3.0 mol per mol of AGU) was added dropwise, and the reaction was performed for 24 hours until propylene oxide was consumed and the refluxing stopped. After the reaction, the cellulose kept a fluid powder state. 10.0 g of this reaction finished product was collected and neutralized with acetic acid to obtain a light brown solid. The neutralized product was purified by a dialysis membrane (fraction molecular weight 1000), and then the aqueous solution was lyophilized to obtain purified C-HPC (8).
From the elemental analysis of the obtained purified C-HPC (8), the chlorine content was 2.1%. The hydroxypropoxy group content was 49.2%. The degree of substitution of the cationized ethyleneoxy group and propyleneoxy group was calculated as 0.18 and 2.0, respectively. The average degree of polymerization of purified C-HPC (8) was 832. The results are shown in Table 3.

Production Example 9 [Production of C-HPC (9)]
The raw material pulp was changed to the raw material pulp shown in Table 3, and the production process of the low crystalline powdered cellulose, the cationization process, and the hydroxypropylation process were performed in the same manner as in Production Example 8 except that the conditions shown in Table 3 were changed. . The results of the purified C-HPC (9) obtained are shown in Table 3.
Production Example 10 [Production of C-HPC (10)]
It carried out similarly to manufacture example 8 except having changed the hydroxypropylation process into the conditions shown in Table 3. The results of the purified C-HPC (10) obtained are shown in Table 3.

Production Example 11 [Production of Cationized Cellulose (1)]
A cationized cellulose (1) was obtained in the same manner as in Production Example 5 except that the addition reaction of propylene oxide was not performed.

Production Example 12 [Production of C-HPC (11)]
(1) Chip forming step Sheet wood pulp [Biofloc HV +, manufactured by Tenbeck Co., Ltd., average polymerization degree 1481, crystallinity 74%, moisture content 4.6%] sheet pelletizer ("SGG-220" manufactured by Horai Co., Ltd.) To form a 3-5 mm square chip.
(2) Alkaline cellulose conversion step 100 g of chip-like pulp obtained in the above step (1) and 23.6 g of 0.7 mm granular NaOH (1.0 mol equivalent per mol of AGU) were mixed with a batch-type vibration mill (Central Chemical Machinery). “MB-1” manufactured by Co., Ltd .: The total volume of the container is 3.5 L, the rod is φ30 mm, the length is 218 mm, the cross-sectional shape is 13 SUS304 rods with a circular shape, and the filling rate is 57%. (Frequency 20 Hz, amplitude 8 mm, temperature 30 to 70 ° C.). The obtained cellulose / NaOH mixed pulverized product (average particle diameter of cellulose: 65 μm) was transferred to a mortar, and 50 g of water was added by spraying. The water content of the pulverized cellulose / NaOH mixture was 57% with respect to cellulose. The mixture was mixed with a pestle at 20 ° C. for 5 minutes to obtain alkali cellulose (average polymerization degree: 1175).
(3) Hydroxypropylation reaction step The alkali cellulose obtained in the above step (2) was charged into a kneader (Irie Shokai Co., Ltd., PNV-1 type, volume 1.0 L) equipped with a reflux tube and a dropping funnel and oxidized. 85.7 g of propylene (equivalent to 2.5 moles per mole of AGU) was added and reacted at 50 ° C. for 6 hours while stirring. In the reaction, propylene oxide was added dropwise over 5 hours, followed by aging for 1 hour.
(4) Cationization reaction step 5.8 g of the reaction mixture obtained in the above step (3) was put in a mortar and 2.10 g of 65% 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution (manufactured by Yokkaichi Synthesis Co., Ltd.) 0.50 mole equivalent per mole of AGU) was added, mixed for 5 minutes, transferred to a 50 ml glass bottle, and reacted at 50 ° C. for 7 hours to produce crude C-HPC.
5.0 g of this crude C-HPC powder was collected and neutralized with lactic acid. In order to determine the degree of substitution of propyleneoxy groups and cationized ethyleneoxy groups, the neutralized product was purified by a dialysis membrane (fractional molecular weight 1000), and then the aqueous solution was lyophilized to obtain purified C-HPC (11). .
From elemental analysis of the obtained purified C-HPC (11), the chlorine element content was 3.3% and the hydroxypropoxy group content was 38.8%. Moreover, the substitution degree of the cationized ethyleneoxy group and the substitution degree of the propyleneoxy group were calculated as 0.27 and 1.5, respectively. The average degree of polymerization was 643. The results are shown in Table 4.

