JP2015227412A - Method for manufacturing cationized glycerol cellulose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing cationized glycerol cellulose capable of adding excellent sliding property, maintenance feeling thereof and coat feeling during rinsing hair when blended to a hair cosmetic such as a hair cleaner and a hair cosmetic composition.SOLUTION: There are provided [1] a method for manufacturing cationized glycerol cellulose obtained by reacting raw material cellulose selected from cellulose and a cellulose derivative, at least glycidol and a cationization agent, having a process of reacting raw material cellulose and glycidol in presence of a basic compound of over 0.9 mol equivalent and 1.6 mol equivalent or less per 1 mole of an anhydroglucose unit in the raw material cellulose in a solvent of 10 mass% to 200 mass% based on a cellulose part of the raw material cellulose (Process 1), a process of mixing a reaction mixture 1 obtained in the Process 1 with acid to adjust the amount of the basic compound at 0.1 mol equivalent to 0.9 mol equivalent per 1 mole of the anhydroglucose unit in the raw material cellulose and further reacting raw material cellulose and glycidol (Process 2), and a process of adding the cationization agent after the Process 2 and reacting to obtain cationized glycerol cellulose (Process 3), and [2] a hair cosmetic composition containing cationized glycerol cellulose obtained by the manufacturing method [1], a surfactant and water.

Description

  The present invention relates to a method for producing cationized glycerolated cellulose.

  It is known that hair derivatives are blended with a cellulose derivative in particular to impart a conditioning effect. Cellulose ether, which is one type of cellulose derivative, can be produced by performing an etherification reaction of raw material cellulose using an epoxy compound and an alkali catalyst.

Patent Document 1 includes a main chain derived from anhydroglucose for blending with hair cosmetics and the like to impart a smoothness, moist feeling, softness and moisturizing feeling, and the anhydroglucose Cationized glycerolated cellulose having a specific structure in which the degree of substitution of cationized alkyleneoxy groups per unit is 0.01 to 0.18 and the degree of substitution of glycerol groups is 0.5 to 5.0, and a method for producing the same Is disclosed.
Patent Document 2 includes hydroxyethyl cellulose (HEC) having hydroxyethyl groups uniformly distributed on a cellulose main chain for the purpose of improving rheological properties when used as a rheology modifier. The proportion of unsubstituted trimer is less than about 0.21, the solubility in water is greater than about 90%, and the molar substitution degree of the hydroxyethyl is greater than about 0.7 and less than about 1.3. Certain compositions are disclosed.
Patent Document 3 discloses a method for etherifying alkali cellulose obtained by treating cellulose with an alkaline aqueous solution with propylene oxide for the purpose of producing hydroxypropyl cellulose having excellent solubility in alcohols and water. In addition, in the presence of 100 to 700 parts by weight of a hydrophilic organic solvent with respect to 100 parts by weight of cellulose, 20 to 80% of the total addition amount of propylene oxide was added to cause an etherification reaction. A method for producing hydroxypropyl cellulose is disclosed, characterized in that 20 to 90% of the alkali amount is neutralized, and subsequently 80 to 20% of the total amount of propylene oxide is added to cause an etherification reaction.

International Publication No. 2013/137474 Special table 2008-536959 gazette JP 2000-186101 A

In recent years, there has been a demand for hair cosmetics that have very high slipperiness during hair rinsing, a long-lasting feeling, a coat feeling, and the like against hair that is highly damaged by coloring or the like. And also in the cellulose derivative which can provide the conditioning effect to hair cosmetics, it is desired to obtain efficiently what can express such high slipperiness, its sustaining feeling, and a coat feeling.
The present invention is a method capable of efficiently producing cationized glycerolated cellulose capable of imparting excellent slipperiness during hair rinsing and its long-lasting feeling as well as a coat feeling when blended into a hair cosmetic such as a hair cleanser, Another object of the present invention is to provide a hair cosmetic composition containing the cationized glycerolated cellulose obtained by the method.

The present inventor can impart excellent slipperiness, a long-lasting feeling, and a feeling of coat when rinsing hair by blending into a hair cosmetic such as a hair washing agent by producing cationized glycerolated cellulose by a specific method. It has been found that a cationized glycerolated cellulose can be obtained, and that the above problems can be solved by a hair cosmetic composition containing the cationized glycerolated cellulose.
That is, the present invention provides the following [1] and [2].
[1] A method for producing a cationized glycerolated cellulose obtained by reacting a raw material cellulose selected from cellulose and a cellulose derivative with at least glycidol and a cationizing agent, comprising the following steps 1 to 3 A method for producing glycerolated cellulose.
Step 1: The raw material cellulose and glycidol are added to the cellulose portion of the raw material cellulose in the presence of a base compound of more than 0.9 molar equivalent and 1.6 molar equivalents or less per mole of anhydroglucose unit in the raw material cellulose. Step of obtaining a reaction mixture 1 containing glycerolated cellulose by reacting in a solvent of 10% by mass or more and 200% by mass or less Step 2: Mixing the reaction mixture 1 obtained in Step 1 with an acid, The step of adjusting the amount to 0.1 to 0.9 molar equivalent per mole of anhydroglucose unit in the raw material cellulose, and further reacting the raw material cellulose and glycidol Step 3: After Step 2, a cationizing agent is added Step of adding and reacting to obtain cationized glycerolated cellulose [2] Cations obtained by the production method according to [1] above Glycerol cellulose, surfactant, and a hair cosmetic composition containing water.

  According to the present invention, when blended with a hair cosmetic such as a hair cleansing agent, cationized glycerolated cellulose capable of imparting excellent slipperiness during hair rinsing, its long-lasting feeling, and a feeling of coating can be efficiently produced. be able to. Therefore, the composition containing the cationized glycerolated cellulose can be suitably used as a hair cosmetic.

[Method for producing cationized glycerolated cellulose]
The production method of the cationized glycerolated cellulose of the present invention (hereinafter also referred to as “the production method of the present invention”) includes a raw material cellulose selected from cellulose and a cellulose derivative (hereinafter also simply referred to as “raw material cellulose”), and at least glycidol. And a method for producing cationized glycerolated cellulose obtained by reacting with a cationizing agent, comprising the following steps 1 to 3.
Step 1: The raw material cellulose and glycidol are added to the cellulose portion of the raw material cellulose in the presence of a base compound of more than 0.9 molar equivalent and 1.6 molar equivalents or less per mole of anhydroglucose unit in the raw material cellulose. Step of obtaining a reaction mixture 1 containing glycerolated cellulose by reacting in a solvent of 10% by mass or more and 200% by mass or less Step 2: Mixing the reaction mixture 1 obtained in Step 1 with an acid, The step of adjusting the amount to 0.1 to 0.9 molar equivalent per mole of anhydroglucose unit in the raw material cellulose, and further reacting the raw material cellulose and glycidol Step 3: After Step 2, a cationizing agent is added Step of adding and reacting to obtain cationized glycerolated cellulose In the present invention, “cationized glycerolated cellulose” Scan "refers to a cellulose having at least a cationic group and glycerol group. As will be described later, the cationized glycerolated cellulose may be hydrophobically modified.

Cation excellent in slipperiness and persistence during hair rinsing and coating feeling (hereinafter also referred to as “rinsing feeling”) when blended into a hair cosmetic such as a hair cleanser by the production method of the present invention. The reason for obtaining glycerolated cellulose (hereinafter also referred to as “CGC”) is not clear, but is considered as follows.
In the production method of the present invention, first, raw material cellulose and glycidol are reacted in a solid phase in the presence of a specific amount of a base compound and a small amount of a solvent (step 1). During the reaction, an acid is mixed to reduce the effective amount of the base compound (step 2), and further, a cationizing agent is reacted to obtain CGC (step 3).
In the above production method, since a relatively large amount of the basic compound is initially present in Step 1, glycerolation of the raw material cellulose is promoted, and the surface of the raw material cellulose can be glycerolated in a short time. Next, the acid is mixed in Step 2, and a part of the base compound in the reaction mixture obtained in Step 1 is neutralized, whereby the base compound on the cellulose surface is reduced and alcoholated by the base compound. A part of becomes a hydroxyl group. Since glycidol has a hydroxyl group and is hydrophilic, it easily penetrates into the cellulose from the hydroxylated portion. For this reason, it is thought that glycerolation advances uniformly by performing step 2. Furthermore, when the cationization reaction in Step 3 is performed in this state, it is considered that the cationizing agent permeates into the cellulose from the glycerolated site, and uniformly cationized CGC is obtained.
Since the CGC thus obtained has a uniform distribution of cationic groups without unevenness, when it is added to a hair cosmetic such as a hair cleanser, it will remain on the surface of an anionic hair even after washing the hair. It is thought that it remains in a molecular unit, and it is thought that it can provide a slipperiness, a persistence feeling, and a coat feeling when rinsing hair.

The production method of the present invention preferably further includes a step of adding a hydrophobic group-introducing agent and reacting as step 4 from the viewpoint of obtaining CGC excellent in rinsing feeling when blended in a hair cosmetic. Step 4 may be carried out at any stage of the production method of the present invention, but it is preferable to have Step 4 before Step 1 or between Step 2 and Step 3, and between Step 2 and Step 3. More preferably, step 4 is included.
As the hydrophobic group introducing agent, from the viewpoint of obtaining the above effect, an introducing agent having one or more hydrophobic sites selected from a hydroxyalkyl moiety having 3 or more carbon atoms and an oxyalkylene moiety having 3 or more carbon atoms is preferable. A group-introducing agent containing a hydrocarbon group having 3 to 18 carbon atoms, which will be described later, is more preferable.

<Raw material cellulose>
The raw material cellulose used in the present invention is selected from cellulose and cellulose derivatives, and cellulose is preferred. First, cellulose used as raw material cellulose will be described.

〔cellulose〕
Although there is no restriction | limiting in particular in the kind of the said cellulose used as raw material cellulose, From a viewpoint of cellulose purity, a polymerization degree, and an availability, various wood chips; Wood pulp manufactured from wood, Fiber around cotton seed Pulp such as cotton linter pulp obtained from is preferred.

The average degree of polymerization of the cellulose is preferably 100 or more, more preferably 200 or more, still more preferably 500 or more, and still more preferably 1,000, from the viewpoint of obtaining CGC excellent in rinsing feeling when blended in a hair cosmetic. From the same viewpoint, it is preferably 12,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, and still more preferably 2,500 or less. In addition, in this invention, an average degree of polymerization means the viscosity average degree of polymerization measured by the copper-ammonia method etc. which are described in an Example.
The shape of cellulose is not particularly limited as long as it does not hinder introduction into the production apparatus, but from the viewpoint of operation, it is preferably in the form of a sheet, pellet, chip, or powder, and chip or powder. Is more preferable, and a powder form is still more preferable.

Powdered cellulose can be obtained by pulverizing cellulose such as the above pulps. There is no particular limitation on the pulverizer used for pulverizing cellulose, and any device that can pulverize cellulose may be used.
Specific examples of the pulverizer include a high pressure compression roll mill, a roll mill such as a roll rotating mill, a vertical roller mill such as a ring roller mill, a roller race mill or a ball race mill, a rolling ball mill, a vibration ball mill, a vibration rod mill, and a vibration tube. Container driven medium mills such as mills, planetary ball mills or centrifugal fluidization mills, tower pulverizers, stirring tank mills, medium stirring mills such as flow tank mills or annular mills, compaction such as high-speed centrifugal roller mills and angling mills Examples include a shear mill, a mortar, a stone mill, a mass collider, a fret mill, an edge runner mill, a knife mill, a pin mill, and a cutter mill.
Among these, from the viewpoint of cellulose pulverization efficiency and productivity, a container-driven medium mill or a medium stirring mill is preferable, a container-driven medium mill is more preferable, such as a vibration ball mill, a vibration rod mill, or a vibration tube mill. A vibration mill is more preferable, and a vibration rod mill is still more preferable. The pulverization method may be either batch type or continuous type.

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

The water content during cellulose pulverization is preferably small, and the lower limit of the water content during pulverization is 0% by mass with respect to cellulose, but it is difficult to reduce the water content to 0% by mass. Therefore, the water content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 1% by mass or more with respect to cellulose. In addition, the water content during pulverization is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less with respect to cellulose.
Further, from the viewpoint of improving the reaction activity of cellulose, the pulverization of cellulose can be performed in the presence of a base compound. Base compounds 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 amines such as trimethylamine and triethylamine. Etc. 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 basic compounds can be used alone or in combination of two or more.
When a basic compound is used at the time of pulverization, the amount of the basic compound is from 0 to 1 mol of anhydroglucose unit (hereinafter also referred to as “AGU”) in cellulose from the viewpoint of improving the reaction activity of cellulose. 6 molar equivalents or more are preferable, 0.7 molar equivalents or more are more preferable, and 0.8 molar equivalents or more are more preferable. From the same viewpoint, the amount of the base compound during pulverization is preferably 1.5 molar equivalents or less, more preferably 1.3 molar equivalents or less, and even more preferably 1.2 molar equivalents or less.
There are no particular limitations on the method of adding the base compound, and batch addition or divided addition may be used.
Although there is no restriction | limiting in particular in the form at the time of adding a base compound, From a viewpoint of a grinding | pulverization efficiency, it is preferable that it is a solid. When the base compound is added in a solid state, the base compound is preferably in the form of pellets, granules or powders from the viewpoints of handleability during production and the viewpoint of uniformly dispersing the base compound in cellulose. More preferably, it is in the form of particles or particles.

Although there is no limitation in particular in the temperature at the time of cellulose grinding | pulverization, from a viewpoint of the decomposition | disassembly suppression of a cellulose, and a viewpoint of operation cost, -100 degreeC or more is preferable, 0 degreeC or more is more preferable, 30 degreeC or more is more preferable, 200 degrees C or less Is preferable, 100 degrees C or less is more preferable, and 70 degrees C or less is still more preferable.
What is necessary is just to adjust suitably the time of a grinding | pulverization so that a cellulose may be pulverized. The pulverization time varies depending on the pulverizer used, the amount of energy used, etc., but is usually 1 minute or more and 12 hours or less, preferably 3 minutes or more from the viewpoint of sufficient pulverization, more preferably 4 minutes or more, 5 minutes or more is more preferable, and from the viewpoint of productivity, 3 hours or less is preferable, 1 hour or less is more preferable, and 20 minutes or less is still more preferable.

