JP2020094129A - Manufacturing method of cationized hydroxyalkyl cellulose - Google Patents

Abstract

To provide a manufacturing method of cationized hydroxyalkyl cellulose blended with a hair cleaning agent good in slipperiness of foam during washing and smoothness of hair during rinsing and after drying, and a manufacturing method of a hair cosmetic containing the cationized hydroxyalkyl cellulose.SOLUTION: There is provided a manufacturing method of cationized hydroxyalkyl cellulose including following processes 1 and 2 in this order. Process 1: a process for pulverizing pulp with 18 mass% sodium hydroxide soluble component of 5.6 mass% or less to obtain powdered cellulose. Process 2: a process for getting the powdered cellulose obtained in the process 1 in reaction with alkylene oxide and a cationization agent.SELECTED DRAWING: None

Description

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

BACKGROUND ART Conventionally, a cationic polymer is generally blended with a conditioning agent for hair cosmetics in order to improve finger combability, softness and cohesion.
Patent Document 1 discloses a surfactant and a cationization agent for the purpose of providing a hair cosmetic composition which does not have a sticky feeling after use and can impart excellent finger combability, coat feeling, and cohesive feeling to hair. A hair cosmetic containing hydroxypropyl cellulose, wherein the cationized hydroxypropyl cellulose has a main chain derived from anhydroglucose, and the degree of substitution of the cationized ethyleneoxy group is 0.01 to 2.5. And a hair cosmetic having a propyleneoxy group substitution degree of 0.1 to 2.8 is disclosed.
It is also known to add hemicellulose in order to improve the set holding power of hair.
Patent Document 2 discloses a hair cosmetic composition characterized by containing one or more hemicelluloses for the purpose of providing a hair cosmetic composition having excellent set-holding power and having a good feeling in use. ing.

International Publication No. 2011/059063 JP, 7-258041, A

Patent Document 1 describes the use of a specific cationized hydroxypropyl cellulose as a hair cosmetic composition that does not give a sticky feeling after use and can impart excellent finger combability, coat feeling, and cohesive feeling to hair. In Patent Document 2, it is described that by blending hemicellulose, the settability of the hair is improved, but with regard to the smoothness of the foam during washing, the smoothness of the hair after rinsing and after drying, Still not enough.
An object of the present invention is to obtain a hair cleansing agent which has good smoothness of foam during hair washing and is excellent in smoothness of hair after rinsing and after drying, and a method for producing a cationized hydroxyalkyl cellulose to be blended therein and the method. The present invention relates to a method for producing a hair cosmetic containing cationized hydroxyalkyl cellulose.

The present inventors have found that the above problems can be solved by using a specific pulp raw material.
That is, the present invention relates to the following [1] and [2].
[1] A method for producing a cationized hydroxyalkyl cellulose, which comprises the following Step 1 and Step 2 in this order.
Step 1: Step of crushing pulp having 18% by mass of sodium hydroxide soluble content of 5.6% by mass or less to obtain powdery cellulose Step 2: The powdery cellulose obtained in Step 1 is added with alkylene oxide and cation Step [2] of reacting with an agent A method for producing a hair cosmetic, which comprises mixing a cationized hydroxyalkyl cellulose obtained by the method according to [1] with a surfactant.

According to the present invention, a method for producing a cationized hydroxyalkyl cellulose and a cationized hydroxyalkyl cellulose which are blended in a hair cleansing agent which has good smoothness of foam during hair washing and is excellent in smoothness of hair after rinsing and after drying. There is provided a method for producing a hair cosmetic containing the.

[Method for producing cationized hydroxyalkyl cellulose]
The method for producing cationized hydroxyalkyl cellulose (hereinafter, also referred to as “C-HAC”) of the present invention is characterized by having the following Step 1 and Step 2 in this order.
Step 1: Step of crushing pulp having 18% by mass of sodium hydroxide soluble content of 5.6% by mass or less to obtain powdery cellulose Step 2: The powdery cellulose obtained in Step 1 is added with alkylene oxide and cation Step of reacting with an agent

In hair cosmetics containing cationized hydroxyalkyl cellulose, sufficient foam slip during washing and smoothness of hair during rinsing and after drying may not be obtained in some cases.
As a result of studying the pulp as a raw material, the present inventors have solved the above-mentioned problem by using a pulp raw material having a sodium hydroxide-soluble content of 18 mass% of 5.6 mass% or less. , And found that stable and excellent performance was obtained. The detailed mechanism is unknown, but it is presumed as follows.
It is generally known that the 18 mass% sodium hydroxide-soluble content (hereinafter, also referred to as S18) according to ISO692:1982 has a correlation with the amount of hemicellulose (see, for example, JP-A-2013-179036). See, for example, TAPPI T235) as a measuring method. It is considered that the pulp having a low content of 18% by mass of sodium hydroxide (S18) has a low amount of hemicellulose. Here, the present inventors have added to the shampoo agent, together with the cationized hydroxyalkyl cellulose, hemicellulose extracted separately from the pulp and evaluated, and together with the cationized hydroxyalkyl cellulose, the hemicellulose was added separately. With the shampoo agent, the foam did not slip smoothly during cleaning, and the foam became crushed. Also, when rinsed, the hair was inferior in smoothness and became more squeaky. Therefore, in a hair cosmetic such as a shampoo, when a raw material having a large amount of hemicellulose is used, excellent effects such as slipping of foam during washing and smoothness of hair after rinsing and after drying can be sufficiently obtained. Assuming that there is no hemicellulose, 18% by mass sodium hydroxide-soluble content was used as an indicator of the amount of hemicellulose, and the 18% by mass sodium hydroxide-soluble content of the raw material pulp and the obtained cationized hydroxyalkyl cellulose were used for hair makeup. As a result of evaluating the relationship with the evaluation when blended in the raw material, it was found that an excellent effect can be obtained by using the pulp having the 18% by mass sodium hydroxide-soluble content of 5.6% by mass or less. It is a thing.
The reason for this is unknown, but the main components of hemicellulose include xylan, arabinoxylan, mannan, glucomannan, glucuronoxylan, etc., and the presence of polysaccharides having these branched chains stabilizes the foam film. It is thought to have an effect on. In addition, it is considered that when the above-mentioned branched-chain polysaccharide is adsorbed on the hair, it affects the uniform adsorption of the cationized hydroxyalkyl cellulose on the hair, so that the original function of the cationized hydroxyalkyl cellulose cannot be exhibited. Be done.
Hereinafter, each component and each step used in the production method of the present invention will be sequentially described.