Production Example 13 [Production of C-HPC (12)]
(1) Low crystalline powder cellulose manufacturing process It carried out similarly to manufacture example 12 (1), and obtained the chip-like pulp of 3-5 mm square. 1 kg of the obtained chip-like pulp was put into a dryer (trade name: VO-402, manufactured by Advantech Toyo Co., Ltd.), dried at 105 ° C. for 2 hours, and dried chip-like pulp (water content 0.8%) )
920 g of the obtained dried chip-like pulp was batch-type vibration mill (Chuo Kako Co., Ltd., “FV-10”: total container volume 35 L, rod 30 mm, length 510 mm, circular cross section SUS304 rod 63. The filling rate was 65%. A pulverization treatment (frequency 20 Hz, amplitude 8 mm, temperature 10 to 40 ° C.) was performed for 10 minutes to obtain powdered cellulose (crystallinity 14%, average polymerization 1198, water content 1.0%).
(2) Alkaline cellulose conversion step 369 g of the powdered cellulose obtained in the above step (1) is put into a mixer (manufactured by Matsubo Co., Ltd., “Ledige mixer”, capacity 5 L), and stirred at a main wing 250 rpm and a chopper blade 2500 rpm. However, 212 g of a 42.5% aqueous sodium hydroxide solution (equivalent to 1.0 mol per mol of NaOH: AGU, 33% with respect to water: cellulose) was added by spraying over 1.5 minutes. After spraying, the internal temperature was raised to 50 ° C. and aged for 3 hours to obtain alkali cellulose.
(3) Hydroxypropylation reaction step 607 g of alkali cellulose obtained in the above step (2) was heated to 50 ° C. with stirring at 50 rpm main blade and 400 rpm chopper blade in the above-mentioned Redige mixer, and then propylene oxide 187 g (equivalent to 1.6 mole per mole of AGU) was added dropwise over 3.5 hours. After completion of dropping, the mixture was aged at 50 ° C. for 2 hours.
(4) Cationization reaction step 11.4 g of the reaction mixture obtained in the above step (3) was placed in a mortar, and 4.31 g of 65% 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution (0.5 mol per mol of AGU). Equivalent amount) and 0.84 g of ion-exchanged water were added, mixed for 5 minutes, transferred to a 50 ml glass bottle, and reacted at 50 ° C. for 5 hours to obtain crude C-HPC. This crude C-HPC powder was neutralized, purified and lyophilized in the same manner as in Production Example 12 (4) to obtain purified C-HPC (12).
From the elemental analysis of the obtained purified C-HPC (12), the chlorine element content was 4.3% and the hydroxypropoxy group content was 24.3%. Moreover, the substitution degree of the cationized ethyleneoxy group and the substitution degree of the propyleneoxy group were calculated as 0.25 and 0.8, respectively. The average degree of polymerization was 659. The results are shown in Table 5.

Production Example 14 [Production of C-HPC (13)]
(1) Low crystalline powder cellulose manufacturing process It carried out similarly to manufacture example 13 (1), and obtained the powder cellulose (The crystallinity degree 14%, the average degree of polymerization 1198, water content 1.0%).
(2) Alkaline cellulose conversion step 530.5 g of powdered cellulose obtained in the above step (1) and 307 g of 42.5% aqueous sodium hydroxide solution (1.0 mol equivalent per 1 mol of NaOH: AGU, water: relative to cellulose) 34%) was used in the same manner as in Production Example 13 (2) to obtain alkali cellulose.
(3) Hydroxypropylation reaction step 825 g of the alkali cellulose obtained in the above step (2) was heated to 50 ° C. while stirring with the main blade 50 rpm and the chopper blade 400 rpm in the Redige mixer, and then propylene oxide 467 g (equivalent to 2.6 moles per mole of AGU) was added dropwise over 6 hours. After completion of dropping, the mixture was aged at 50 ° C. for 2 hours.
(4) Cationization reaction step 12.3 g of the reaction mixture obtained in the above step (3) was placed in a mortar and 65% 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution 4.31 (0.5 mol per mol of AGU). Equivalent amount) and 0.84 g of ion exchange water were added, mixed for 5 minutes, transferred to a 50 ml glass bottle, and reacted at 50 ° C. for 5 hours to obtain crude C-HPC. This crude C-HPC powder was neutralized, purified and lyophilized in the same manner as in Production Example 13 (4) to obtain purified C-HPC (13).
From elemental analysis of the obtained C-HPC (13), the chlorine element content was 2.5% and the hydroxypropoxy group content was 38.5%. Moreover, the substitution degree of the cationized ethyleneoxy group and the substitution degree of the propyleneoxy group were calculated to be 0.19 and 1.4, respectively. The average degree of polymerization was 1186. The results are shown in Table 5.