[Cellulose derivative]
The cellulose derivative used as the raw material cellulose is preferably a hydrophobically modified cellulose in which a hydrophobic group is introduced into the cellulose from the viewpoint of obtaining CGC excellent in rinsing feeling when blended in a hair cosmetic. From the viewpoint of obtaining the above effect, the hydrophobically modified cellulose is preferably a cellulose having one or more hydrophobic sites selected from a hydroxyalkyl moiety having 3 or more carbon atoms and an oxyalkylene moiety having 3 or more carbon atoms. From the above viewpoint, the number of carbon atoms of the hydrophobic portion is preferably 4 or more, preferably 18 or less, more preferably 16 or less, still more preferably 12 or less, still more preferably 8 or less, and even more preferably 7 or less. More preferably, it is 6 or less.
From the viewpoint of obtaining CGC excellent in rinsing feeling when blended in hair cosmetics, the hydrophobically modified cellulose used in the present invention is represented by the following general formula (1) and represented by the following general formulas (2) to (4). The substitution degree of the group containing a hydrocarbon group having 3 to 18 carbon atoms (hereinafter also referred to as “hydrocarbon group-containing group”) is more preferably 0.0001 or more and 0.2 or less cellulose. . The preferred carbon number of the hydrocarbon group-containing group is the same as the preferred carbon number of the hydrophobic moiety.
The hydrophobically modified cellulose is obtained by performing step 4 before step 1. That is, it can be obtained by performing the step of reacting the above-described cellulose with a hydrocarbon group-containing group introducing agent as a hydrophobic group introducing agent as step 4 before step 1. Step 4 will be described later.

(In the general formula (1), R ¹ , R ² and R ³ each independently represents a substituent consisting of one or more structural units selected from the following general formulas (2) to (4), or a hydrogen atom. N represents the average degree of polymerization of the main chain derived from anhydroglucose, and is a number from 100 to 12,000.)

(In the general formula (1), the structural units represented by the general formulas (2) to (4) represent groups containing a hydrocarbon group having 3 to 18 carbon atoms. R ⁴ and R ⁵ are independent of each other. Represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms, wherein R ⁶ is an alkyl group or alkenyl group having 3 to 18 carbon atoms. , An aralkyl group, or an aryl group, and p represents an integer of 0 or 1. In the structural units represented by the general formulas (2) and (3), the oxygen atom is a hydrogen atom or the general formula (2). To the carbon atom of the structural unit represented by any one of (4).

<< Substituents R ¹ , R ² and R ³ >>
In the general formula (1), when the substituent R ¹ is a substituent composed of one or more structural units selected from the formulas (2) to (4), the substituent R ¹ is represented by the formula (2) to A substituent composed of a plurality of structural units selected from (4), a substituent in which a hydrogen atom is bonded to an oxygen atom of only one structural unit selected from formulas (2) and (3), Or the substituent which consists only of structural units of Formula (4) may be sufficient.
When the substituent R ¹ is a substituent composed of a plurality of structural units selected from the formulas (2) and (3), the structural units include an oxygen atom of one structural unit and a carbon of the other structural unit. An oxygen atom that is bonded to an atom and is not bonded to a carbon atom of another structural unit, for example, an oxygen atom located at the end of a substituent is bonded to a hydrogen atom or a structural unit of the formula (4) .
Moreover, there is no limitation in particular in the combination of a structural unit, One type of structural unit chosen from Formula (2) and (3) may be couple | bonded, and 2 chosen from Formula (2)-(4). More than one type of structural unit may be bonded. In the general formula (1), when R ¹ is a substituent having two or more kinds of structural units, the bonding mode may be any of a block bond, a random bond, and an alternating bond.

When the substituent R ¹ is a substituent composed of one or more structural units selected from the formulas (2) to (4), the terminal carbon atom is an oxygen atom of the hydroxyl group of the main chain derived from anhydroglucose. Are connected.
Incidentally, when the substituent R ¹ is a substituent consisting of one or more structural units selected from the formulas (2) to (4), the substituent as long as it does not impair the effects of the present invention, the formula ( A structural unit other than the structural unit selected from 2) to (4) may be included.
When the substituent R ² is a substituent composed of one or more structural units selected from the formulas (2) to (4), the embodiment of the substituent is such that the substituent R ¹ is the formula (2) to ( This is the same as in the case where the substituent is composed of one or more structural units selected from 4).
When the substituent R ³ is a substituent composed of one or more structural units selected from the formulas (2) to (4), the embodiment of the substituent is such that the substituent R ¹ is the formula (2) to ( This is the same as in the case where the substituent is composed of one or more structural units selected from 4).
The substituents R ¹ , R ² , and R ³ are independent and may be the same or different from each other.

In the present invention, the group containing a hydrocarbon group having 3 to 18 carbon atoms refers to a structural unit represented by the general formulas (2) to (4). CGC which is excellent in the feeling of rinsing when blended in hair cosmetics can be obtained because the cellulose derivative which is raw material cellulose has the structural unit.
The group containing a hydrocarbon group having 3 or more and 18 or less carbon atoms is a structure represented by the above general formulas (2) and (3) from the viewpoint of obtaining CGC excellent in rinsing feeling when blended in hair cosmetics. One or more structural units selected from the units are preferred.
In the above formulas (2) and (3), R ⁴ and R ⁵ are each independently a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. Therefore, the formulas (2) and (3) contain a hydrocarbon group having 3 to 18 carbon atoms. Specific examples of R ⁴ and R ⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and isopentyl group. , Neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, vinyl group, 1-propenyl group, 2-propenyl group, Examples include 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 2-heptenyl group, octenyl group and the like.
In these, when mix | blending with hair cosmetics, from a viewpoint of obtaining CGC excellent in a rinse feeling, a C1-C14 alkyl group or a C2-C14 alkenyl group is preferable, and C1-C1 An alkyl group having 10 or less carbon atoms or an alkenyl group having 2 to 10 carbon atoms is more preferable, an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms is more preferable, and an alkyl group having 1 to 5 carbon atoms. Group or an alkenyl group having 2 to 5 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. More preferably, a methyl group or an ethyl group is still more preferable, and an ethyl group is still more preferable.

In the formula (4), R ⁶ is an alkyl group, alkenyl group, aralkyl group or aryl group having 3 to 18 carbon atoms. Specific examples thereof include an n-propyl group, an isopropyl group, n -Butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2- Examples include butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 2-heptenyl group, phenyl group, methylphenyl group, and benzyl group. Among these, from the viewpoint of obtaining a CGC excellent in rinsing feeling when blended in a hair cosmetic, one or more selected from alkyl groups, alkenyl groups, and phenyl groups having 3 to 6 carbon atoms is preferable. One or more selected from an alkyl group and an alkenyl group having 3 to 6 carbon atoms is more preferable, and an alkyl group having 3 to 6 carbon atoms is more preferable.

≪Degree of substitution of hydrocarbon-containing group having 3 to 18 carbon atoms≫
The degree of substitution of a group containing a hydrocarbon having 3 to 18 carbon atoms in the hydrophobically modified cellulose represented by the general formula (1) (hereinafter also referred to as “MS (HC)”) is the hydrophobically modified cellulose. The average value of the number of groups containing a hydrocarbon having 3 to 18 carbon atoms represented by the above formulas (2) to (4) per anhydroglucose unit constituting the main chain Say. MS (HC) is measured and calculated by the method described in Examples below.
The MS (HC) of the hydrophobically modified cellulose represented by the general formula (1) is preferably 0.0001 or more and 0.2 or less. When MS (HC) is within this range, a cationized glycerolated cellulose excellent in rinsing feeling when blended into a hair cosmetic can be obtained. In this respect, MS (HC) is more preferably 0.0005 or more, further preferably 0.001 or more, still more preferably 0.005 or more, still more preferably 0.01 or more, and still more preferably 0.02. That's it. In view of the above viewpoint and production cost, MS (HC) is more preferably 0.15 or less, further preferably 0.10 or less, still more preferably 0.08 or less, still more preferably 0.06 or less, and still more. Preferably it is 0.04 or less.

Next, each process in the manufacturing method of this invention is demonstrated.
(Process 1)
In step 1, the raw material cellulose and glycidol are added to the cellulose portion of the raw material cellulose in the presence of a base compound of more than 0.9 molar equivalent and 1.6 molar equivalents or less per mole of anhydroglucose unit in the raw cellulose. In contrast, it is a step of reacting in a solvent of 10% by mass or more and 200% by mass or less to obtain a reaction mixture 1 containing glycerolated cellulose.
In Step 1, since a reaction between the raw material cellulose and glycidol proceeds rapidly by using a predetermined amount of a base compound and a solvent, the reaction mixture 1 containing glycerolated cellulose can be obtained efficiently.

Examples of the basic compound used in Step 1 include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, trimethylamine and triethylamine. And tertiary amines. Among these, from the viewpoint of the reaction rate of the glycerolation reaction, alkali metal hydroxides or alkaline earth metal hydroxides are preferred, alkali metal hydroxides are more preferred, and sodium hydroxide and potassium hydroxide are further preferred. preferable. These basic compounds can be used alone or in combination of two or more.
There are no particular limitations on the method of adding the base compound, and batch addition or divided addition may be used. The base compound may be added in a solid state or may be added as an aqueous solution.

The amount of the base compound used in Step 1 is more than 0.9 molar equivalent and 1.6 molar equivalent or less per mole of AGU in the raw material cellulose. When the amount of the base compound is 0.9 mole equivalent or less per mole of AGU, the raw material cellulose is not sufficiently activated, the reaction does not proceed sufficiently at the initial stage, the reaction becomes non-uniform, and the resulting cationized glycerol The rinsing feeling of the modified cellulose deteriorates. Moreover, when the amount of the base compound exceeds 1.6 molar equivalents per mole of AGU in the raw material cellulose, the reaction proceeds too fast, so that the reaction proceeds only on the raw material cellulose surface, and the rinsing feeling of the obtained CGC deteriorates. .
From the above viewpoint, the amount of the base compound used in Step 1 is preferably 0.95 molar equivalent or more, more preferably 1.0 molar equivalent or more, and still more preferably 1.1 molar equivalent per mole of AGU in the raw material cellulose. Further, it is preferably 1.5 molar equivalents or less, more preferably 1.3 molar equivalents or less, and still more preferably 1.2 molar equivalents or less.

As a solvent used at the process 1, 1 or more types chosen from an organic solvent and water are mentioned, From the viewpoint of the dispersibility and the reactivity of raw material cellulose powder, it is preferable that it is water. The organic solvent is preferably an organic solvent capable of dissolving glycidol, for example, a secondary or tertiary lower alcohol having 3 to 4 carbon atoms such as isopropyl alcohol and tert-butyl alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Examples include ketones having 3 to 6 carbon atoms; ethers such as tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and aprotic polar solvents such as dimethyl sulfoxide. Among these, ethers such as tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, and secondary or tertiary lower alcohols having 3 to 4 carbon atoms such as isopropyl alcohol and tert-butyl alcohol are preferable. Specifically, tetrahydrofuran, isopropyl alcohol, and tert-butyl alcohol are more preferable.
In addition, the solvent in step 1 is preferably from 0 to 10 in mass ratio of organic solvent to water (organic solvent / water) from the viewpoint of causing the reaction uniformly and improving the rinsing feeling of the obtained CGC. Preferably they are 0 or more and 6 or less, More preferably, they are 0 or more and 4 or less, More preferably, they are 0 or more and 1 or less, More preferably, they are 0 or more and 0.5 or less, More preferably, they are 0 or more and 0.1 or less.

The usage-amount of the solvent in the process 1 is 10 to 200 mass% with respect to the cellulose part of raw material cellulose. When the amount of the solvent used in Step 1 is less than 10% by mass with respect to the cellulose portion of the raw material cellulose, the solvent is too small, so that glycidol does not react uniformly with the raw material cellulose, and the rinsing feeling of the obtained CGC deteriorates. To do. On the other hand, if it exceeds 200% by mass, the dispersion efficiency of the raw cellulose and glycidol is lowered, so that glycidol does not react uniformly with the raw cellulose, and the rinsing feeling of the obtained CGC is deteriorated. From the above viewpoint, the amount of the solvent used in Step 1 is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and still more preferably 50% with respect to the cellulose portion of the raw material cellulose. It is at least mass%, preferably at most 180 mass%, more preferably at most 150 mass%, still more preferably at most 120 mass%.
In addition, “to the cellulose part of the raw material cellulose” means “to the raw material cellulose” when using cellulose (non-derivative cellulose) as the raw material cellulose, and “when using a cellulose derivative as the raw material cellulose” It means “to cellulose before being made into a derivative”. In particular, when hydrophobically modified cellulose is used as the cellulose derivative, it means “relative to cellulose before introducing a hydrophobic group”.

In the solvent in Step 1, water is preferably 10% by mass or more and 100% by mass or less based on the cellulose portion of the raw material cellulose. When the amount of water in the solvent in Step 1 is in the above range, the efficiency of dispersion of the raw cellulose and glycidol is improved with an appropriate amount of solvent, and the glycidol reacts uniformly with the raw cellulose to obtain CGC. The feeling of rinsing is improved. From the same viewpoint, the amount of water in the solvent in Step 1 is more preferably 15% by mass or more, further preferably 20% by mass or more, and still more preferably 25% by mass or more, with respect to the cellulose portion of the raw material cellulose. Yes, more preferably 80% by mass or less, still more preferably 70% by mass or less, and still more preferably 60% by mass or less.
Moreover, when the solvent in the process 1 contains the organic solvent, it is preferable that the organic solvent is 10 mass% or more and 100 mass% or less with respect to the cellulose part of raw material cellulose in this solvent. When the amount of the organic solvent in the solvent in the step 1 is in the above range, the amount of the solvent is moderate and the efficiency of dispersion is improved, glycidol reacts uniformly with the raw material cellulose, and the resulting CGC has a feeling of rinsing. improves. From the above viewpoint, the amount of the organic solvent in the solvent in Step 1 is more preferably 20% by mass or more, further preferably 40% by mass or more, and still more preferably 60% by mass or more, with respect to the cellulose portion of the raw material cellulose. Yes, more preferably 90% by mass or less, still more preferably 80% by mass or less.