<Step 1>
(pulp)
The pulp used as a raw material in the present invention has a sodium hydroxide-soluble content of 18 mass% of 5.6 mass% or less. Here, the 18% by mass sodium hydroxide-soluble content is considered to be correlated with the amount of hemicellulose in the pulp, and a large amount of 18% by mass sodium hydroxide-soluble content means that the contained hemicellulose content is large. To do.
Here, the content of 18% by mass of sodium hydroxide is 5.6% by mass or less, preferably 5.6% by mass or less, from the viewpoint of obtaining a hair cleansing agent which has good foam slip during cleaning and is excellent in smoothness of hair after rinsing and after drying. Is 5.5 mass% or less, more preferably 5.4 mass% or less, and further preferably 5.3 mass% or less. The lower limit of the 18% by mass sodium hydroxide-soluble content is not particularly limited, but is preferably 3% by mass or more, and more preferably 4% by mass or more from the viewpoint of easiness of pulp production and availability. is there.
The 18% by mass sodium hydroxide-soluble content is measured by the method described in Examples.

The content of 18% by mass of sodium hydroxide in the pulp can be set to 5.6% by mass or less by selecting the type of wood as a raw material and the conditions during pulp production.
As the pulp raw material, either hardwood or softwood may be used, but from the viewpoint of efficiently obtaining pulp with S18 of 5.6% by mass or less, softwood is preferable, and for example, pine is preferable.
Further, when the wood is made into pulp by the cooking process and the bleaching process, the hot alkali process of the cooking process is particularly important, and the amount of hemicellulose can be controlled by the temperature and time of the hot alkali process.

In the present invention, it is preferable to further include a step of confirming that the 18% by mass sodium hydroxide-soluble content (S18) of the pulp is 5.6% by mass or less before the step 1.
In the step of confirming above, 18% by mass sodium hydroxide-soluble content (S18) of the raw material pulp in the method for producing C-HAC of the present invention is measured, and if S18 is 5.6% by mass or less, This is a step of determining that the material is suitable for use as the raw material of the present invention.
Here, when S18 has already been measured and there is a pulp of the same lot in which S18 was 5.6% by mass or less, or pulp in which S18 is guaranteed to be 5.6% by mass or less Since it has been confirmed that S18 is 5.6% by mass, the measurement may be omitted.

The intrinsic viscosity number (Viscosity) of the pulp used as a raw material in the present invention is a viewpoint that the viscosity average molecular weight of cellulose is adjusted to improve the smoothness of bubbles during hair washing, smoothness of hair during rinsing and after drying. From the above, preferably 1450 mL/g or more, more preferably 1490 mL/g or more, further preferably 1510 mL/g or more, and preferably 1600 mL/g or less, more preferably 1570 mL/g or less, further preferably 1550 mL/g. It is below.
The intrinsic viscosity of pulp is measured by the method described in Examples.

In step 1, a sheet-shaped or roll-shaped pulp having high cellulose purity obtained as a general-purpose raw material can be crushed to prepare powdered cellulose. The method for preparing the powdered cellulose is not particularly limited. For example, the methods described in JP-A-62-236801, JP-A-2003-64184, JP-A-2004-331918 and the like can be mentioned.
Examples of the pulverization treatment method in the step 1 include a method in which pulp having S18 of 5.6% by mass or less is cut and dried as needed, and then pulverized by a pulverizer. As will be described later in particular, it is preferable to employ a method in which the crushing treatment is performed in multiple stages, that is, a method in which the pulp is roughly crushed and then the particle size is reduced. The crushing treatment is preferable because it can pulverize the pulp and reduce the crystallization index described later, and the reactivity with the cationizing agent and the alkylene oxide in step 2 is improved. The cutting process, the drying process and the crushing process will be described below.

(Cutting process)
Depending on the type and shape of pulp, it is preferable to perform a cutting treatment as a pretreatment. The method of cutting the pulp can be appropriately selected depending on the type and shape of the pulp, and examples thereof include a method of using one or more cutting machines selected from a shredder, a slitter cutter and a rotary cutter.
When using sheet-like pulp, it is preferable to use a shredder or a slitter cutter as a cutting machine, and it is more preferable to use a slitter cutter from the viewpoint of improving productivity.
The slitter cutter is a cutting machine that vertically cuts with a roll cutter in the vertical direction along the longitudinal direction of the sheet to form a long and narrow strip, and then horizontally cuts with a fixed blade and a rotary blade in the width direction of the sheet. By using a slitter cutter, the shape of the raw material pulp can be diced. As the slitter cutter, a cutting machine (super cutter) manufactured by Ogino Seiki Co., Ltd., a sheet pelletizer manufactured by Horai Co., Ltd., or the like can be preferably used.

The size of the cellulose-containing raw material obtained after the cutting treatment is preferably 1 mm square or more, more preferably 1.5 mm square or more, from the viewpoint of improving productivity, and reduces the load required for crushing in the subsequent crushing treatment. From the viewpoint of the above, and from the viewpoint of efficiently and easily carrying out the drying treatment described later, it is preferably 70 mm square or less, more preferably 50 mm square or less.