  Average polymerization degree of C-HPC obtained in Production Examples 1 to 10 and 12 to 14, substitution degree of cationized ethyleneoxy group, substitution degree of propyleneoxy group, average polymerization degree of cationized cellulose (1) and The degree of substitution of the cationized ethyleneoxy group is shown in Table 6.

Examples 1 to 23, 50 to 52 (Manufacture and evaluation of conditioners)
Using C-HPC (1) to (10) and (12) to (14) as the component (A), conditioners having compositions shown in Tables 5 to 8 were prepared by a conventional method.
Specifically, component (A) was dissolved or uniformly dispersed in water to prepare a 2% aqueous polymer solution. Appropriate amounts of water and surfactant (C) were placed in a beaker, and the polymer aqueous solution was added to the aqueous solution mixed by heating to 80 ° C. and mixed uniformly. The melted oil (B), cetyl alcohol and stearyl alcohol were 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).

Examples 24-26
Component (A) was dissolved or uniformly dispersed in water to prepare a 2% aqueous polymer solution. To this polymer aqueous solution, an appropriate amount of water, a surfactant (C) and an equimolar amount of a pH adjusting agent (50% aqueous citric acid solution) were added and heated to 80 ° C. The melted oil (B), cetyl alcohol, stearyl alcohol and surfactant (C) were 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 1 g of the conditioners of Examples 1 to 26 and 50 to 52 were applied and applied. 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, stickiness, and cohesion of hair according to the following evaluation criteria and evaluation methods. The results are shown in Tables 7-10.

(Plain shampoo composition)
(Ingredient) (%)
Polyoxyethylene lauryl ether sulfate Na 11.3
(42.0% as Emar E-27C (Kao Corporation, effective 27% by weight))
Palm oil fatty acid N-methylethanolamide 3.0
(Aminone C-11S (Kao Corporation))
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 property 5: Very good fingering 4: Good fingering 3: Normal fingering 2: Bad fingering 1: Very bad fingering • Stickiness 5: Not sticky 4: Not very sticky 3: Normal 2: Slightly sticky 1: Sticky / Smoothness 5: Very good hair cohesion 4: Good hair cohesion 3: Normal 2: Poor hair cohesion 1: No hair cohesion The score was obtained by averaging the evaluation results of the five panelists, with the fingering, stickiness, and cohesiveness as the reference score of 3.

Comparative Examples 1-8
The component (A) of Example 1 is not added (Comparative Example 1), or various compositions shown in Table 7 are used instead of the component (A) (Comparative Examples 2 to 8), and the composition shown in Table 7 is obtained. A conditioner was prepared as in Example 1. In addition, the pH of the conditioners of Comparative Examples 1 to 8 was adjusted to 5 with a pH adjuster (50% citric acid aqueous solution). The conditioners of Comparative Examples 1-8 were evaluated in the same manner as in Examples 1-26. The results are summarized in Table 7.

  From Tables 7 to 10, the conditioners of Examples 1 to 26 and 50 to 52 do not have an oily stickiness after drying, and can impart good fingering and unity as compared with the conditioners of Comparative Examples 1 to 8. I understand that.