The amount of glycidol used in Step 1 is not particularly limited as long as the substitution degree of the glycerol group of the obtained CGC is in a desired range, but is preferably 0.2 mol or more per 1 mol of AGU in the raw material cellulose, 0.4 mol or more is more preferable, 0.6 mol or more is more preferable, 30 mol or less is preferable, 15 mol or less is more preferable, 10 mol or less is further preferable, 5 mol or less is further more preferable, and 2 mol or less is Even more preferred is 1.5 moles or less.
The addition method of glycidol may be any of batch, intermittent, and continuous, but continuous addition is preferable from the viewpoint of increasing the reaction yield.

In step 1, the order of addition of the raw cellulose, glycidol, base compound, and solvent is not particularly limited. From the viewpoint of efficiently performing the glycerolation reaction after activating the raw cellulose, first, the raw cellulose, base compound It is preferable that the solvent is mixed and stirred under heating conditions, and then glycidol is added.
From the viewpoint of activating the raw material cellulose, the heating temperature is preferably 40 ° C. or higher, and more preferably 50 ° C. or higher. Moreover, from a viewpoint of productivity, 100 degrees C or less is preferable and 80 degrees C or less is more preferable. The stirring time of the mixture is preferably 0.5 hours or more, more preferably 1 hour or more from the viewpoint of activating the raw material cellulose, and preferably 5 hours or less, more preferably 3 hours or less from the viewpoint of productivity. It is.

Examples of the apparatus used in Step 1 include a mixer such as a Readyge mixer that can be stirred, and a mixer such as a so-called kneader that is used for kneading powders, high-viscosity substances, resins, and the like.
In Step 1, there is no particular limitation on the reaction temperature when the raw material cellulose and glycidol are reacted, but from the viewpoint of the reaction rate, 0 ° C. or higher is preferable, 20 ° C. or higher is more preferable, and 30 ° C. or higher is even more preferable. Moreover, from a viewpoint of the decomposition | disassembly suppression of glycidol, 200 degrees C or less is preferable, 100 degrees C or less is more preferable, and 80 degrees C or less is still more preferable.
The reaction time may be appropriately adjusted depending on the amount of glycerol group introduced and the like. The reaction time is usually 0.1 hours or more and 12 hours or less after the start of the addition of glycidol. From the viewpoint of reaction yield, 0.2 hours or more is preferable, and 0.5 hours or more is more preferable. 1 hour or more is further preferable, and from the viewpoint of productivity, 8 hours or less is preferable, 5 hours or less is more preferable, and 3 hours or less is more preferable.
By performing the above step 1, the reaction mixture 1 containing glycerolated cellulose is obtained. In addition, it is preferable to perform reaction of the process 1 in inert gas atmosphere, such as nitrogen, as needed from a viewpoint which suppresses coloring and the molecular weight fall of the principal chain derived from anhydroglucose.

(Process 2)
In step 2, the reaction mixture 1 obtained in step 1 and an acid are mixed, so that the amount of the base compound is 0.1 to 0.9 molar equivalents per 1 mol of anhydroglucose unit in the raw cellulose. It is a step of adjusting and further reacting raw material cellulose and glycidol. By performing step 2, a part of the base compound in the reaction mixture obtained in step 1 is neutralized, the base compound on the cellulose surface is reduced, and a part of the alcoholate by the base compound is a hydroxyl group. Become. For this reason, it is considered that hydrophilic glycidol is likely to penetrate into the cellulose, and glycerolation proceeds uniformly. Furthermore, the cationization reaction in the subsequent step 3 is considered to proceed uniformly.

<Acid>
The acid used in Step 2 can be used without particular limitation as long as it can be adjusted to a desired amount by neutralizing a part of the base compound in the reaction mixture 1. In Step 2, either an organic acid or an inorganic acid can be used, but an organic acid is preferable from the viewpoint of solubility in a solvent, and a weak acid is more preferable from the viewpoint of suppressing a local reaction.
The organic acid is preferably at least one selected from acetic acid, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, succinic acid, fumaric acid, and adipic acid, more preferably at least one selected from acetic acid and lactic acid. Preferably, acetic acid is more preferable.

The amount of acid used in step 2 is an amount that can adjust the amount of the base compound to 0.1 to 0.9 molar equivalents per mole of anhydroglucose unit in the raw material cellulose. In addition, it can be appropriately selected depending on the kind of acid.
From the viewpoint of obtaining the effect of the present invention, the amount of the base compound after mixing the reaction mixture 1 and the acid in Step 2 (hereinafter also referred to as “effective base compound amount”) is the anhydroglucose unit in the raw material cellulose. 0.1 mole equivalent or more per mole, preferably 0.2 mole equivalent or more, more preferably 0.3 mole equivalent or more, still more preferably 0.5 mole equivalent or more, preferably 0.9 mole equivalent or less, preferably Is 0.8 molar equivalent or less, more preferably 0.7 molar equivalent or less. When the amount of the effective base compound in step 2 is less than 0.1 molar equivalent per mole of AGU in the raw material cellulose, glycerolation of the raw material cellulose and subsequent cationization are not uniformly performed. CGC excellent in the feeling of rinsing cannot be obtained. If the amount of the effective base compound exceeds 0.9 molar equivalents per mole of AGU in the raw material cellulose, the glycerolation reaction and the subsequent cationization reaction proceed too quickly, so that the reaction proceeds locally and the resulting CGC is rinsed. The feeling gets worse.
In the present invention, the effective base compound amount refers to an amount (molar equivalent) obtained by subtracting the amount of the acid used in Step 2 from the amount of the base compound in the reaction mixture 1.

  From the viewpoint of the reaction uniformity and the rinsing feeling of the obtained CGC, in step 2, the equivalent ratio of the amount of the basic compound after mixing the reaction mixture 1 and the acid with respect to the amount of the basic compound in the reaction mixture 1 (reaction mixture 1 The amount of the basic compound after mixing the acid and the acid / the amount of the basic compound in the reaction mixture 1) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, preferably It is 0.7 or less, more preferably 0.6 or less, and still more preferably 0.55 or less.

Here, the step 2 may include the step of adding glycidol and reacting simultaneously with the mixing of the reaction mixture 1 obtained in the step 1 and the acid, or after mixing the reaction mixture 1 and the acid. preferable. By performing this step, the glycerolation reaction and the subsequent cationization reaction proceed uniformly, and the rinsing feeling of the obtained CGC is improved.
When performing this step, the mass ratio of the amount of glycidol used in Step 2 to the total amount of glycidol used in Step 1 and Step 2 (the amount of glycidol used in Step 2 / the glycidol used in Step 1 and Step 2) The total amount) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and still more preferably from the viewpoint of allowing the reaction to proceed uniformly and improving the rinsing feeling of the obtained CGC. Preferably it is 0.5 or more, More preferably, it is 0.6 or more, Preferably it is 0.95 or less, More preferably, it is 0.9 or less, More preferably, it is 0.85 or less.

The temperature at which Step 2 is performed is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and further preferably 30 ° C. or higher, from the viewpoint of further proceeding the glycerolation reaction. Further, from the viewpoint of suppressing the degradation of glycidol, it is preferably 200 ° C. or lower, more preferably 100 ° C. or lower, still more preferably 80 ° C. or lower, and further preferably 60 ° C. or lower.
The reaction time of step 2 is usually 0.1 hours or more and 72 hours or less after the mixing of the reaction mixture 1 and the acid is completed, and preferably 0.2 hours or more from the viewpoint of reaction yield and productivity. More preferably, it is 0.5 hour or more, More preferably, it is 1 hour or more, More preferably, it is 3 hours or more. Moreover, it is preferably 36 hours or less, more preferably 18 hours or less, still more preferably 12 hours or less, and still more preferably 8 hours or less.
In addition, it is preferable to perform the process 2 in inert gas atmosphere, such as nitrogen, as needed from a viewpoint which suppresses coloring and the molecular weight fall of the principal chain derived from anhydroglucose.

<Degree of substitution of glycerol group>
From the viewpoint of obtaining a CGC excellent in rinsing feeling when blended in a hair cosmetic, in Step 1 and Step 2, the degree of substitution of glycerol groups per AGU in the obtained CGC is 0.5 or more and 5.0 or less. It is preferable to be performed as follows. The degree of substitution of the glycerol group is more preferably 0.7 or more, still more preferably 0.8 or more, still more preferably 1.0 or more, still more preferably 1.2 or more, still more preferably 1.5 or more. It is. The degree of substitution is more preferably 4.0 or less, still more preferably 3.5 or less, still more preferably 3.0 or less, and still more preferably 2.5 or less. Examples of the method for adjusting the degree of substitution of the glycerol group include a method for adjusting the amount of glycidol and a base compound used, a method for adjusting the amount of a solvent used, and the like.
In the present invention, the degree of substitution of glycerol groups (hereinafter also referred to as “MS (Gly)”) refers to the number of glycerol groups present in a CGC molecule per anhydroglucose unit constituting the main chain. Mean value. MS (Gly) is measured and calculated by the method described in Examples below.

(Process 3)
Step 3 is a step of adding a cationizing agent after step 2 and reacting with glycerolated cellulose to obtain cationized glycerolated cellulose.
<Cationizing agent>
Examples of the cationizing agent used in the present invention include compounds represented by the following general formula (5) or (6).

In the general formulas (5) and (6), R ^{7 to} R ¹² are each independently a linear or branched alkyl group having 1 to 3 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, Examples include an n-propyl group and an isopropyl group. Among these, from the viewpoint of water solubility of the obtained CGC, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
In the general formulas (5) and (6), Q ⁻ and W ⁻ represent anions which are counter ions of quaternary ammonium ions. Q ⁻ and W ⁻ are not particularly limited as long as they are anions, and specific examples thereof include alkyl sulfate ions having 1 to 3 carbon atoms, sulfate ions, phosphate ions, fatty acid ions having 1 to 3 carbon atoms, and halides. And ions.
Among these, from the viewpoint of ease of production, one or more selected from alkyl sulfate ions having 1 to 3 carbon atoms, sulfate ions, and halide ions are preferable, and halide ions are more preferable. Examples of the halide ion include fluoride ion, chloride ion, bromide ion and iodide ion. From the viewpoint of water solubility and chemical stability of CGC, chloride ion and bromide ion are preferable, and chloride ion. Is more preferable.
t and u are integers of 0 or more and 3 or less. From the viewpoint of easy availability of raw materials, t and u are preferably 1.
Z represents a halogen atom. R ^{7 to} R ¹² may be the same as or different from each other.

Specific examples of the compound represented by the general formula (5) or (6) include chloride, bromide, or iodide of glycidyltrimethylammonium, glycidyltriethylammonium, and glycidyltripropylammonium, and 3-chloro-2- Hydroxypropyltrimethylammonium, 3-chloro-2-hydroxypropyltriethylammonium, or 3-chloro-2-hydroxypropyltripropylammonium chloride, 3-bromo-2-hydroxypropyltrimethylammonium, 3-bromo-2- Hydroxypropyltriethylammonium or 3-bromo-2-hydroxypropyltripropylammonium bromide, 3-iodo-2-hydroxypropyltrimethylammonium, 3-iodo- - hydroxypropyl triethylammonium, or 3-iodo-2-hydroxypropyl respectively iodide tripropyl ammonium.
Among these, glycidyltrimethylammonium or glycidyltriethylammonium chloride or bromide; 3-chloro-2-hydroxypropyltrimethylammonium or 3-chloro-2-hydroxypropyl, from the viewpoint of availability of raw materials and chemical stability Triethylammonium chloride; 3-bromo-2-hydroxypropyltrimethylammonium or 3-bromo-2-hydroxypropyltriethylammonium bromide is preferred, glycidyltrimethylammonium chloride and 3-chloro-2-hydroxypropyltrimethylammonium chloride 1 or more types selected from are more preferable.
These cationizing agents can be used alone or in combination of two or more, and it is more preferable to use glycidyltrimethylammonium chloride and 3-chloro-2-hydroxypropyltrimethylammonium chloride in combination.

  The amount of the cationizing agent to be used may be appropriately selected in consideration of the desired degree of substitution of the cationic group and the reaction yield. However, the water solubility of CGC, particularly the feeling of rinsing when blended in hair cosmetics. From the viewpoint of obtaining excellent CGC, 0.01 mol or more is preferable, 0.03 mol or more is more preferable, 0.05 mol or more is more preferable, and 0.1 mol or more is further more preferable with respect to 1 mol of AGU in the raw material cellulose. preferable. Moreover, 10 mol or less is preferable, 8 mol or less is more preferable, 5 mol or less is further more preferable, and 1 mol or less is still more preferable.

The cationization reaction in step 3 is preferably performed in a solvent in the presence of a base compound. The base compound and solvent contained in the reaction mixture containing glycerolated cellulose used in Step 3 can also be used as they are.
As the base compound used in step 3, the same compounds as the base compounds used in the above-described steps can be used. 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 basic compounds can be used alone or in combination of two or more.
From the viewpoint of reaction yield, the amount of the base compound in step 3 is preferably 0.1 molar equivalent or more, more preferably 0.15 molar equivalent or more, and still more preferably 0.2 mole per mole of AGU in the raw material cellulose. From the same viewpoint, it is preferably 0.6 molar equivalent or less, more preferably 0.5 molar equivalent or less, still more preferably 0.4 molar equivalent or less, and still more preferably 0.3 molar equivalent or less. is there.
The amount of the basic compound in step 3 refers to the amount of the basic compound that is effectively present during the cationization reaction in step 3.

As a solvent used at the process 3, 1 or more types chosen from an organic solvent and water are mentioned, Water is preferable. As an organic solvent, the thing similar to what was used at the process 1 mentioned above is mentioned. Among them, secondary or tertiary lower alcohols having 3 to 4 carbon atoms such as isopropyl alcohol and tert-butyl alcohol are preferable, and isopropyl alcohol is more preferable.
The solvent in Step 3 is preferably a mass ratio of organic solvent to water (organic solvent / water) of 0 or more and 2 or less from the viewpoint of uniformly promoting the cationization reaction and improving the rinsing feeling of the obtained CGC. More preferably, it is 0 or more and 1.5 or less, More preferably, it is 0 or more and 1.2 or less.