(Drying process)
In general, commercially available pulps usually contain about 5 to 30% by mass of water. Therefore, it is usually preferable to adjust the water content of the pulp by drying the pulp, preferably a cut product obtained after the cutting process.
As a drying method, a known drying means may be appropriately selected. For example, the method described in “Introduction to Powder Engineering” (edited by Japan Powder Industrial Technology Association, Powder Engineering Information Center, 1995), page 176. Can be mentioned. Examples of the drying means include a hot air heat receiving drying method, a conductive heat receiving drying method, a dehumidifying air drying method, a cold air drying method, a microwave drying method, an infrared drying method, a sun drying method, a vacuum drying method and a freeze drying method. ..
These drying methods may be used alone or in combination of two or more, and the conduction heat receiving drying method is preferable from the viewpoint of efficient drying. The drying treatment may be either batch treatment or continuous treatment, but continuous treatment is preferred from the viewpoint of improving productivity.

The lower limit of the water content of the pulp subjected to the pulverization treatment after the drying treatment is 0 mass% with respect to the pulp, but from the viewpoint of improving productivity, the water content is preferably 0.1 mass% or more. , And more preferably 0.5% by mass or more. In addition, from the viewpoint of efficiently crushing and crystallizing the pulp in the crushing treatment, and from the viewpoint of improving the transparency of the finally obtained aqueous solution of C-HAC, the water content is preferably 2.5% by mass or less. And more preferably 2.0% by mass or less, and further preferably 1.8% by mass or less.
The water content can be specifically measured by the method described in Examples.

(Crushing process)
From the viewpoint of obtaining powdered cellulose having a low water content, it is preferable to carry out the pulverization treatment under the condition that the water content in the pulp is 2.5% by mass or less.
From the viewpoint of efficiently pulverizing and low-crystallizing the pulp and improving the reactivity in the step 2, it is preferable to carry out the pulverization treatment in multiple stages. When the crushing treatment is performed in multiple stages, a method in which the pulp subjected to the cutting treatment and the drying treatment is roughly crushed, and then the particle size reduction treatment is performed is preferable.
The crusher used in the crushing treatment is not particularly limited, and may be any device capable of reducing the crystallization index to a predetermined value or less by pulverizing pulp, but it is preferable to use a vibrating rod mill described later, a vibrating rod mill and a high speed. It is more preferable to use a rotary fine pulverizer. More specifically, it is more preferable to use a vibrating rod mill in the coarse crushing process and to use a high-speed rotary fine crusher in the small particle size reducing process.

[Coarse crushing treatment]
In the coarse crushing process, the pulp that has been subjected to the cutting process and the drying process as necessary is coarsely crushed to be powdered and crystallized. In the coarse pulverization treatment, a large amount of treatment can be carried out in a short time, so that low crystallized powdery cellulose can be efficiently obtained. Hereinafter, the cellulose obtained after the coarse pulverization treatment is also referred to as “coarse pulverized cellulose”.
Specific examples of the crusher used for the coarse crushing treatment include a high pressure compression roll mill, a roll mill such as a roll rotation mill, a ring roller mill, a vertical roller mill such as a roller race mill or a ball race mill, a rolling ball mill, and a vibrating ball mill. , Vibrating rod mills, vibrating tube mills, container-driven medium mills such as planetary ball mills or centrifugal fluidizing mills, consolidation shear mills such as high-speed centrifugal roller mills and ong mills, mortars, stone mills, mass colloiders, fret mills, edge runner mills, knife mills. , A cutter mill and the like. These crushers can be used alone or in combination of two or more kinds.
Among these, from the viewpoint of improving the pulverization efficiency and low crystallization efficiency of pulp, a container-driven medium mill is preferable, a vibrating ball mill, a vibrating rod mill or a vibrating mill such as a vibrating tube mill is more preferable, and a vibrating rod mill is further preferable. .. The crushing method may be a batch method or a continuous method.
The material of the crusher used for the crushing treatment, as the material of the medium, from the viewpoint of crushing efficiency of the cellulose-containing raw material, iron, stainless steel, zirconia, silicon carbide, silicon nitride is preferable, further from the viewpoint of industrial use, iron or Stainless steel is more preferable.

By the above treatment method, coarsely pulverized cellulose can be efficiently obtained from pulp. In the coarse pulverization treatment, reaggregation of coarsely pulverized cellulose can be suppressed, and the pulverized material can be treated by a dry method without being fixed to the inside of the pulverizer.
Further, since the low crystallization of cellulose is mainly performed in the coarse pulverization treatment, the crystallization index of the coarsely pulverized cellulose obtained by the coarse pulverization treatment is preferably −3.5% or less.
The D ₅₀ of the coarsely pulverized cellulose after the coarse pulverization is preferably 80 μm or more, and preferably 300 μm or less.

[Small particle size treatment]
In the particle size reduction treatment, the coarsely pulverized cellulose obtained in the coarse pulverization treatment is further pulverized to reduce the particle size. By performing the coarse pulverization treatment and then the particle size reduction treatment, it is possible to efficiently obtain powdery cellulose having a further reduced volume median particle diameter (D ₅₀ ).
A high-speed rotary fine pulverizer is preferable as the pulverizer used for the particle size reduction treatment. The high-speed rotary fine pulverizer is a device that pulverizes the coarsely pulverized cellulose loaded in the pulverizing cylinder by impacting and shearing by rotating a hammer, a blade, a pin and the like at high speed.