Examples 27 to 49 (production and evaluation of shampoo)
Using C-HPC (2) as the component (A), shampoos having the compositions shown in Tables 11 to 13 were prepared by a conventional method.
Specifically, the surfactant (C) and an appropriate amount of water were taken in a beaker, heated to 60 ° C. and dissolved. After cooling to 50 ° C., a polymer solution prepared in the same manner as in Example 1 was added and mixed uniformly. Oil agent (B) was added there, and it 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 7 with a pH adjuster (50% citric acid aqueous solution and 48% sodium hydroxide aqueous solution) as necessary.
The hair bundle washed with the plain shampoo used in Example 1 was sufficiently moistened with warm water of 35 to 40 ° C., then washed with the shampoo of Examples 27 to 49, rinsed with warm water, dehydrated with a towel, combed I arranged the hair bundle. Then, it dried with the warm air of the dryer, arranged the hair | bristle bundle with the comb for the finish, and obtained the trace for evaluation. In the evaluation, the fingering property, stickiness, and feeling of unity of Comparative Example 12 were set as a reference score of 3, and the evaluation results of five panelists were averaged to obtain a score. The results are shown in Tables 11-13.

Comparative Examples 9-13
A shampoo having the composition shown in Table 9 was prepared in the same manner as in Example 27 using various polymers shown in Table 9 instead of the component (A) in Example 27. In addition, the pH of the shampoos of Comparative Examples 9 to 13 was adjusted to 7 with a pH adjusting agent (50% citric acid aqueous solution and 48% sodium hydroxide aqueous solution) as necessary. The shampoos of Comparative Examples 9 to 13 were evaluated in the same manner as in Example 27. The results are shown in Table 11.

Comparative Example 14
A shampoo of Comparative Example 14 was prepared in the same manner as in Example 27 except that the oil agent (B) was not added. The prepared shampoo of Comparative Example 14 was evaluated in the same manner as the shampoo of Example 27. The results are shown in Table 12.

  As is clear from Tables 11 to 13, the shampoos of Examples 27 to 49 do not have an oily stickiness after drying, and can provide good fingering and unity as compared with the shampoos of Comparative Examples 9 to 14. It was.

  The hair cosmetic composition of the present invention is suitably used in the fields of hair shampoo, hair rinse, treatment, conditioner, non-washing type hair conditioner, hair cream, blow lotion, hair pack, hair color, conditioning gel, conditioning foam, etc. Can do.

Claims (8)

A hair cosmetic comprising cationized hydroxypropylcellulose (A), an oil agent (B), and a surfactant (C),
The cationized hydroxypropylcellulose (A) has a main chain derived from anhydroglucose represented by the following general formula (1), and the substitution degree of the cationized ethyleneoxy group is 0.01 to 2.9 mol. Yes, the degree of substitution of propyleneoxy group is 0.1-4.0 mol,
The oil agent (B) is selected from an ester compound represented by the following general formula (4), a dialkyl carbonate compound represented by the following general formula (5), and a dialkyl ether compound represented by the following general formula (6). Hair cosmetics that are one or more compounds.

(In the formula, R ¹ , R ² and R ³ each independently represent a substituent having a cationized ethyleneoxy group and a propyleneoxy group represented by the following general formula (2), and n is an average of anhydroglucose. The degree of polymerization is 50 to 5000.)

(In the formula, ^one of Y ¹ and Y ² represents a hydrogen atom, the other represents a cationic group represented by the following general formula (3), PO represents a propyleneoxy group, and p represents a general formula (2 ) Represents the number of cationized ethyleneoxy groups (—CH (Y ¹ ) —CH (Y ² ) —O—) contained in the group, q represents the number of propyleneoxy groups (—PO—), and each represents 0 or When both p and q are not 0, the addition order of the cationized ethyleneoxy group and the propyleneoxy group is not limited, and when p and / or q is 2 or more, a block bond or Any of random bonds may be used.)