  It is preferable to perform the process 3 in 50 to 800 mass% solvent with respect to the cellulose part of raw material cellulose from a viewpoint of the yield of a cationization reaction. From the above viewpoint, the amount of the solvent is more preferably 80% by mass or more, further preferably 100% by mass or more, more preferably 400% by mass or less, and still more preferably 300% by mass with respect to the cellulose portion of the raw material cellulose. % Or less.

In the solvent in the step 3, it is preferable that water is 50% by mass or more and 500% by mass or less with respect to the cellulose part of the raw material cellulose. When the amount of water in the solvent in Step 3 is in the above range, the amount of the solvent is moderate and the efficiency of dispersion becomes good, the cationizing agent reacts uniformly, and the rinsing feeling of the obtained CGC is improved. From the above viewpoint, the amount of water in the solvent in Step 3 is more preferably 80% by mass or more, further preferably 100% by mass or more, and still more preferably 120% by mass or more, with respect to the cellulose portion of the raw material cellulose. More preferably, it is 400 mass% or less, More preferably, it is 300 mass% or less, More preferably, it is 200 mass% or less.
Moreover, when the solvent in the process 3 contains the organic solvent, it is preferable that the organic solvent is more than 0 mass% and 500 mass% or less with respect to the cellulose part of raw material cellulose in this solvent. When the amount of the organic solvent in the solvent in the step 3 is in the above range, the dispersion efficiency of the glycerolated cellulose is improved with an appropriate amount of the solvent, the cationizing agent reacts uniformly, and the resulting CGC rinse feeling Will improve. From the above viewpoint, the amount of the organic solvent in the solvent in the step 3 is more preferably 400% by mass or less, and further preferably 350% by mass or less with respect to the cellulose portion of the raw material cellulose.
When using more organic solvent than water, from the viewpoint of improving the reactivity, the amount of the organic solvent in the solvent in Step 3 is preferably 200% by mass or more, more preferably, relative to the cellulose portion of the raw material cellulose. 300% by mass or more.
When using less organic water than water, the amount of organic solvent in the solvent in step 3 is preferably relative to the cellulose portion of the raw material cellulose from the viewpoint of improving the dispersion efficiency of glycerolated cellulose and increasing the reactivity. Is 10 mass% or less, and it is more preferable not to use an organic solvent.

There is no restriction | limiting in particular in the addition method at the time of adding a cationizing agent, Collective, division | segmentation, continuous addition, or these combination may be sufficient. From the viewpoint of efficiently dispersing the cationizing agent, it is preferable to add the cationizing agent continuously or dividedly.
There is no restriction | limiting in particular also in the form of the cationizing agent at the time of addition. When the cationizing agent is in a liquid state, it may be used as it is or in a form diluted with the solvent.

The temperature during the cationization reaction in step 3 is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, further preferably 30 ° C. or higher, from the viewpoint of reaction rate, and 200 ° C. or lower from the viewpoint of inhibiting decomposition of the cationizing agent. Is preferable, 100 ° C. or lower is more preferable, and 80 ° C. or lower is still more preferable.
What is necessary is just to adjust reaction time suitably with the reaction rate of a cationizing agent, the introduction amount of a desired cationic group, etc. The reaction time is usually 0.1 hours or more and 72 hours or less, and from the viewpoint of reaction yield, 0.2 hours or more is preferable, 0.5 hours or more is more preferable, 1 hour or more is further preferable, and productivity is improved. From the viewpoint, it is preferably 36 hours or less, more preferably 18 hours or less, still more preferably 12 hours or less, and even more preferably 8 hours or less.
In addition, it is preferable to perform cationization reaction in inert gas atmosphere, such as nitrogen, as needed from a viewpoint which suppresses coloring and the molecular weight fall of the main chain derived from anhydroglucose.

<Degree of substitution of cationic group>
It is preferable to perform the process 3 so that the substitution degree of the cationic group per anhydroglucose unit in CGC obtained may be 0.01 or more and 1.0 or less. When the substitution degree of the cationic group is within the above range, the rinsing feeling is improved when CGC is blended in the hair cosmetic.
In the present invention, the degree of substitution of the cationic group of CGC (hereinafter also referred to as “MS (N +)”) is the number of cationic groups present in the molecule of CGC, which is an anhydroglucose unit constituting the main chain. The average value per unit. MS (N +) is measured and calculated by the method described in Examples below.
From the above viewpoint, the MS (N +) of CGC obtained by the production method of the present invention is more preferably 0.03 or more, still more preferably 0.06 or more, still more preferably 0.1 or more, and still more preferably 0. .15 or more, more preferably 0.5 or less, still more preferably 0.3 or less, still more preferably 0.22 or less, and still more preferably 0.19 or less.

<Cation charge density>
Step 3 is preferably performed so that the cationic charge density of the obtained CGC is 0.05 mmol / g or more and 2.0 mmol / g or less. When the cationic charge density falls within the above range, the rinsing feeling is improved when blended into the hair cosmetic. From the above viewpoint, the cation charge density of the obtained CGC is more preferably 0.1 mmol / g or more, still more preferably 0.2 mmol / g or more, still more preferably 0.3 mmol / g or more, still more preferably 0.00. 4 mmol / g or more, more preferably 0.45 mmol / g or more, more preferably 0.8 mmol / g or less, still more preferably 0.7 mmol / g or less, still more preferably 0.6 mmol / g or less, particularly Preferably it is 0.55 mmol / g or less.
In the present invention, the cation charge density of CGC refers to the number of moles of cation charge contained per gram of CGC, and is calculated from the following calculation formula.
Cationic charge density (mmol / g) = nitrogen content (%) ÷ 14 × 10
(In the formula, the nitrogen content (%) is measured by the Kjeldahl method described in the examples.)
Examples of the method for adjusting the substitution degree of the cationic group and the cation charge density include a method for adjusting the amount of the cationizing agent and the base compound, a method for adjusting the amount of the solvent used in Step 3, and the like.

(Process 4)
It is preferable that the production method of the present invention further includes a step of adding a hydrophobic group-introducing agent and reacting as the step 4. Step 4 may be carried out at any stage of the production method of the present invention, but it is preferable to have Step 4 before Step 1 or between Step 2 and Step 3, and between Step 2 and Step 3. More preferably, step 4 is included.
For example, when step 4 is performed before step 1, step 4 is a step of reacting cellulose and a hydrophobic group introducing agent. As a result, a hydrophobically modified cellulose in which a hydrophobic group is introduced into the cellulose is obtained, and thus the hydrophobically modified cellulose is subjected to Step 1 as a cellulose derivative which is a raw material cellulose.
When Step 4 is performed after Step 2 and before Step 3, Step 4 is a step of reacting the glycerolated cellulose obtained in Step 2 with the hydrophobic introduction agent. Thus, a hydrophobic group is introduced into the glycerolated cellulose, and the obtained hydrophobically modified glycerolated cellulose is subjected to Step 4 to react with a cationizing agent.
When Step 4 is performed after Step 3, Step 4 is a step of introducing a hydrophobic group into CGC by reacting the CGC obtained in Step 3 with a hydrophobic introduction agent.
When the production method of the present invention has the above step 4, hydrophobically modified CGC is finally obtained, and when the CGC is blended in a hair cosmetic such as a hair cleanser, the slipperiness more excellent at the time of rinsing the hair is obtained. This is preferable because it can provide a feeling of sustain and a feeling of coating.
As the hydrophobic group-introducing agent, from the viewpoint of obtaining the above effect, an introducing agent having one or more hydrophobic sites selected from a hydroxyalkyl moiety having 3 or more carbon atoms and an oxyalkylene moiety having 3 or more carbon atoms is preferable. An introduction agent for a group (hydrocarbon group-containing group) containing a hydrocarbon having 3 to 18 carbon atoms represented by any one of formulas (2) to (4) is more preferable. Hereinafter, with respect to Step 4, an example in which a hydrocarbon group-containing group introduction agent is used as the hydrophobic group introduction agent will be described.

<Introducing agent for hydrocarbon group-containing group>
The hydrocarbon group-containing group-introducing agent used in the present invention is not limited as long as it can introduce the structural unit represented by any one of the general formulas (2) to (4).
Examples of the introducing agent capable of introducing the structural unit represented by the general formula (2) or (3) include compounds represented by the following general formula (7) or (8).

In general formulas (7) and (8), R ¹³ , R ¹⁴ and preferred embodiments thereof are the same as R ^{4 in} general formula (2) and R ^{5 in} general formula (3). A represents a halogen atom.
Specific examples of the compound represented by the general formula (7) include propylene oxide, 1,2-butylene oxide, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,2-epoxyoctadecane and the like can be mentioned.
Specific examples of the compound represented by the general formula (8) include 1-chloro-2-propanol, 1-chloro-2-butanol, 1-bromo-2-butanol, 1-chloro-2-pentanol, 1-chloro-2-hexanol, 1-chloro-2-heptanol, 1-chloro-2-octanol, 1-chloro-2-nonanol, 1-chloro-2-decanol, 1-chloro-2-undecanol, 1- Chloro-2-dodecanol, 1-chloro-2-tridecanol, 1-chloro-2-tetradecanol, 1-chloro-2-pentadecanol, 1-chloro-2-hexadecanol, 1-chloro-2- Examples include 1-halo-2-alkanol having 3 to 18 carbon atoms such as heptadecanol and 1-chloro-2-octadecanol.
Among these, the compound represented by the general formula (7) is preferable from the viewpoints of no salt by-product during the reaction, easy availability of raw materials, and chemical stability, and is incorporated into hair cosmetics. From the viewpoint of obtaining a cationized glycerolated cellulose having excellent rinsing feeling, at least one selected from propylene oxide, 1,2-butylene oxide, 1,2-epoxypentane, and 1,2-epoxyhexane is preferable. One or more selected from oxides and 1,2-butylene oxide are more preferable, and 1,2-butylene oxide is still more preferable. These can be used alone or in combination of two or more.

  Examples of the introducing agent capable of introducing the structural unit represented by the general formula (4) include compounds represented by the following general formulas (9) to (11).

In the general formulas (9) to (11), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and preferred embodiments thereof are the same as R ^{6 in the} general formula (4). q and preferred embodiments thereof are the same as p in the general formula (4). B represents a halogen atom. In the general formula (11), R ¹⁷ and R ¹⁸ may be different but are preferably the same.
When the compound represented by the general formula (10) is used, the glycerol group and the structural unit represented by the general formula (4) (where p is 0) can be introduced simultaneously.
Specific examples of the compound represented by the general formula (9) include 1-chloropropane, 1-propane bromide, 1-butane chloride, 1-butane bromide, 1-pentane chloride, 1-pentane bromide, 1-chlorohexane, 1-hexane bromide, 1-heptane chloride, 1-heptane bromide, 1-octane chloride, 1-chlorodecane, 1-chloride dodecane, 1-chloride tetradecane, 1-hexadecane chloride, 1-chloride Alkanes having 3 to 18 carbon atoms such as octadecane, 1-chloro-3-butene, benzyl chloride, halides of alkenes, alkenes or arylalkanes; Carboxyl having 4 to 19 carbon atoms such as butanoic acid chloride and hexanoic acid chloride And acid halides. Among these, it is preferable to use an alkane halide having 3 to 7 carbon atoms.
Specific examples of the compound represented by the general formula (10) include propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, lauryl glycidyl ether. , Glycidyl ether having an alkyl group having 3 to 18 carbon atoms, such as tetradecyl glycidyl ether and stearyl glycidyl ether; glycidyl ether having an alkenyl group having 3 to 18 carbon atoms; phenyl glycidyl ether, tolyl glycidyl ether, benzyl glycidyl Examples include ether.
Specific examples of the compound represented by the general formula (11) include butanoic acid anhydride, hexanoic acid anhydride, octanoic acid anhydride, decanoic acid anhydride, lauric acid anhydride, tetradecanoic acid anhydride, stearin Examples thereof include carboxylic acid anhydrides having an alkyl group having 3 to 18 carbon atoms, such as acid anhydrides.
In these, the compound represented by the said General formula (9) or (10) is preferable from a viewpoint of the availability of a raw material and chemical stability, and it is excellent in the rinse feeling at the time of mix | blending with hair cosmetics. From the viewpoint of obtaining cationized glycerolated cellulose, one or more selected from halides of alkanes having 3 to 18 carbon atoms and glycidyl ethers having an alkyl group having 3 to 18 carbon atoms are preferable, and those having 3 to 7 carbon atoms. 1 or more selected from glycidyl ethers having an alkane halide and an alkyl group having 3 to 7 carbon atoms, more preferably glycidyl ethers having an alkyl group having 3 to 7 carbon atoms. Specifically, one or more kinds selected from 1-bromohexane, 1-octane chloride, 1-dodecane chloride, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, and hexyl glycidyl ether are preferable. One or more kinds selected from chlorohexan, 1-octane chloride, 1-dodecane chloride, propyl glycidyl ether and butyl glycidyl ether are more preferred, and butyl glycidyl ether is still more preferred. These can be used alone or in combination of two or more.

The amount of the hydrocarbon group-containing group introduction agent to be used may be appropriately selected in consideration of the desired MS (HC) and reaction yield. From the viewpoint of the water solubility of CGC and the effect of the present invention, Preferably it is 0.01 mol or more with respect to 1 mol of AGU in cellulose, More preferably, it is 0.03 mol or more, More preferably, it is 0.05 mol or more, From a viewpoint of the said viewpoint and manufacturing cost, Preferably it is 2 mol or less. More preferably, it is 1 mol or less, More preferably, it is 0.5 mol or less.
The method for adding the hydrocarbon group-containing group introduction agent may be any of batch, intermittent, and continuous.