By the above-mentioned pulverization treatment, powderization and low crystallization of pulp proceed, and powdery cellulose suitable for the production method of the present invention can be obtained.
From the viewpoint of improving the water solubility of the finally obtained C-HAC and from the viewpoint of improving the reactivity with the cationizing agent and the alkylene oxide used in step 2, the powdery cellulose obtained after the pulverization treatment is crystalline. Amorphous cellulose having a chemical index of 30% or less is preferable. Here, the amorphous cellulose means a state in which the ratio of the amorphous portion is large in the crystal structure of cellulose. Specifically, the crystallization index according to the following calculation formula (1) is preferably 30% or less, more preferably 0% or less, further preferably -5.0% or less, and from the viewpoint of productivity, preferably -30. It is 0.0% or more. When the crystallization index of the powdery cellulose is within the above range, the reactivity with the cationizing agent and the alkylene oxide is excellent, and the difference in the reaction rate between the crystal part and the amorphous part is small, and the cationizing agent and the alkylene oxide are small. The reaction homogeneity with is improved.
Crystallization index (%)=[(I _22.6 −I _18.5 )/I _22.6 ]×100 (1)
(In the formula, I _22.6 indicates the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ=22.6°) in X-ray diffraction, and I _18.5 indicates the amorphous part (diffraction angle 2θ=18). The diffraction intensity at 0.5° is shown.)

The viscosity average molecular weight of the cellulose of the powdery cellulose obtained in the step 1 improves the smoothness of foam during washing when the obtained C-HAC is mixed with a detergent, and the smoothness of hair after rinsing and after drying. From the viewpoint, it is preferably 100,000 or more, more preferably 110,000 or more, further preferably 120,000 or more, still more preferably 130,000 or more, and from the same viewpoint, preferably 180,000 or less, more preferably 170,000 or less. , More preferably 160,000 or less, still more preferably 150,000 or less.
The viscosity average molecular weight of cellulose is measured by the method described in Examples.

From the viewpoint of improving the reaction uniformity with the cationizing agent and the alkylene oxide, the powdery cellulose obtained after the pulverization treatment has a water content of preferably 2.5% by mass or less, more preferably 2.0% by mass or less, More preferably, it is 1.8 mass% or less. From the viewpoint of cost, the water content is 0% by mass or more, preferably 0.1% by mass or more, and more preferably 0.5% by mass or more.

From the viewpoint of the productivity of the powdery cellulose, the D _{50 of the} powdery cellulose obtained after the pulverization treatment is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more. Further, from the viewpoint of improving the reaction uniformity with the cationizing agent and the alkylene oxide in step 2, D ₅₀ is preferably 300 μm or less, more preferably 200 μm or less, and further preferably 100 μm or less.

In step 1, it is preferable to perform the crushing treatment without adding the basic compound. When the basic compound stays in the crusher, it may cause contamination and instability of product quality, but this can be avoided.

<Step 2>
In step 2, the powdered cellulose obtained in step 1 is reacted with an alkylene oxide and a cationizing agent to obtain cationized hydroxyalkyl cellulose (C-HAC). In addition, in the following description, the alkylene oxide and the cationizing agent are collectively referred to as a “reacting agent”.
The reaction order of the alkylene oxide and the cationizing agent is not particularly limited, and the powdery cellulose may be reacted simultaneously with the alkylene oxide and the cationizing agent, or the powdery cellulose may be reacted with the cationizing agent. After that, the alkylene oxide may be reacted, or conversely, the powdered cellulose may be reacted with the alkylene oxide and then the cationizing agent may be reacted. Among these, from the viewpoint of reactivity, it is preferable to react the powdered cellulose with the alkylene oxide and then to react with the cationizing agent.

The reactant is preferably reacted with the powdery cellulose in the presence of the basic compound. Alkaline cellulose produced from powdery cellulose and a basic compound has high reaction activity with a reaction agent. The basic compound also acts as a reaction catalyst in the reaction between the cellulose and the reactant. Therefore, C-HAC can be efficiently obtained by reacting the powdery cellulose with the reaction agent in the presence of a predetermined amount of the basic compound.

More specifically, the reaction in step 2 is preferably carried out by adding a reactant in the presence of a predetermined amount of a basic compound while stirring the powdery cellulose.
The order of addition of the basic compound and the reaction agent is not particularly limited, but it is preferable that the powdery cellulose and the basic compound are mixed and then the reaction agent is added and reacted. This is because by mixing the powdery cellulose and the basic compound, alkali cellulose having high reaction activity is generated, and hence the subsequent reaction with the reaction agent proceeds efficiently.

The reaction of step 2 is preferably performed in a solid state. The reaction in the solid phase refers to the reaction in the state where the liquid phase does not substantially exist, and is different from the reaction in the solution or the suspension.
By carrying out the reaction of step 2 in the solid state, the reaction between the powdery cellulose and the reaction agent proceeds efficiently. In addition, for example, when a large excess of water is present in the reaction system of step 2, when the alkylene oxide is reacted with the alkylene oxide, a hydration reaction (side reaction) of the alkylene oxide or the like occurs, resulting in generation of a by-product and reduction in yield. Is more likely to occur. Therefore, by carrying out the reaction of step 2 in a solid state and reducing the amount of water during the reaction, the above side reaction can be suppressed and the yield can be improved.

From the viewpoint of uniformly dispersing the basic compound and the reactant in the powdery cellulose, the water content at the time of the reaction in step 2 is preferably more than 0% by mass with respect to the cellulose in the powdery cellulose, and more preferably It is 5% by mass or more, and more preferably 15% by mass or more. From the viewpoint of suppressing the side reaction and improving the yield, it is preferably 100% by mass or less, more preferably 85% by mass or less.
The amount of cellulose in the powdery cellulose means a value obtained by subtracting the amount of water in the powdery cellulose from the mass of the powdery cellulose. The water content at the time of reaction in step 2 means the sum of the water content in the powdery cellulose provided in step 2 and the amount of water added in step 2.