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represents a linear or branched alkyl group having 1 to 3 carbon atoms, and X ⁻ represents an anionic group.)
_{^{R 7 O- (AO) m -COR}} 8 (4)
(In the formula, R ⁷ represents a carbon hydrogen group having 6 to 20 carbon atoms containing at least one substituted or unsubstituted aromatic ring, and R ⁸ is a linear or branched alkyl group having 1 to 25 carbon atoms. AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and m is a number from 1 to 50. When m is 2 or more, the m AO groups are the same or different. May be good.)
_{^{R 9 O (CH 2 CH 2}} O) r CO (OCH 2 CH 2) s -OR 10 (5)
(In the formula, R ⁹ and R ¹⁰ each represent a linear or branched alkyl group and / or alkenyl group having 6 to 22 carbon atoms, and r and s are each 0 or a number of 1 to 50.)
R ¹¹ —O—R ¹² (6)
(In the formula, R ¹¹ and R ¹² each represent a linear or branched alkyl group and / or alkenyl group having 6 to 22 carbon atoms.)   The hair cosmetic according to claim 1, wherein the content of the cationized hydroxypropylcellulose (A) is 0.001 to 10% by mass.   The hair cosmetic composition according to claim 1 or 2, wherein the content of the oil agent (B) is 0.01 to 20% by mass.   Hair cosmetics in any one of Claims 1-3 whose content of surfactant (C) is 0.01-50 mass%. The hair cosmetic composition according to claim 1, wherein the cationized hydroxypropylcellulose (A) is obtained by the following steps (a-1) to (a-3).
Step (a-1): A step of adding a cationizing agent to the cellulose-containing raw material and carrying out a pulverizer treatment Step (a-2): Adding a base to the pulverizer treated product obtained in step (a-1) The step of obtaining a cationized cellulose by reacting the cellulose-containing raw material with a cationizing agent while carrying out a pulverizer treatment Step (a-3): The cationized cellulose and propylene oxide obtained in Step (a-2) Process for obtaining cationized hydroxypropylcellulose (A) by reaction The hair cosmetic according to claim 1, wherein the cationized hydroxypropylcellulose (A) is obtained by the following steps (b-1) to (b-4).
Step (b-1): A step of obtaining a cellulose-containing raw material containing cellulose having a crystallinity of 10 to 50% by pulverizing the cellulose-containing raw material Step (b-2): Step (b-1) 20 to 100 masses with respect to cellulose in the cellulose-containing raw material obtained in step 0.6 to 1.5 times mole of base per mole of anhydroglucose unit constituting the cellulose, and cellulose in the cellulose-containing raw material. Step for obtaining alkali cellulose by adding% water Step (b-3): Step for obtaining hydroxypropyl cellulose by reacting alkali cellulose obtained in step (b-2) with propylene oxide Step (b- 4): Process for obtaining cationized hydroxypropylcellulose (A) by reacting the hydroxypropylcellulose obtained in step (b-3) with a cationizing agent. The hair cosmetic according to claim 1, wherein the cationized hydroxypropylcellulose (A) is obtained by the following steps (c-1) to (c-4).
Step (c-1): Cellulose-containing raw material and a mixture of 0.6 to 1.5-fold moles of base per mole of anhydroglucose unit constituting cellulose in the cellulose-containing raw material, cellulose in the cellulose-containing raw material Step (c-2): Step (c-1) for obtaining a cellulose / base mixed pulverized product having an average particle size of cellulose of 10 to 150 μm by treating with a pulverizer under a condition that the water content is 10% by weight or less Water was added to the cellulose / base mixed pulverized product obtained in Step 3, and the water content in the cellulose / base mixed pulverized product was adjusted to 30 to 100 with respect to the cellulose in the cellulose-containing raw material used in step (c-1). Step of obtaining alkali cellulose by adjusting to mass% Step (c-3): Reacting the alkali cellulose obtained in step (c-2) with propylene oxide to produce hydroxy Pills cellulose obtained. Step (c-4): Step (c-3) obtained by reacting the hydroxypropyl cellulose and cationic agent to obtain a cationized hydroxypropyl cellulose (A)   It is a manufacturing method of the hair cosmetics containing a cationized hydroxypropyl cellulose (A), an oil agent (B), and surfactant (C), Comprising: A cationized hydroxypropyl cellulose (A) is described in Claim 1. It has a main chain derived from anhydroglucose represented by the general formula (1), the degree of substitution of the cationized ethyleneoxy group is 0.01 to 2.9 mol, and the degree of substitution of the propyleneoxy group is 0.00. 1 to 4.0 mol, and the oil agent (B) is an ester compound represented by the general formula (4) according to claim 1, a dialkyl carbonate compound represented by the general formula (5), and a general formula ( 6) one or more compounds selected from the dialkyl ether compounds represented by formula (6), wherein the steps (a-1) to (a-3) according to claim 5 and the step (b-1) according to claim 6 are performed. ) To (b-4) or claim Step (c-1) ~ according to 7 with a (c-4), the manufacturing method of hair cosmetics.