The introduction reaction of the hydrocarbon group-containing group is preferably performed in the presence of a base compound. Examples of the base compound used in the reaction include the same compounds as those exemplified in the above step. Among these, from the viewpoint of the reaction rate of the introduction reaction of the hydrocarbon group-containing group, an alkali metal hydroxide or an alkaline earth metal hydroxide is preferable, an alkali metal hydroxide is more preferable, sodium hydroxide, More preferred is potassium hydroxide. These basic compounds can be used alone or in combination of two or more.
There are no particular limitations on the method of adding the base compound, and batch addition or divided addition may be used. The base compound may be added in a solid state or may be added after an aqueous solution. In addition, when the cellulose powder or reaction mixture to be subjected to Step 4 contains a base compound, the base compound in the cellulose powder or reaction mixture may be used as it is without newly adding a base compound.

  The amount of the base compound used in the introduction reaction of the hydrocarbon-containing group is preferably 0.1 molar equivalent or more with respect to 1 mol of AGU in the raw material cellulose from the viewpoint of reaction selectivity of the hydrocarbon group-containing group introduction agent. More preferably 0.2 molar equivalents or more, still more preferably 0.5 molar equivalents or more, preferably 2.0 molar equivalents or less, more preferably 1.3 molar equivalents or less, still more preferably 1.2 molar equivalents. It is as follows.

There is no particular limitation on the form of the hydrocarbon group-containing group introduction agent when it is added. When the hydrocarbon group-containing group introduction agent is in a liquid state, it may be used as it is, or may be used in a form diluted with water or a non-aqueous solvent.
Non-aqueous solvents used for dilution include generally used secondary or tertiary lower alcohols having 3 to 4 carbon atoms such as isopropyl alcohol and tert-butyl alcohol; carbons such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples include ketones having a number of 3 or more and 6 or less; ethers such as tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and aprotic polar solvents such as dimethyl sulfoxide.
The introduction reaction of the hydrocarbon group-containing group can also be performed in the presence of a nonaqueous solvent from the viewpoint of the reaction yield of the hydrocarbon group-containing group introduction agent. As the non-aqueous solvent, the same non-aqueous solvent as described above can be used.
When these non-aqueous solvents are used, the amount used is preferably 100% by mass or more, more preferably 1,000% by mass or more, based on the cellulose portion of the raw material cellulose from the viewpoint of the effect of addition of the non-aqueous solvent. More preferably, it is 5,000% by mass or more, and from the viewpoint of productivity and reaction yield, it is preferably 100,000% by mass or less, more preferably 50,000% by mass or less, and still more preferably 20,000% by mass. It is as follows.

Examples of the apparatus used for the introduction reaction of the hydrocarbon group-containing group include the same apparatus as exemplified in the above-mentioned step 1.
The temperature during the reaction is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and further preferably 30 ° C. or higher, from the viewpoint of the reaction rate. Further, from the viewpoint of suppressing decomposition of the hydrocarbon group-containing group introduction agent, it is preferably 200 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 80 ° C. or lower.
The reaction time may be appropriately adjusted depending on the reaction rate of the hydrocarbon group-containing group introduction agent. The reaction time is usually 0.1 hours or more and 72 hours or less, and from the viewpoint of reaction yield and productivity, preferably 0.2 hours or more, more preferably 0.5 hours or more, and further preferably 1 hour or more. . Moreover, it is preferably 36 hours or less, more preferably 12 hours or less, still more preferably 8 hours or less, and even more preferably 6 hours or less.
The introduction reaction of the hydrocarbon group-containing group is preferably performed in an atmosphere of an inert gas such as nitrogen as necessary from the viewpoint of coloring and suppressing a decrease in the molecular weight of the main chain derived from anhydroglucose.

<Degree of substitution of hydrophobic group>
Step 4 is preferably performed so that the degree of substitution of the hydrophobic group of the obtained CGC, preferably the degree of substitution of the hydrocarbon group-containing group (MS (HC)) is 0.0001 or more and 0.2 or less. . If MS (HC) is this range, CGC excellent in the rinse feeling at the time of mix | blending with hair cosmetics can be obtained. In this respect, MS (HC) is more preferably 0.0005 or more, further preferably 0.001 or more, still more preferably 0.005 or more, still more preferably 0.01 or more, and still more preferably 0.02. That's it. In view of the above viewpoint and production cost, MS (HC) is more preferably 0.15 or less, further preferably 0.10 or less, still more preferably 0.08 or less, still more preferably 0.06 or less, and still more. Preferably it is 0.04 or less.
MS (HC) is measured and calculated by the method described in Examples below.

After completion of the reaction, the alkali can be neutralized with an acid. As the acid, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid and lactic acid can be used.
The obtained CGC is separated by filtration or the like, if necessary, and washed with hot water, hydrous isopropyl alcohol, hydrous acetone solvent, or the like to remove unreacted cationizing agent or glycidol, cationizing agent or glycidol-derived by-product. It can also be used after removing salts by-produced by organisms and neutralization. In addition, as a purification method, a general purification method such as reprecipitation purification, centrifugation, or dialysis can be used.

<Average polymerization degree>
The average degree of polymerization of CGC obtained by the production method of the present invention varies depending on the average degree of polymerization of the raw material cellulose used and a pretreatment method such as pulverization of the raw material cellulose, but is preferably 100 or more and 12,000 or less. When the average degree of polymerization is within this range, an excellent rinsing feeling can be obtained particularly when blended in a hair cosmetic.
The average degree of polymerization is preferably 200 or more, more preferably 500 or more, still more preferably 1,000 or more, particularly from the viewpoint of obtaining an excellent rinsing feeling when blended in a hair cosmetic. From the viewpoint of handling properties, the average degree of polymerization is preferably 10,000 or less, more preferably 5,000 or less, and still more preferably 2,500 or less.

[Hair cosmetic composition]
The hair cosmetic composition of the present invention contains CGC obtained by the production method of the present invention, a surfactant, and water.

<CGC>
The content of CGC in the hair cosmetic composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 0.1% by mass or more from the viewpoint of obtaining an excellent rinsing feeling. Further preferred. Moreover, 10 mass% or less is preferable from a viewpoint of the handleability of a hair cosmetic composition, 5 mass% or less is more preferable, and 1 mass% or less is still more preferable.

<Surfactant>
The hair cosmetic composition of the present invention contains one or more surfactants.
As the surfactant, any surfactant can be used as long as it is usually used in pharmaceuticals, quasi drugs, cosmetics, toiletries, miscellaneous goods and the like. Specifically, one or more types selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants can be mentioned.
When the hair cosmetic composition of the present invention is a hair cleanser composition such as shampoo, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant from the viewpoint of obtaining particularly excellent rinsing feeling. One or more selected from agents are preferred.

(Anionic surfactant)
As the anionic surfactant, sulfate ester salts, sulfonate salts, carboxylate salts, phosphate ester salts and amino acid salts having a hydrophobic site are preferable.
Specifically, sulfate esters having a hydrophobic site such as alkyl sulfates, alkenyl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, polyoxyalkylene alkyl phenyl ether sulfates; sulfosuccinic acid Alkyl ester salt, polyoxyalkylene sulfosuccinic acid alkyl ester salt, alkane sulfonate, acyl isethionate, sulfonate having a hydrophobic site such as acyl methyl taurate; higher fatty acid salt having 8 to 16 carbon atoms, poly Carboxylate having a hydrophobic moiety such as oxyalkylene alkyl ether acetate; Phosphate ester salt having a hydrophobic moiety such as alkyl phosphate and polyoxyalkylene alkyl ether phosphate; Acyl glutamate, alanine derivatives Glycine derivatives, amino acid salts and the like having a hydrophobic moiety, such as arginine derivatives.
An anionic surfactant is an alkyl group or an alkenyl group having 8 or more carbon atoms as a hydrophobic site from the viewpoint of detergency, foaming properties and foam quality of a hair cosmetic composition, particularly from the viewpoint of obtaining an excellent rinsing feeling. Preferably having an alkyl group or alkenyl group having 10 or more carbon atoms, more preferably having an alkyl group or alkenyl group having 20 or less carbon atoms, and an alkyl group or alkenyl group having 16 or less carbon atoms. More preferably.

  Among these, alkyl sulfates such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate (sodium laureth-2 sulfate), potassium laurate, etc. Higher fatty acid salts, polyoxyethylene alkyl ether acetates such as sodium polyoxyethylene lauryl ether acetate (sodium laureth-4,5 acetate), sulfosuccinic acid alkyl ester salts such as sodium laureth-2 sulfosuccinate, N-acyl-L -One or more kinds selected from acyl glutamate acyl isethionate and acyl methyl taurate such as sodium glutamate (sodium cocoyl glutamate) are preferable. At least one member selected from ether sulfates and alkyl sulfates are more 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, Polyethylene glycol type nonionic surfactant such as oxyalkylene (hardened) castor oil, polyhydric alcohol type nonionic surfactant such as sucrose fatty acid ester, polyglycerin alkyl ether, polyglycerin fatty acid ester, alkylglycoside and fatty acid And alkanolamides.
The nonionic surfactant is an alkyl having 8 to 20 carbon atoms as a hydrophobic site from the viewpoint of detergency of the hair cosmetic composition, the amount of foam at the time of washing, and the foam quality, particularly from the viewpoint of obtaining an excellent rinsing feeling. It preferably has a group or an alkenyl group.
In these, 1 or more types chosen from polyoxyalkylene alkyl ether, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide, and alkyl glycoside are preferable, and C8 or more, such as decylglucoside, 18 or less, Preferably it is 12 or less Selected from alkyl glucoside, polyoxyethylene lauryl ether, polyoxyethylene alkyl ethers such as polyoxyethylene cetostearyl ether, coconut oil fatty acid monoethanolamide, and fatty acid monoalkanolamides such as coconut oil fatty acid N-methyl monoethanolamide One or more selected from the above are more preferable.

(Amphoteric surfactant)
Examples of amphoteric surfactants include betaine surfactants such as imidazoline betaines, alkyldimethylaminoacetic acid betaines, fatty acid amidopropyl betaines, and sulfobetaines, and amine oxide surfactants such as alkyldimethylamine oxides.
Among these, from the viewpoints of the washing properties of the hair cosmetic composition and the amount of foam at the time of washing, the foam quality, and particularly the feeling of rinsing, imidazoline-based betaine, alkyldimethylaminoacetic acid betaine, fatty acid amidopropyl betaine, And at least one selected from alkylhydroxysulfobetaines, specifically, at least one selected from coconut oil fatty acid amidopropylbetaine, laurylcarbomethoxymethylhydroxyimidazolium betaine, and laurylhydroxysulfobetaine.

(Cationic surfactant)
As the cationic surfactant, a quaternary ammonium salt, pyridinium salt, or tertiary amine having a hydrocarbon group having 12 to 28 carbon atoms which may be separated by an amide group, an ester group or an ether group. And salts of mineral acids or organic acids. Specifically, mono-long-chain alkyltrimethylammonium salts such as cetyltrimethylammonium salt, stearyltrimethylammonium salt, behenyltrimethylammonium salt, okdadecyloxypropyltrimethylammonium salt, distearyldimethylammonium salt, diisotetradecyldimethylammonium Examples thereof include dilong-chain alkyldimethylammonium salts such as salts, and monolong-chain alkyldimethylamine salts such as stearyldimethylamine, behenyldimethylamine, octadecyloxypropyldimethylamine hydrochloric acid, citric acid, and lactate.
Among these, a mono long chain alkyltrimethylammonium salt is preferable from the viewpoint of imparting an excellent rinsing feeling to the hair cosmetic composition.

(Surfactant content)
The content of the surfactant in the hair cosmetic composition of the present invention is preferably 1 from the viewpoints of detergency, foaming properties and foam quality of the hair cosmetic composition, particularly from the viewpoint of obtaining an excellent rinsing feeling. It is at least 5 mass%, more preferably at least 5 mass%, preferably at most 80 mass%, more preferably at most 50 mass%, still more preferably at most 36 mass%.
When the hair cosmetic composition of the present invention is used as a hair cleansing composition, the content of the surfactant is 8% by mass or more from the viewpoint of imparting an excellent rinsing feeling to the hair cosmetic composition of the present invention. More preferably, it is more preferably 20% by mass or less.

(Mass ratio of CGC and surfactant)
In the hair cosmetic composition of the present invention, the content ratio of CGC and surfactant is preferably a mass ratio of CGC to surfactant [CGC / surfactant], particularly from the viewpoint of obtaining an excellent rinsing feeling. It is 0.0002 or more, more preferably 0.005 or more, still more preferably 0.01 or more, preferably 10 or less, more preferably 1 or less, still more preferably 0.1 or less.

(Other ingredients)
In the hair cosmetic composition of the present invention, glycerin, humectant, polysaccharide, polypeptide, pearlizing agent, solvent, pigment, fragrance, propellant, edet, usually blended in the hair cosmetic composition. Acetates, chelating agents such as citrate, pH adjusters, preservatives, anti-dandruff agents such as zinc pyrithione and piroctone olamine, and the like can be appropriately blended as necessary.

(Method for producing hair cosmetic composition)
There is no restriction | limiting in particular in the manufacturing method of the hair cosmetic composition of this invention, It can manufacture by a conventional method. Specifically, for example, in the case of a shampoo for liquid hair, water and a surfactant are heated and mixed uniformly. After confirming uniform dissolution, CGC is added and mixed. CGC can be added after previously dispersing or dissolving in water, if necessary. After adding CGC to the surfactant aqueous solution, it can be uniformly dissolved or dispersed, cooled, and added with a pearling agent, a pH adjusting agent, a fragrance, a pigment, and the like, if necessary.
Further, the dosage form of the hair cosmetic composition of the present invention is not particularly limited, and can be any dosage form such as liquid, foam, paste, cream, solid, powder, etc. It is preferable to be in the form of a paste, cream or cream, and it is particularly preferable that the liquid is used. In the case of a liquid state, it is preferable to use water, polyethylene glycol, ethanol or the like as the liquid medium, and the blending amount of water is 10% by mass or more and 90% by mass or less in the entire composition. preferable.

  The hair cosmetic composition of the present invention is preferably a hair cleanser composition such as a hair shampoo from the viewpoint of the effect of the present invention that an excellent rinsing feeling is obtained. The hair cosmetic composition of the present invention is a hair shampoo, hair rinse, hair conditioner, hair treatment, hair pack, hair cream, styling lotion, styling mousse, conditioning mousse, hair mousse, hair spray, shampoo, non-washing conditioner, permanent or It can be suitably used as a hair cosmetic such as a basic hair color or a permanent agent.