For example, in step 2, first, powdery cellulose, a basic compound and, if necessary, water are added, mixed and stirred. When water is added, the addition amount is adjusted so that the amount of water during the reaction in step 2 is preferably within the above range.
When water is added, the order of adding the basic compound and water is not particularly limited, and (i) a method of adding water after the addition of the basic compound, (ii) a method of simultaneously adding the basic compound and water, ( iii) Any method of dissolving the basic compound in a part or all of water to be added and adding the basic compound in the form of an aqueous solution may be used. From the viewpoint of operability in production, the method (iii) is preferable.

(Basic compound)
Examples of the basic compound 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. And the like. Among these, at least one selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides is preferable, alkali metal hydroxides are more preferable, and the group consisting of sodium hydroxide and potassium hydroxide is preferable. One or more selected are more preferable, and sodium hydroxide is still more preferable.
The above basic compounds may be used alone or in combination of two or more.
The amount of the basic compound used is 1 mol of anhydroglucose unit (hereinafter, also referred to as “AGU”) constituting the cellulose of the powdery cellulose from the viewpoint of efficiently promoting the reaction between the powdery cellulose and the reaction agent. On the other hand, it is preferably 0.05 molar equivalent or more, more preferably 0.1 molar equivalent or more, still more preferably 0.5 molar equivalent or more, still more preferably 0.8 molar equivalent or more.
On the other hand, the amount of the basic compound used in Step 2 is from the viewpoint of suppressing the by-products in the reaction with the reactant, improving the yield (reactant standard), and avoiding the removal treatment of the excess basic compound. The amount is preferably 3.0 molar equivalents or less, more preferably 2.0 molar equivalents or less, still more preferably 1.5 molar equivalents or less, relative to 1 mole of AGU of the powdery cellulose.

As a method of adding the basic compound, a method of spraying an aqueous solution of the basic compound onto the powdery cellulose is preferable from the viewpoint of uniformly dispersing the basic compound in the powdery cellulose.

The temperature at the time of adding powdery cellulose, a basic compound, and optionally water and stirring is preferably 35° C. or higher, more preferably 40° C. or higher from the viewpoint of activating cellulose, and From the viewpoint of suppressing the decrease in the degree of polymerization, the temperature is preferably 90°C or lower, more preferably 80°C or lower.
The stirring time is preferably 0.1 hours or more, more preferably 0.2 hours or more, from the viewpoint of the production efficiency of alkali cellulose. From the viewpoint of productivity, it is preferably 24 hours or less, more preferably 12 hours or less.
From the viewpoint of avoiding coloring of cellulose and avoiding a decrease in molecular weight due to cleavage of cellulose chains during the reaction, the stirring and the subsequent reaction are preferably carried out in an atmosphere of an inert gas such as nitrogen.

(Reactant)
Then, the reactant is added to the alkali cellulose (mixture of the powdery cellulose, the basic compound and water) obtained by the above method to react the powdery cellulose with the reactant.
The reaction agent used in step 2 is a compound capable of reacting with a primary or secondary hydroxyl group of cellulose to introduce a substituent, and is a cationizing agent and an alkylene oxide.
When the cationizing agent and the alkylene oxide are used, the order of adding the reactants is not particularly limited, but as described above, it is preferable to first react the powdery cellulose and the alkylene oxide, and then to react with the cationizing agent. By using this reaction sequence, the reactivity is further improved. It is considered that the reason is that by adding the alkylene oxide, which is a reaction agent having a smaller molecular volume, first, the addition of the cationizing agent to be subsequently reacted easily proceeds uniformly.

[Alkylene oxide]
The amount of alkylene oxide used is not limited, and may be appropriately adjusted depending on the desired amount of introduction. The amount of alkylene oxide used is the powder used in Step 2 from the viewpoint of improving the slipperiness of foam during washing when the resulting C-HAC is mixed with a detergent, and the smoothness of hair after rinsing and after drying. It is preferably 0.1 mol or more, more preferably 1.0 mol or more, still more preferably 3.0 mol or more, still more preferably 3.5 mol or more, per 1 mol of AGU of the cellulosic cellulose. From the viewpoint of cost, the amount of alkylene oxide used is preferably 20 mol or less, more preferably 10 mol or less, still more preferably 8.0 mol or less, per 1 mol of AGU of the powdery cellulose used in Step 2. It is more preferably 5.0 mol or less.

When the alkylene oxide is a gas, the reaction is preferably carried out under pressure.
The alkylene oxide may be added all at once, or may be added continuously or sequentially, but it is preferable to add the alkylene oxide continuously or sequentially so as to attain the above-mentioned reaction pressure.
The alkylene oxide is preferably an alkylene oxide having 2 or more and 4 or less carbon atoms, more preferably ethylene oxide or propylene oxide, from the viewpoints of good foam slippage during hair washing and excellent smoothness of hair during rinsing and after drying. More preferably, it contains propylene oxide.

[Cationizing agent]
The cationizing agent used in the present invention is preferably a compound represented by the following formula (1) or formula (2).

In formulas (1) and (2), R ^{21 to} R ²³ each independently represent a hydrocarbon group having 1 to 24 carbon atoms, A represents a halogen atom, X ⁻ represents an anion, and t is 0. An integer of 3 or less is shown.

In formula (1) and formula (2), R ^{21 to} R ²³ each independently represent a hydrocarbon group having 1 to 24 carbon atoms, which is a linear or branched hydrocarbon group having 1 to 4 carbon atoms. Preferably. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and an isobutyl group. Among these, a methyl group or an ethyl group is preferable, all of R ^{21 to} R ²³ are more preferably a methyl group or an ethyl group, and it is further preferable that all of R ^{21 to} R ²³ are a methyl group.
In the formulas (1) and (2), t represents an integer of 0 or more and 3 or less, preferably 1 or more and 3 or less, more preferably 1 or 2, and further preferably 1.
X ⁻ represents an anion and is a counter ion of a quaternary ammonium cation. Specifically, alkyl sulfate ion having 1 to 3 carbon atoms, sulfate ion, phosphate ion, carboxylate ion having 1 to 3 carbon atoms (formate ion, acetate ion, propionate ion), and halide ion It is illustrated.
Among these, X ⁻ is preferably one or more selected from an alkylsulfate ion having a carbon number of 1 or more and 3 or less, a sulfate ion, and a halide ion, from the viewpoint of the ease of production and the availability of raw materials. A halide ion is preferable. Examples of the halide ion include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion. From the viewpoint of water solubility and chemical stability of the obtained polysaccharide derivative, a chloride ion and a bromide ion are preferable. One or more selected from the above, and more preferably a chloride ion.
X ⁻ may be one type alone or two or more types.