The present invention discloses the following method for producing cationized glycerolated cellulose and a hair cosmetic composition with respect to the embodiment described above.
<1>
A method for producing cationized glycerolated cellulose obtained by reacting raw material cellulose selected from cellulose and cellulose derivatives with at least glycidol and a cationizing agent, comprising the following steps 1 to 3: Manufacturing method.
Step 1: Raw material cellulose and glycidol are more than 0.9 molar equivalent per mole of anhydroglucose unit in the raw material cellulose, preferably 0.95 molar equivalent or more, more preferably 1.0 molar equivalent or more, still more preferably Is 1.1 molar equivalents or more, 1.6 molar equivalents or less, preferably 1.5 molar equivalents or less, more preferably 1.3 molar equivalents or less, and even more preferably 1.2 molar equivalents or less. Below, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and still more preferably 50% by mass or more, based on the cellulose portion of the raw material cellulose. Reacted in a solvent of 200% by weight or less, preferably 180% by weight or less, more preferably 150% by weight or less, and still more preferably 120% by weight or less. Step 2: Obtaining reaction mixture 1 containing glycerolated cellulose Step 2: Mixing reaction mixture 1 obtained in Step 1 and an acid, the amount of base compound is 0 per mole of anhydroglucose unit in raw cellulose. 0.1 molar equivalent or more, preferably 0.2 molar equivalent or more, more preferably 0.3 molar equivalent or more, still more preferably 0.5 molar equivalent or more, 0.9 molar equivalent or less, preferably 0.8 mole Step of adjusting the amount to not more than the equivalent, more preferably not more than 0.7 molar equivalent, and further reacting the raw material cellulose and glycidol Step 3: After step 2, the cationizing agent is added and reacted to obtain cationized glycerolated cellulose Process

<2>
Production of the cationized glycerolated cellulose according to the above <1>, wherein in step 2, the reaction mixture 1 and the acid are mixed simultaneously or after the reaction mixture 1 and the acid are mixed, glycidol is further added and reacted. Method.

<3>
In the solvent in Step 1, the mass ratio of the organic solvent to water (organic solvent / water) is 0 or more and 10 or less, preferably 0 or more and 6 or less, more preferably 0 or more and 4 or less, and still more preferably 0 or more and 1 or less. The method for producing a cationized glycerolated cellulose according to the above <1> or <2>, preferably 0 or more and 0.5 or less, and more preferably 0 or more and 0.1 or less.

<4>
In the solvent in Step 1, water is 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and 100% by mass or less, based on the cellulose portion of the raw material cellulose. Preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less, The manufacturing method of the cationized glycerolated cellulose in any one of said <1>-<3>.

<5>
In the solvent in Step 1, the organic solvent is 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 60% by mass or more, and 100% by mass with respect to the cellulose portion of the raw material cellulose. The method for producing cationized glycerolated cellulose according to any one of <1> to <4> above, preferably 90% by mass or less, more preferably 80% by mass or less.

<6>
The amount of the base compound in Step 3 is 0.1 molar equivalent or more, preferably 0.15 molar equivalent or more, more preferably 0.2 molar equivalent or more, per mole of anhydroglucose unit in the raw material cellulose, 0.6 The cation according to any one of the above items <1> to <5>, having a molar equivalent or less, preferably 0.5 molar equivalent or less, more preferably 0.4 molar equivalent or less, and still more preferably 0.3 molar equivalent or less. Process for producing glycerolated cellulose.

<7>
Step 3 is 50% by mass or more, preferably 80% by mass or more, more preferably 100% by mass or more, and 800% by mass or less, preferably 400% by mass or less, more preferably 300% by mass with respect to the cellulose portion of the raw material cellulose. The method for producing a cationized glycerolated cellulose according to any one of the above <1> to <6>, which is carried out in a solvent of not more than mass%.

<8>
<7> above, wherein the mass ratio of the organic solvent to water (organic solvent / water) in the solvent in Step 3 is 0 or more and 2 or less, preferably 0 or more and 1.5 or less, more preferably 0 or more and 1.2 or less. A process for producing the cationized glycerolated cellulose described in 1.

<9>
In the solvent in Step 3, water is 50% by mass or more, preferably 80% by mass or more, more preferably 100% by mass or more, still more preferably 120% by mass or more, and 500% by mass or less with respect to the cellulose portion of the raw material cellulose. The method for producing cationized glycerolated cellulose according to the above <7> or <8>, preferably 400% by mass or less, more preferably 300% by mass or less, and still more preferably 200% by mass or less.

<10>
In the solvent in the step 3, the organic solvent is 0% by mass or more, preferably 200% by mass or more, more preferably 300% by mass or more, and 500% by mass or less, preferably 400% by mass or less, with respect to the cellulose portion of the raw material cellulose. The method for producing a cationized glycerolated cellulose according to any one of <7> to <9>, more preferably 350% by mass or less.

<11>
In step 2, the equivalent ratio of the amount of the base compound after mixing the reaction mixture 1 and the acid to the amount of the base compound in the reaction mixture 1 is 0.1 or more, preferably 0.2 or more, more preferably 0.3. The method for producing cationized glycerolated cellulose according to any one of <1> to <10> above, which is 0.7 or less, preferably 0.6 or less, and more preferably 0.55 or less.

<12>
The acid is an organic acid, preferably at least one selected from acetic acid, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, succinic acid, fumaric acid, and adipic acid, more preferably at least one selected from acetic acid and lactic acid. The method for producing a cationized glycerolated cellulose according to any one of <1> to <11>, more preferably acetic acid.

<13>
Furthermore, as step 4, a group containing a hydrophobic group-introducing agent, preferably a hydrocarbon having 3 to 18 carbon atoms represented by any one of formulas (2) to (4) (hydrocarbon group-containing group) The method for producing cationized glycerolated cellulose according to any one of the above <1> to <12>, which comprises a step of reacting by adding the introduction agent.

<14>
The method for producing a cationized glycerolated cellulose according to the above <13>, which has Step 4 before Step 1 or between Step 2 and Step 3.

<15>
The cellulose derivative is hydrophobically modified cellulose, preferably having 3 or more carbon atoms, preferably 4 or more, 18 or less, preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, still more preferably 7 or less, The cationized glycerolated cellulose according to any one of the above <1> to <14>, which is a cellulose having one or more hydrophobic sites selected from hydroxyalkyl sites and oxyalkylene sites, more preferably 6 or less. Manufacturing method.

<16>
The hydrophobically modified cellulose is represented by the following general formula (1) and represented by the following general formulas (2) to (4), having 3 or more carbon atoms, preferably 4 or more, 18 or less, preferably 16 or less More preferably 12 or less, still more preferably 9 or less, even more preferably 7 or less, and even more preferably 6 or less, the degree of substitution of the group containing a hydrocarbon group of 0.0001 or more, preferably 0.0005 or more, More preferably 0.001 or more, still more preferably 0.005 or more, still more preferably 0.01 or more, still more preferably 0.02 or more, 0.2 or less, preferably 0.15 or less, more preferably The cationization according to the above <15>, wherein is 0.10 or less, more preferably 0.08 or less, still more preferably 0.06 or less, and still more preferably 0.04 or less. Method of manufacturing a Riseroru cellulose.

(In the general formula (1), R ¹ , R ² and R ³ each independently represents a substituent consisting of one or more structural units selected from the following general formulas (2) to (4), or a hydrogen atom. N represents the average degree of polymerization of the main chain derived from anhydroglucose, and is 100 or more, preferably 200 or more, more preferably 500 or more, still more preferably 1,000 or more, and 12,000 or less, preferably 10 2,000 or less, more preferably 5,000 or less, and still more preferably 2,500 or less.)

(In the general formula (1), the structural units represented by the general formulas (2) to (4) represent groups containing a hydrocarbon group having 3 to 18 carbon atoms. R ⁴ and R ⁵ are independent of each other. Represents a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms, preferably an alkyl group having 1 to 14 carbon atoms or 2 or more carbon atoms. An alkenyl group having 14 or less carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms. Group, more preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms. Even more preferably having 1 to 4 alkyl group having a carbon even more preferably methyl or ethyl, even more preferably an ethyl group .R ⁶ is having 3 to 18 carbon atoms, an alkyl group, an alkenyl group, An aralkyl group or an aryl group, preferably an alkyl group and an alkenyl having 3 to 6 carbon atoms, preferably one or more selected from an alkyl group, an alkenyl group, and a phenyl group, more preferably an alkyl group having 3 to 6 carbon atoms 1 or more selected from the group, more preferably an alkyl group having 3 to 6 carbon atoms, p represents an integer of 0 or 1. In the structural units represented by the general formulas (2) and (3), The oxygen atom is bonded to a hydrogen atom or a carbon atom of the structural unit represented by any one of the general formulas (2) to (4).

<17>
The cationic charge density of the cationized glycerolated cellulose is 0.05 mmol / g or more, preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, still more preferably 0.3 mmol / g or more, and even more preferably. Is 0.4 mmol / g or more, more preferably 0.45 mmol / g or more, 2.0 mmol / g or less, preferably 0.8 mmol / g or less, more preferably 0.7 mmol / g or less, still more preferably The method for producing a cationized glycerolated cellulose according to any one of the above <1> to <16>, wherein Step 3 is performed so as to be 0.6 mmol / g or less, more preferably 0.55 mmol / g or less.

<18>
The degree of substitution of the cationic group per anhydroglucose unit in the cationized glycerolated cellulose is 0.01 or more, preferably 0.03 or more, more preferably 0.06 or more, still more preferably 0.1 or more, even more Preferably it is 0.15 or more, 1.0 or less, preferably 0.5 or less, more preferably 0.3 or less, further preferably 0.22 or less, and still more preferably 0.19 or less. 3. The method for producing a cationized glycerolated cellulose according to any one of <1> to <17>, wherein step 3 is performed.

<19>
The degree of substitution of glycerol groups per anhydroglucose unit in cationized glycerolated cellulose is 0.5 or more, preferably 0.7 or more, more preferably 0.8 or more, still more preferably 1.0 or more, and still more preferably Is 1.2 or more, more preferably 1.5 or more, 5.0 or less, preferably 4.0 or less, more preferably 3.5 or less, still more preferably 3.0 or less, and still more preferably 2. The method for producing a cationized glycerolated cellulose according to any one of the above <1> to <18>, wherein the step 1 and the step 2 are performed so as to be 5 or less.

<20>
A hair cosmetic composition comprising cationized glycerolated cellulose obtained by the production method according to any one of <1> to <19>, a surfactant, and water.

<21>
The hair cosmetic composition according to the above <20>, which is a hair cleansing composition.

<22>
The content of cationized glycerolated cellulose is 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and 10% by mass or less, preferably 5% by mass or less. The hair cosmetic composition according to <20> or <21>, preferably 1% by mass or less.

<23>
The mass ratio of the amount of cationized glycerolated cellulose to surfactant is 0.0002 or more, preferably 0.005 or more, more preferably 0.01 or more, 10 or less, preferably 1 or less, more preferably 0. The hair cosmetic composition according to any one of <20> to <22>, which is 1 or less.

In the following examples and comparative examples, “%” means “% by mass”. In the above general formulas (2) and (3), the groups in which R ⁴ and R ⁵ are methyl groups are collectively referred to as “oxypropylene groups” in the following examples. Also called “oxybutylene group”. Various physical properties were measured by the following methods.

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

(2) Measurement of viscosity average degree of polymerization of cellulose (copper ammonia method)
(I) Preparation of solution for measurement After adding 0.5 g of cuprous chloride and 20-30 mL of 25% aqueous ammonia to a measuring flask (100 mL) and completely dissolving, 1.0 g of cupric hydroxide and 25% Aqueous ammonia was added to make up the volume, and the mixture was stirred for 3 hours to completely dissolve.
(Ii) Preparation of Sample After adding 25 mg of the measurement sample to the measuring flask (25 mL), the solution prepared above was added until the meniscus coincided with the mark of the flask. This was stirred for 6 hours and completely dissolved.
(Iii) Measurement of viscosity average degree of polymerization The obtained copper ammonia aqueous solution was put into an Ubbelohde viscometer and allowed to stand in a thermostatic bath (20 ± 0.1 ° C.) for 1 minute, and then the flow rate of the liquid was measured. From the flow time (t (second)) of the copper ammonia solution having various sample concentrations (g / L) and the flow time (t ₀ (second)) of the copper ammonia aqueous solution without addition of the sample, the relative viscosity η sought _r .
η _r = t / t ₀
Next, the reduced viscosity (η _sp / c) at each concentration was determined from the following equation.
η _sp / c = (η _r −1) / c (c: sample concentration (g / dL))
Further, the reduced viscosity was extrapolated to c = 0 to determine the intrinsic viscosity [η], and the viscosity average polymerization degree (n) was determined from the following formula.
n = 2000 × [η]
In the examples, the average degree of polymerization of CGC was considered to be the same as the average degree of polymerization of the raw material cellulose used in the production.

(3) Calculation of substitution degree of substituent in CGC Degree of substitution of glycerol group (MS (Gly)) of CGC, substitution degree of cationic group (MS (N +)), substitution degree of hydrocarbon group-containing group (MS ( HC)) was calculated by the following simultaneous equations (1) to (3).
-A x (glycerol group content (%)) x MS (HC) + (74.1-74.1 x (glycerol group content (%))) x MS (Gly)-b x (glycerol group Content (%)) × MS (N +) = 162.1 × (glycerol group content (%)) (1)
-A x (nitrogen content (%)) x MS (HC)-74.1 x (nitrogen content (%)) x MS (Gly) + (bb-nitrogen content (mass%)) x MS (N +) = 162.1 × (nitrogen content (%)) (2)
(Aa- (content of hydrocarbon group-containing group (%))) × MS (HC) -74.1 × (content of hydrocarbon group-containing group (%)) × MS (Gly) -b × (Content of hydrocarbon group-containing group (%)) × MS (N +) = 162.1 × (Content of hydrocarbon group-containing group (%)) (3)
(In the formula, a represents the molecular weight of the hydrocarbon group-containing group, and b represents the molecular weight of the cationic group.

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

(4) Calculation of substitution degree of substituent in cationized hydroxypropylcellulose Cationic hydroxypropylcellulose (hereinafter also referred to as “C-HPC”. Reacting cellulose with propylene oxide and 3-chloro-2-hydroxypropyltrimethylammonium chloride. The average value per number of AGUs constituting the cellulose skeleton that is the main chain of C-HPC (hereinafter also referred to as “degree of substitution of cationic groups”) of the cationic groups introduced into the cellulose ether obtained by The average value of the number of oxypropylene groups introduced into C-HPC per AGU of the main chain of C-HPC (hereinafter also referred to as “degree of substitution of oxypropylene groups”) is a measurement of the amount of chlorine element by elemental analysis. Value and the analysis target is C-HPC instead of hydroxypropylcellulose. From the values obtained according to the hydroxypropyl cellulose analysis method described in the 15th revision Japanese Pharmacopoeia.
Specifically, an aqueous solution of C-HPC was purified by a dialysis membrane (fraction molecular weight 1000), and the aqueous solution was lyophilized to obtain purified C-HPC. The chlorine content (%) of the obtained C-HPC was measured by elemental analysis, and the number of cationic groups contained in the purified C-HPC and the number of counter ions as chloride ions were approximated to be the same number. From the following calculation formula (4), the amount (a (mol / g)) of the cationic group contained in the C-HPC unit mass was determined.
a (mol / g) = chlorine content obtained from elemental analysis (%) / (35.5 × 100) (4)
Next, the content of hydroxypropoxy group in purified C-HPC according to "Analytical method of hydroxypropyl cellulose" described in the 15th revision Japanese Pharmacopoeia, except that the object of analysis is not purified hydroxypropylcellulose but purified C-HPC (%) Was measured. From the following formula (5), 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 chromatographic analysis (%) / (75.09 × 100) (5)
From the obtained a and b and the following formulas (6) and (7), the degree of substitution (k) of the cationic group and the degree of substitution (m) of the oxypropylene group of C-HPC were calculated.
a = k / (162 + k × 151.5 + m × 58) (6)
b = m / (162 + k × 151.5 + m × 58) (7)
[In formula, k shows the substitution degree of the cationic group of C-HPC. m represents the degree of substitution of the oxypropylene group. ]

Example 1 [Production of CGC (1)]
(1) Cellulose pulverization process Sheet wood pulp ("BioflocXV18" manufactured by Tenbeck, average polymerization degree 1882) was shredded ("MSX2000-IVP440F" manufactured by Meiko Shokai Co., Ltd.) to form chips. Then, the drying process was performed under 105 degreeC pressure reduction for 12 hours, and the chip-shaped dry pulp was obtained. Next, 920 g of the obtained dry chip-like pulp was made into a batch type vibration mill (Chuo Kako Co., Ltd. “FV-10”: container total volume 35 L, as a rod, φ30 mm, length 510 mm, circular sectional shape made of SUS304 It was put into 63 rods (filling rate 70%) and pulverized for 10 minutes (frequency 20 Hz, amplitude 8 mm, temperature 10 to 20 ° C.) to obtain powdery cellulose. The obtained powdered cellulose was fitted with a screen having a mesh opening of 0.7 mm using a high-speed rotary fine pulverizer (“Dalton Co., Ltd.“ Sample Mill, KIIW-1 ”), and the rotor peripheral speed was 81 m / s. And at the same time, powdered cellulose was supplied from the raw material supply section at a rate of 18 kg / h. Next, an SUS screen with a sieve area of 0.196 m ² and an opening of 150 μm is attached to a circular vibrating sieve (“KGC-500” manufactured by Kowa Kogyo Co., Ltd.), and a vibration frequency of 30 Hz (vibration speed of 1800 r / min). Driven with a longitudinal single piece amplitude of 3 mm, a transverse single piece amplitude of 3 mm, and a weight phase angle of 60 °, the raw material is supplied from the raw material supply section at a supply rate of 14 kg / h to remove coarse powder, It recovered as a diameter cellulose powder.

(2) Glycerization reaction (step 1)
While charging 91.3 g (moisture content 1.4% by mass) of the cellulose powder obtained in the above (1) into a 1 L kneader (Irie Shokai Co., Ltd., PNV-1 type) equipped with a reflux tube, while performing nitrogen flow Stir for 10 minutes. Thereafter, 74.5 g (1.2 molar equivalent / AGU) of 35.8% NaOH aqueous solution was dropped over 15 minutes, and then the jacket temperature was adjusted to 50 ° C. and stirred for 2 hours to obtain a cellulose powder mixture. It was.
After adjusting the jacket temperature to 40 ° C., 32.9 g of glycidol (0.8 mol / AGU, manufactured by Kanto Chemical Co., Inc.) was added dropwise to the cellulose powder mixture over 1 hour, and the reaction was carried out with stirring to produce glycerolated cellulose. A reaction mixture (1) containing was obtained.
(Process 2)
While stirring the resulting reaction mixture (1), 20.0 g of acetic acid (0.6 molar equivalent / AGU, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at a jacket temperature of 40 ° C. over 30 minutes, partially. Neutralization was performed. Next, 131.7 g (3.2 mol / AGU, manufactured by Kanto Chemical Co., Inc.) of glycidol was added dropwise over 4 hours, and the reaction was carried out with stirring to obtain a reaction mixture (2) containing glycerolated cellulose.

(3) Introduction reaction of hydrocarbon group-containing group (step 4)
After adjusting the jacket temperature to 50 ° C., while stirring the obtained reaction mixture (2), 5.7 g of butylene oxide (0.14 mol / AGU, Tokyo Chemical Industry Co., Ltd.) as a hydrocarbon group-containing group introducing agent. Product) was added dropwise and reacted for 1 hour. By this reaction, an oxybutylene group, which is a hydrocarbon group-containing group, was introduced into the glycerolated cellulose in the reaction mixture (2) to obtain a reaction mixture (3) containing glycerolated cellulose that was hydrophobically modified.

(4) Cationization reaction (step 3)
While stirring the obtained reaction mixture (3), 56.2 g (0.35 mol / AGU) of 65% 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution (manufactured by Yokkaichi Chemical Co., Ltd.) and 72% glycidyl A cationizing agent aqueous solution in which 1.2 g (0.01 mol / AGU) of trimethylammonium chloride (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) and 60.4 g of ion-exchanged water was mixed was dropped over 1 minute (water content during reaction: The jacket temperature was adjusted to 65 ° C. and the reaction was carried out for 3 hours with respect to the cellulose portion of the raw material cellulose. By this reaction, the hydrophobically modified glycerolated cellulose in the reaction mixture (3) was cationized to obtain a light yellow powder containing the cationized glycerolated cellulose.

(5) Neutralization and purification process 90% lactic acid (manufactured by Musashino Chemical Laboratory Co., Ltd.) was added dropwise to the obtained pale yellow powder over 1 minute to neutralize, and then 5.0 g of the final reaction product was used. 1% by weight aqueous solution was prepared. Purification was performed by dialysis with ion-exchanged water using a dialysis membrane (“Spectrapore 6” manufactured by Wako Pure Chemical Industries, Ltd., molecular weight cut-off 8000). Specifically, after 500 g of the 1% by mass aqueous solution is sealed in a dialysis membrane, it is immersed in ion exchange water at least 20 times by mass with respect to the 1% by mass aqueous solution, and dialyzed at least for 3 hours or more. The water outside the membrane was exchanged with ion-exchanged water three times, and then allowed to stand for 3 hours or more. After completion of the dialysis purification, freeze-drying was performed to obtain a white solid CGC (1). The analysis results of the obtained CGC (1) are shown in Tables 1 and 2.

Example 2 [Production of CGC (2)]
(1) Cellulose powderization process The same operation as (1) of Example 1 was performed.

(2) Glycerization reaction (step 1)
In a Redige mixer (manufactured by Matsubo Co., Ltd., capacity 5 L), 295.6 g (moisture content 2.17%) of the cellulose powder obtained in the above (1) was charged, and nitrogen substitution was performed. While stirring at a main wing of 250 rpm and a chopper blade of 2500 rpm, 237.2 g (1.2 molar equivalent / weight) of a 36.1% NaOH aqueous solution prepared with granular sodium hydroxide (manufactured by Kishida Chemical Co., Ltd., special grade reagent) and ion-exchanged water. AGU) was added by spraying over 30 seconds. After spraying, the internal temperature was raised to 50 ° C. and stirred for 2 hours.
After adjusting the internal temperature to 40 ° C., 105.8 g of glycidol (0.8 mol / AGU, manufactured by Kanto Chemical Co., Inc.) was stirred for 1 hour while stirring the obtained cellulose powder mixture with a main wing 250 rpm and a chopper wing 2500 rpm. The reaction mixture was added dropwise and stirred to obtain a reaction mixture (1) containing glycerolated cellulose.
(Process 2)
While stirring the obtained reaction mixture (1) with a main wing of 250 rpm and a chopper blade of 2500 rpm, 64.3 g of acetic acid (0.6 molar equivalent / AGU, manufactured by Wako Pure Chemical Industries, Ltd.) was applied over 30 minutes at an internal temperature of 40 ° C. The solution was added dropwise and partially neutralized. Subsequently, 423.1 g of glycidol (3.2 mol / AGU, manufactured by Kanto Chemical Co., Ltd.) was added dropwise over 4 hours, the reaction was carried out at an internal temperature of 40 ° C. with stirring, and a reaction mixture containing glycerolated cellulose (2 )

(3) Introduction reaction of hydrocarbon group-containing group (step 4)
After adjusting the internal temperature to 50 ° C., while stirring the obtained reaction mixture (2) with a main blade of 250 rpm and a chopper blade of 2500 rpm, 9.4 g (0.07 mol / 0.03) of butylene oxide was introduced as a hydrocarbon group-containing group introduction agent. AGU, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and reacted for 1 hour. By this reaction, an oxybutylene group, which is a hydrocarbon group-containing group, was introduced into the glycerolated cellulose in the reaction mixture (2) to obtain a reaction mixture (3) containing glycerolated cellulose that was hydrophobically modified.

(4) Cationization reaction (step 3)
While stirring the obtained reaction mixture (3) at a main wing of 250 rpm and a chopper blade of 2500 rpm, 179.0 g (0.35 mol) of 65% 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution (manufactured by Yokkaichi Gosei Co., Ltd.) / AGU), 72% glycidyltrimethylammonium chloride (Sakamoto Yakuhin Kogyo Co., Ltd.) 27.6 g (0.07 mol / AGU), ion-exchanged water 651.4 g, and 2-propanol (Wako Pure Chemical Industries, Ltd.) 964 A cationizing agent aqueous solution mixed with 0.0 g (333% by mass with respect to the cellulose part of the raw material cellulose) was dropped over 1 minute (water content during reaction: 400% by mass with respect to the cellulose part of the raw material cellulose), and the internal temperature Reaction was performed at 50 degreeC for 3 hours. By this reaction, the hydrophobically modified glycerolated cellulose in the reaction mixture (3) was cationized to obtain a light yellow powder containing the cationized glycerolated cellulose.

(5) Neutralization and purification step The same operation as in (5) Neutralization and purification step of Example 1 was performed to obtain CGC (2). The analytical results of the obtained CGC (2) are shown in Tables 1 and 2.

Example 3 [Production of CGC (3)]
In Example 1, except that the amount of ion-exchanged water added in the cationization reaction (step 3) of (4) was changed to 159.3 g (water content during reaction: 250% by mass with respect to the cellulose portion of the raw material cellulose). Performed the same operation as Example 1 to obtain CGC (3). The analysis results of the obtained CGC (3) are shown in Tables 1 and 2.

Example 4 [Production of CGC (4)]
In Example 1, the amount of glycidol was changed to 125.5 g (3.05 mol / AGU) in step 2 of (2) glycerolation reaction, and 72% glycidyltrimethyl was used in the cationization reaction (step 3) of (4). Except that ammonium chloride was changed to 5.8 g (0.05 mol / AGU) and the amount of ion-exchanged water added was changed to 37.9 g (water content during reaction: 115% by mass with respect to the cellulose portion of the raw material cellulose). The same operation as in Example 1 was performed to obtain CGC (4). The analytical results of the obtained CGC (4) are shown in Tables 1 and 2.

Example 5 [Production of CGC (5)]
In Example 4, 74.5 g (1.2 molar equivalents / AGU) of 35.8% aqueous NaOH solution was added to 61.9 g (1.0 molar equivalents / AGU) of 35.8% aqueous NaOH solution in Step 1 of (2) glycerolation reaction. AGC) was carried out in the same manner as in Example 4 except that the amount of acetic acid was changed to 13.3 g (0.4 molar equivalent / AGU) in Step 2 of the (2) glycerolation reaction, and CGC (5) Got. The analysis results of the obtained CGC (5) are shown in Tables 1 and 2.

Example 6 [Production of CGC (6)]
In Example 1, the cationizing agent aqueous solution of the cationization reaction (step 3) of (4) was mixed with 32.2 g (0.2 mol / AGU) of 65% aqueous 3-chloro-2-hydroxypropyltrimethylammonium chloride solution. CGC (6) was obtained in the same manner as in Example 1 except that the solution was changed to a solution in which 18.7 g (0.16 mol / AGU) of 72% glycidyltrimethylammonium chloride and 64.0 g of ion-exchanged water were mixed. It was. The analytical results of the obtained CGC (6) are shown in Tables 1 and 2.

Example 7 [Production of CGC (7)]
(1) Cellulose pulverization process Sheet wood pulp ("BioflocXV18" manufactured by Tenbeck, average polymerization degree 1882) was shredded ("MSX2000-IVP440F" manufactured by Meiko Shokai Co., Ltd.) to form chips. Then, the drying process was performed under 105 degreeC pressure reduction for 12 hours, and the chip-shaped dry pulp was obtained. Next, 100 g of the obtained dried chip-like pulp and 23.8 g of granular sodium hydroxide (1.0 molar equivalent / AGU, manufactured by Kishida Chemical Co., Ltd.) were mixed with a batch vibration mill (manufactured by Chuo Kako Co., Ltd. “MB-1”: A container having a total volume of 3.5 L, a rod of φ30 mm, a length of 218 mm, and 13 SUS304 rods with a circular cross-sectional shape, a filling rate of 57%. A cellulose powder mixture was obtained by pulverizing for 10 minutes (frequency 20 Hz, amplitude 8 mm, temperature 10 ° C.).