Specific examples of the compound represented by the formula (1) or (2) include chloride or bromide of glycidyltrimethylammonium or glycidyltriethylammonium from the viewpoint of easy availability of raw materials and chemical stability; Chloro-2-hydroxypropyltrimethylammonium or chloride of 3-chloro-2-hydroxypropyltriethylammonium; selected from 3-bromo-2-hydroxypropyltrimethylammonium or bromide of 3-bromo-2-hydroxypropyltriethylammonium 1 One or more kinds are preferable, and one or more kinds selected from glycidyl trimethyl ammonium chloride and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride are more preferable.
These cationizing agents can be used alone or in combination of two or more kinds.

The amount of the cationizing agent used is from the viewpoint of improving the smoothness of the foam during washing when the resulting C-HAC is mixed with a detergent and the smoothness of hair after rinsing and drying. The amount is preferably 0.01 mol or more, more preferably 0.1 mol or more, still more preferably 0.3 mol or more, still more preferably 0.5 mol or more, based on the above viewpoints and the production of C-HAC. From the viewpoint of cost, it is preferably 10 mol or less, more preferably 5 mol or less, still more preferably 3 mol or less, still more preferably 1 mol or less.

The cationizing agent may be added all at once, intermittently or continuously.
As a method of adding the reactant, a method of spraying and adding the reactant or the reactant solution to the powdery cellulose is preferable from the viewpoint of uniformly dispersing the reactant in the powdery cellulose.

The reaction temperature and reaction time with the reaction agent in step 2 are not particularly limited and can be appropriately selected depending on the type of the reaction agent used and the like.

The preferred manufacturing method in the present invention is as follows.
First, powdery cellulose, a basic compound and, if necessary, water are added by the above-mentioned method, mixed and stirred, and then alkylene oxide is added and reacted to obtain hydroxyalkyl cellulose. Then, a cationizing agent is added and reacted with hydroxyalkyl cellulose to obtain cationized hydroxyalkyl cellulose. With this reaction sequence, better reactivity can be obtained.
The type and amount of each component used, the reaction conditions, and their preferred embodiments are the same as described above.

The device used in step 2 preferably has a mechanical stirring mixer having a stirring blade inside and a spraying device for spraying the basic compound and the reactant into the stirring tank.
The spray device for supplying the basic compound and the reactant into the mechanical stirring mixer is not particularly limited. For example, a spraying device having a spraying nozzle such as a one-fluid nozzle or a two-fluid nozzle is preferable.
The spray pattern by the spray nozzle is not particularly limited, and examples thereof include a full cone, an empty cone, a full pyramid, and a fan shape.

After completion of the reaction in step 2, C-HAC can be isolated by performing a purification operation such as neutralization of a basic compound, washing with a water-containing isopropanol solvent, a water-containing acetone solvent and the like, if necessary.

<Cationized hydroxyalkyl cellulose>
(Substitution degree)
The degree of substitution of the alkyleneoxy group of the cationized hydroxyalkyl cellulose (C-HAC) obtained by the present invention is preferably from the viewpoint of good smoothness of foam during washing and excellent smoothness of hair during rinsing and after drying. 0.1 or more, more preferably 1 or more, still more preferably 1.5 or more, even more preferably 2 or more, even more preferably 2.2 or more, and from the same viewpoint, preferably 3 or less, more preferably It is 2.8 or less, and more preferably 2.6 or less.
In the present invention, the degree of substitution with an alkyleneoxy group refers to the average number of moles of the alkyleneoxy group present in the C-HAC molecule per mole of anhydroglucose units constituting the cellulose main chain. The substitution degree of the alkyleneoxy group is measured by the method described in Examples below.

The degree of substitution of the cationic group of C-HAC obtained by the present invention is preferably 0.01 or more, and more preferably 0.01 or more, from the viewpoint of good foam slippage during washing and excellent smoothness of hair during rinsing and after drying. Is 0.05 or more, more preferably 0.1 or more, still more preferably 0.15 or more, and from the same viewpoint, preferably 1 or less, more preferably 0.5 or less, and further preferably It is 0.3 or less, and more preferably 0.25 or less.
In the present invention, the degree of substitution of the cationic group refers to the average number of moles of the cationic group present in the C-HAC molecule with respect to 1 mole of anhydroglucose unit constituting the cellulose main chain. The degree of substitution of the cationic group is measured by the method described in Examples below.

(transparency)
The C-HAC obtained by the present invention preferably has a high transparency of its aqueous solution. Specifically, when C-HAC is a 2% aqueous solution, it is preferable that the appearance is excellent in transparency.

(Use)
The use of C-HAC obtained by the present invention is not particularly limited, and for example, a wide range of fields such as a blending component of a hair cosmetic composition such as shampoo, rinse, treatment, conditioner, dispersant, modifier, coagulant and the like. Can be used at. The C-HAC may be used in a powder state or may be dissolved in water and used in an aqueous solution state.

<Production of cationized hydroxyalkyl cellulose aqueous solution>
The method for preparing the C-HAC aqueous solution obtained by the production method of the present invention is not particularly limited, but for example, it can be prepared by mixing with water and preferably stirring at 40 to 90° C. for 0.5 to 12 hours. The solid content concentration of the aqueous solution is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass from the viewpoint of easy preparation of the aqueous solution. % Or less, more preferably 10% by mass or less.

You may mix|blend various additives, such as a neutralizer and a preservative, with the C-HAC aqueous solution in the range which does not impair the effect of this invention. As the neutralizing agent, either an inorganic acid or an organic acid can be used, but an organic acid is preferable, and for example, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartronic acid, malic acid, tartaric acid, oxyphthalic acid, citric acid. Etc. Among them, dicarboxylic acids having a hydroxyl group and having 2 to 8 carbon atoms are preferable, one or more kinds selected from malic acid and tartaric acid are more preferable, and malic acid is further preferable.
Examples of antiseptics include benzyl alcohol, paraoxybenzoic acid ester, benzoic acid, sorbic acid, dehydroacetic acid and the like.
The additive amount in the C-HAC aqueous solution is usually 0.001% by mass or more and 5.0% by mass or less.
If necessary, the aqueous solution obtained as described above may be filtered using a mesh having a mesh size of 10 μm or more and 300 μm or less.

[Method for producing hair cosmetics]
The method for producing a hair cosmetic composition of the present invention has a step of mixing the C-HAC obtained by the above-described production method of the present invention with a surfactant. That is, the method for producing a hair cosmetic composition of the present invention preferably has the following steps 1 to 3 in this order. The hair cosmetic composition obtained by the production method of the present invention has good foam smoothness during hair washing and excellent smoothness of hair during rinsing and after drying.
Step 1: Step of crushing pulp having 18% by mass of sodium hydroxide soluble content of 5.6% by mass or less to obtain powdery cellulose Step 2: The powdery cellulose obtained in Step 1 is added with alkylene oxide and cation Step of reacting with an agent Step 3: Step of mixing cationized hydroxyalkyl cellulose obtained in Step 2 and a surfactant Steps 1 and 2 are as described above. Step 3 is a step of mixing the cationized hydroxyalkyl cellulose obtained in step 2 and the surfactant, and the mixing method is not particularly limited.
Hereinafter, the content of C-HAC and the surfactant will be described.

The content of C-HAC in the hair cosmetic composition is preferably in the hair cosmetic composition, from the viewpoint of obtaining a hair cosmetic composition having good foam slipperiness during hair washing and excellent in smoothness of hair after rinsing and after drying. 0.005 mass% or more, more preferably 0.02 mass% or more, even more preferably 0.03 mass% or more, even more preferably 0.04 mass% or more, even more preferably 0.05 mass% or more. From the viewpoint of suppressing stickiness after drying of hair treated with hair cosmetics, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, still more preferably 0.5%. The content is less than or equal to mass %, more preferably less than or equal to 0.3 mass %.

The hair cosmetic composition of the present invention further contains one or more surfactants.
Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants.
When used as a cleaning agent for shampoos, anionic surfactants, nonionic surfactants, and amphoteric surfactants are preferable, and when used as rinses, conditioners, treatments, hair styling agents, etc. Ionic surfactants and cationic surfactants are preferred.

As the anionic surfactant, a sulfate ester salt, a sulfonate salt, a carboxylate salt, a phosphate ester salt and an amino acid salt are preferable.
Among these, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkenyl ether sulfates, higher fatty acid salts, polyoxyethylene alkyls from the viewpoint of obtaining smoothness after drying of hair treated with hair cosmetics. Ether acetate, sulfosuccinic acid alkyl ester salt, and acylglutamate are preferable, and polyoxyethylene alkyl ether sulfate or alkyl sulfate represented by the following formula (4) or (5) is particularly preferable.
^{_{{R 7 -O (CH 2 CH}} 2 O) r SO 3} t M (4)
{R ⁸ -OSO ₃ } _t M (5)
(In the formula, R ⁷ represents an alkyl group or an alkenyl group having 10 to 18 carbon atoms, R ⁸ represents an alkyl group having 10 to 18 carbon atoms, M represents an alkali metal, an alkaline earth metal, ammonium or an alkanolamine. It represents a salt or a basic amino acid, r represents the average number of moles of ethyleneoxy groups added, and is 1 to 5. t is the same number as the valence of M.)

The nonionic surfactant is preferably a polyalkylene glycol type or a polyhydric alcohol type nonionic surfactant, from the viewpoint of obtaining smoothness after drying of hair treated with a hair cosmetic, and a polyalkylene glycol type. Among them, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, and polyoxyalkylene hydrogenated castor oil are preferable, and among polyhydric alcohol types, alkyl glycoside is preferable.

Examples of the amphoteric surfactant include betaine-based surfactants and amine oxide-type surfactants.
As the betaine-based surfactant, fatty acid amide propyl betaine and alkylhydroxysulfobetaine are preferable, those having an alkyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms are more preferable, and lauric acid amide propyl betaine and palm are particularly preferable. Nuclear oil fatty acid amide propyl betaine, coconut oil fatty acid amide propyl betaine, lauryl hydroxysulfobetaine, lauryl sulfobetaine, coconut oil fatty acid amide propyl hydroxysulfobetaine, coconut oil fatty acid amide propyl sulfobetaine and the like are preferable.
As the amine oxide type surfactant, alkyl dimethyl amine oxide is preferable, those having an alkyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms are preferable, and lauryl dimethyl amine oxide and myristyl dimethyl amine oxide are particularly preferable.

The content of the surfactant in the hair cosmetic composition of the present invention is preferably 0.11% by mass or more, from the viewpoint of improving the smoothness of the hair treated with the hair cosmetic composition after drying and suppressing the stickiness. It is preferably 1% by mass or more, and preferably 80% by mass or less, more preferably 50% by mass or less, and further preferably 20% by mass or less.
When the hair cosmetic is shampoo (hair wash), the content of the surfactant is preferably 5% by mass or more, more preferably 8% by mass or more, and preferably 20% by mass from the same viewpoint. % Or less, more preferably 15% by mass or less.
When the hair cosmetic is a rinse, conditioner, treatment or hair styling agent, the hair makeup treated from the viewpoint of improving the smoothness after dryness of the hair treated with the hair cosmetic, the finger passage, the dry feeling, and suppressing the stickiness. The content in the material is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less.