(2) Introduction reaction of hydrocarbon group-containing group (step 4)
6 L of cellulose powder mixture obtained in the above (1) (containing 1.0 molar equivalent / AGU of sodium hydroxide) was added to a 1 L kneader (manufactured by Irie Shokai Co., Ltd., PNV-1 type) equipped with a reflux tube. The mixture was stirred and stirred for 10 minutes while flowing nitrogen. Thereafter, 15 g of ion-exchanged water (water content at the time of reaction: 30% by mass with respect to the cellulose portion of the raw material cellulose) was dropped while stirring, and the jacket temperature was adjusted to 50 ° C. Next, while stirring, 4.5 g of butylene oxide (0.20 mol / AGU, manufactured by Tokyo Chemical Industry Co., Ltd.) is added dropwise as a hydrocarbon group-containing group introducing agent, and the reaction is performed at a jacket temperature of 50 ° C. for 4 hours. It was. By this reaction, an oxybutylene group, which is a hydrocarbon group-containing group, was introduced into the cellulose to obtain a reaction mixture containing hydrophobically modified cellulose to be a raw material cellulose.

(3) Glycerization reaction (step 1)
While stirring the reaction mixture containing the hydrophobically modified cellulose obtained in (2) above, 18.3 g of glycidol (0.8 mol / AGU, manufactured by Kanto Chemical Co., Ltd.) was added to 37.1 g of tetrahydrofuran (glycidol concentration of 33% by mass, A solution diluted with Wako Pure Chemical Industries, Ltd.) was added dropwise over 5 hours and reacted at a jacket temperature of 50 ° C. to obtain a reaction mixture (1) containing hydrophobically modified glycerolated cellulose.
(Process 2)
While stirring the obtained reaction mixture (1), 7.4 g of acetic acid (0.4 molar equivalent / AGU, manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 30 minutes at a jacket temperature of 50 ° C., and partially Neutralization was performed. Then, a solution obtained by diluting 57.2 g of glycidol (2.5 mol / AGU, manufactured by Kanto Chemical Co., Inc.) with 116.1 g of tetrahydrofuran (glycidol concentration 33% by mass) was dropped over 15 hours, and the jacket temperature was stirred The reaction was carried out at 50 ° C. to obtain a reaction mixture (2) containing hydrophobically modified glycerolated cellulose.

(4) Cationization reaction (step 3)
15.5 g of the obtained reaction mixture (2) was extracted from the kneader, and tetrahydrofuran was distilled off by nitrogen flow. Thereafter, the reaction mixture (2) was transferred to a mortar, and 1.6 g (0.36) of HAC-65 (65% 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution (manufactured by Yokkaichi Gosei Co., Ltd.)) as a cationizing agent. Mol / AGU) and 1.8 g of ion-exchanged water were added dropwise and mixed with a pestle for 1 minute (water content during reaction: 121% by mass with respect to the cellulose portion of the raw material cellulose). The mixture was transferred to a 100 mL vial, purged with nitrogen, sealed, and allowed to react in a thermostat at 50 ° C. for 5 hours. By this reaction, the hydrophobically modified glycerolated cellulose in the reaction mixture (2) was cationized to obtain a light yellow powder containing the hydrophobically modified cationized glycerolated cellulose.

(5) Neutralization and purification step The same operation as in (5) Neutralization and purification step of Example 1 was performed to obtain CGC (7). The analytical results of the obtained CGC (7) are shown in Tables 1 and 2.

Example 8 [Production of CGC (8)]
In Example 1, (2) the amount of glycidol was 82.3 g (2.0 mol / AGU) in Step 1 of the glycerolation reaction, and the amount of glycidol was 82.3 g (2.0 mol / AGU) in Step 2. Except for the change, the same operation as in Example 1 was performed to obtain CGC (8). The analytical results of the obtained CGC (8) are shown in Tables 1 and 2.

Example 9 [Production of CGC (9)]
In Example 1, (2) the amount of glycidol was 115.2 g (2.8 mol / AGU) in Step 1 of the glycerolation reaction, and the amount of glycidol was 49.4 g (1.2 mol / AGU) in Step 2. Except for the change, the same operation as in Example 1 was performed to obtain CGC (9). The analytical results of the obtained CGC (9) are shown in Tables 1 and 2.

Example 10 [Production of CGC (10)]
In Example 1, the amount of glycidol was changed to 164.6 g (4.0 mol / AGU) in Step 2 of (2) glycerolation reaction, and when the amount of glycidol was 0.5 mol / AGU, acetic acid was CGC (10) was obtained by performing the same operation as in Example 1 except that the reaction was performed by adding. The analysis results of the obtained CGC (10) are shown in Tables 1 and 2.

Example 11 [Production of CGC (11)]
In Example 1, the amount of acetic acid was changed to 31.7 g (0.95 molar equivalent / AGU) in step 2 of (2) glycerolation reaction, and the cationizing agent of cationization reaction (step 3) of (4) Except that the aqueous solution was changed to a mixed solution of 42.1 g (0.36 mol / AGU) of 72% glycidyltrimethylammonium chloride and 69.0 g of ion-exchanged water, the same operation as in Example 1 was performed, and CGC (11) was changed. Obtained. The analysis results of the obtained CGC (11) are shown in Tables 1 and 2.

Example 12 [Production of CGC (12)]
In Example 1, CGC (12) was obtained in the same manner as in Example 1 except that (3) introduction of the hydrocarbon group-containing group (Step 4) was not performed. The analysis results of the obtained CGC (12) are shown in Tables 1 and 2.

Comparative Example 1 [Production of CGC (13)]
In Example 1, (2) glycerolation reaction step 2 was not carried out, but 164.6 g (4.0 mol / AGU) of glycidol was added and reacted in step 1, and (4) cationization reaction (step) The same operation as in Example 1 was carried out except that the amount of the base compound was changed to 0.85 molar equivalent / AGU in 3) to obtain CGC (13). The analysis results of the obtained CGC (13) are shown in Tables 1 and 2.

Comparative Example 2 [Production of CGC (14)]
In Comparative Example 1, (4) cationization in which 69.0 g of ion-exchanged water and 42.1 g of 72% glycidyltrimethylammonium chloride (0.36 mol / AGU) were mixed as a cationizing agent in the cationization reaction (step 3). CGC (14) was obtained in the same manner as in Comparative Example 1, except that an aqueous agent solution was added and the amount of the base compound during the reaction in Step 3 was changed to 1.20 molar equivalent / AGU. The analytical results of the obtained CGC (14) are shown in Tables 1 and 2.

Comparative Example 3 [Production of CGC (15)]
In Comparative Example 1, the same operation as in Comparative Example 1 was carried out except that the introduction of the hydrocarbon group-containing group (3) (Step 4) was not carried out to obtain CGC (15). The analysis results of the obtained CGC (15) are shown in Tables 1 and 2.

Comparative Example 4 [Production of C-HPC (1)]
In Example 12, in the step of (2) glycerolation reaction, the same operation as in Example 12 was performed except that glycidol was changed to propylene oxide (manufactured by Wako Pure Chemical Industries, Ltd.) in the amount shown in Table 1. C-HPC (1) was obtained. The analytical results of the obtained C-HPC (1) are shown in Tables 1 and 2.

[Evaluation of hair cosmetic composition]
Examples 13 to 24, Comparative Examples 5 to 8 (production and evaluation of hair shampoo)
(Manufacturing)
CGC or C-HPC obtained by the methods of Examples 1 to 12 and Comparative Examples 1 to 4, and sodium polyoxyethylene alkylsulfate ("Emar 170J" (70% aqueous solution) manufactured by Kao Corporation), oxy as a surfactant Average addition mole number of ethylene group: 1, alkyl chain length; C10-16), coconut oil fatty acid amide propyl carbobetaine (“Amphitol 55AB” (30% aqueous solution) manufactured by Kao Corporation), coconut oil fatty acid monoethanolamide (river A hair shampoo having an effective amount of each component as shown in Table 3 was prepared using “Amizole CME” manufactured by Ken Fine Chemical Co., Ltd.). Specifically, CGC or C-HPC was dissolved in water to prepare a 2% by mass polymer solution. Separately, each component other than the polymer is taken in a beaker, heated to 80 ° C. and stirred, and uniformly dissolved. Then, the polymer solution is added, uniformly mixed and cooled, and finally the water evaporated by heating is replenished. It was a hair shampoo.
(Evaluation)
Each component having the following composition was taken in a beaker, heated to 80 ° C., mixed and confirmed to be uniformly dissolved, and then cooled to obtain a plain shampoo. A hair bundle (20 g) was washed with the obtained plain shampoo and sufficiently moistened with warm water of 35 to 40 ° C. to obtain an evaluation tress. Next, the evaluation tress was washed with a hair shampoo (0.5 g) having the composition shown in Table 3, and rinsed with warm water (35 to 40 ° C.). Using the hair bundles thus treated, five panelists evaluated the slipperiness, the continuity of slippage, and the coat feeling when rinsing the hair according to the following evaluation criteria and evaluation methods. The evaluation results are shown in Table 3.

(Plain shampoo composition)
(Ingredient) (%)
Polyoxyethylene lauryl ether sulfate Na (Emar E-27C) 11.3
(42.0% as Emar E-27C (Kao Corporation, effective 27%))
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

(Evaluation criteria)
・ Slip:
7: Very good sliding property and no friction feeling 6: Good sliding property and very little friction feeling 5: Good sliding property and little friction feeling 4: Good sliding property and good friction feeling Slightly less 3: Normal 2: Slippery is poor and squeaks (standard: the result of Comparative Example 8 is 2)
1: No sliding at all, squeaky and persistent feeling:
7: Sliding property lasts for 50 seconds or more 6: Sliding property lasts for 30 seconds or more and less than 50 seconds 5: Sliding property lasts for 20 seconds or more but less than 30 seconds 4: Sliding property lasts for 10 seconds or more but less than 20 seconds 3 : Sliding property lasts for 5 seconds or more and less than 10 seconds 2: Sliding property lasts for 1 second or more and less than 5 seconds 1: Sliding property lasts for less than 1 second
7: Excellent coating feeling 6: Excellent coating feeling 5: Feeling the coating feeling 4: Feeling the coating feeling a little 3: Normal 2: Less coating feeling (standard: the result of Comparative Example 8 is 2)
1: A feeling of coat is not felt at all (evaluation method)
Scores were obtained by averaging the evaluation results of five panelists.

  From Table 3, it can be seen that hair cosmetic compositions using CGC (1) to (12) obtained by the production methods of Examples 1 to 12 are excellent in rinsing feeling.

  According to the present invention, when blended with a hair cosmetic such as a hair cleansing agent, cationized glycerolated cellulose capable of imparting excellent slipperiness during hair rinsing, its long-lasting feeling, and a feeling of coating can be efficiently produced. be able to. Therefore, the composition containing the cationized glycerolated cellulose can be suitably used as a hair cosmetic.

Claims (12)

A method for producing cationized glycerolated cellulose obtained by reacting raw material cellulose selected from cellulose and cellulose derivatives with at least glycidol and a cationizing agent, comprising the following steps 1 to 3: Manufacturing method.
Step 1: The raw material cellulose and glycidol are added to the cellulose portion of the raw material cellulose in the presence of a base compound of more than 0.9 molar equivalent and 1.6 molar equivalents or less per mole of anhydroglucose unit in the raw material cellulose. Step of obtaining a reaction mixture 1 containing glycerolated cellulose by reacting in a solvent of 10% by mass or more and 200% by mass or less Step 2: Mixing the reaction mixture 1 obtained in Step 1 with an acid, The step of adjusting the amount to 0.1 to 0.9 molar equivalent per mole of anhydroglucose unit in the raw material cellulose, and further reacting the raw material cellulose and glycidol Step 3: After Step 2, a cationizing agent is added Step of adding and reacting to obtain cationized glycerolated cellulose   The method for producing cationized glycerolated cellulose according to claim 1, wherein in step 2, glycidol is further added and reacted simultaneously with mixing of reaction mixture 1 and acid, or after mixing reaction mixture 1 and acid. .   The method for producing cationized glycerolated cellulose according to claim 1 or 2, wherein the mass ratio of the organic solvent to water (organic solvent / water) in the solvent in Step 1 is 0 or more and 10 or less.   The manufacturing method of the cationized glycerolated cellulose in any one of Claims 1-3 whose water is 10 to 100 mass% in the solvent in the process 1 with respect to the cellulose part of a raw material cellulose.   The cationized glycerolated cellulose according to any one of claims 1 to 4, wherein the amount of the base compound in step 3 is 0.1 to 0.6 molar equivalent per mole of anhydroglucose unit in the raw cellulose. Manufacturing method.   The method for producing cationized glycerolated cellulose according to any one of claims 1 to 5, wherein Step 3 is carried out in a solvent of 50% by mass or more and 800% by mass or less with respect to the cellulose part of the raw material cellulose.   7. The process according to claim 1, wherein in step 2, the equivalent ratio of the amount of the base compound after mixing the reaction mixture 1 and the acid with respect to the amount of the base compound in the reaction mixture 1 is 0.1 or more and 0.7 or less. A method for producing the cationized glycerolated cellulose according to claim 1.   Furthermore, as the process 4, the manufacturing method of the cationized glycerolated cellulose in any one of Claims 1-7 which has the process of adding a hydrophobic group introduction agent and making it react.   The method for producing cationized glycerolated cellulose according to claim 8, which comprises step 4 before step 1 or between step 2 and step 3.   The process according to any one of claims 1 to 9, wherein Step 1 and Step 2 are performed so that the degree of substitution of glycerol groups per anhydroglucose unit in the cationized glycerolated cellulose is 0.5 or more and 5.0 or less. A method for producing cationized glycerolated cellulose.   A hair cosmetic composition containing the cationized glycerolated cellulose obtained by the production method according to claim 1, a surfactant, and water.   The hair cosmetic composition according to claim 11, wherein the content of the cationized glycerolated cellulose is 0.01% by mass or more and 10% by mass or less.