In the hair cosmetic composition of the present invention, the ratio of C-HAC to the surfactant is [C-HAC/surfactant] from the viewpoint of obtaining smoothness, dryness of fingers, and dry feel of hair treated with the hair cosmetic composition. Agent] is preferably 0.001 or more, more preferably 0.003 or more, still more preferably 0.005 or more, and preferably 10 or less, more preferably 2 or less, still more preferably 1 or less. , And more preferably 0.5 or less.
When the hair cosmetic is shampoo (hair cleanser), the ratio of C-HAC to the surfactant (([ C-HAC/surfactant] mass ratio) is preferably 0.001 or more, more preferably 0.003 or more, still more preferably 0.005 or more, and preferably 0.1 or less, more preferably Is 0.05 or less, more preferably 0.01 or less.
When the hair cosmetic is a rinse, conditioner, treatment or hair styling agent, from the viewpoint of improving the smoothness of the hair treated with the hair cosmetic after drying and suppressing the sticky feeling, C-HAC and a surfactant are used. The ratio (mass ratio of [C-HAC/surfactant]) is preferably 0.05 or more, more preferably 0.08 or more, still more preferably 0.1 or more, and preferably 1 or less, more preferably It is preferably 0.5 or less, more preferably 0.35 or less.

The hair cosmetic composition of the present invention may contain a cationic polymer other than C-HAC of the present invention, an amphoteric polymer or an oil component.
The content of the cationic polymer or amphoteric polymer excluding C-HAC in the hair cosmetic composition of the present invention is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, and further preferably 0. It is 1 to 0.5 mass %.
The ratio of C-HAC and the cationic polymer excluding C-HAC and the amphoteric polymer of the present invention is [C-HAC from the viewpoint of suppressing smoothness and stickiness during rinsing and after drying of hair treated with a hair cosmetic composition. /C-HAC cationic polymer and amphoteric polymer] is preferably 0.05 to 20, more preferably 0.1 to 10, further preferably 0.1 to 5, and particularly 0.2 to 1 in terms of mass ratio. preferable.

The hair cosmetic composition of the present invention can be manufactured according to a conventional method. Specifically, for example, in the case of a liquid shampoo, water and a surfactant are heated and uniformly mixed. After confirming uniform dissolution, add oily component and polymer and mix. If necessary, the polymer can be added after being dispersed or dissolved in water in advance. After uniform dissolution or dispersion, the mixture can be cooled, and if necessary, a pearling agent, a pH adjusting agent, a fragrance, a dye and the like can be added to prepare. Similarly, in the case of a conditioner, water and a surfactant are heated, and after uniform mixing, an oily component (higher alcohol etc.) dissolved or melted and a solvent are added to emulsify. Thereafter, the mixture can be cooled and, if necessary, an oily component (silicone or the like), a pearling agent, a pH adjusting agent, a fragrance, a dye and the like can be added to prepare. 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., but liquid, A paste or cream is preferable, and a liquid is particularly preferable.
In the case of a liquid state, it is preferable to use water, polyethylene glycol, ethanol or the like as a liquid medium, and the content of water is preferably 10 to 90% by mass in the whole composition.

Various physical properties were measured and evaluated by the following methods.
In the following Examples and Comparative Examples, parts and% are based on mass unless otherwise specified.

[Measuring method]
(1) Measurement of 18% by mass sodium hydroxide-soluble content (S18) It was measured according to ISO692:1982.

(2) Measurement of Water Content The water content of pulp and powdery cellulose was measured using an infrared moisture meter (“FD-610” manufactured by Kett Scientific Research Institute Co., Ltd.). Using 5 g of the sample per measurement, the sample was flattened and measured at a temperature of 120° C., and the point at which the mass change rate for 30 seconds was 0.1% or less was the end point of the measurement. The value of the measured water content was converted into mass% with respect to the cellulose and used as the value of each water content.

(3) Calculation of Crystallization Index The X-ray diffraction intensity of powdery cellulose was measured using an X-ray diffractometer (“MiniFlexII” manufactured by Rigaku Corporation) under the following conditions, and based on the calculation formula (1). The type I crystallization index of cellulose was calculated.
The measurement conditions were as follows: X-ray source: Cu/Kα-radiation, tube voltage: 30 kV, tube current: 15 mA, measurement range: diffraction angle 2θ=5 to 35°, X-ray scan speed was 40°/min. The measurement sample was prepared by compressing a pellet having an area of 320 mm ² ×thickness of 1 mm.

(4) Measurement powdered _{D 50} of cellulose having a volume-median particle size _{(D 50)} uses a laser diffraction / scattering particle size distribution measuring device (Beckman Coulter Inc. "LS13 320"), a dry method ( Tornado method). Specifically, 20 mL of powdery cellulose was charged into a cell and suctioned for measurement.

(5) Measurement of viscosity average molecular weight (copper-ammonia method)
(I) Preparation of Measurement Solution 0.5 g of cuprous chloride and 20 to 30 mL of 25 mass% ammonia water were added to a volumetric flask (100 mL) and completely dissolved, and then 1.0 g of cupric hydroxide and 25 Mass% ammonia water was added to make the amount up to just before the marked line of the volumetric flask. This was stirred for 30 to 40 minutes and completely dissolved. Then, the powdery cellulose obtained in the examples or comparative examples was added, and 25 mass% aqueous ammonia was added up to the marked line of the volumetric flask. It was sealed so as not to let air in, and was stirred by a magnetic stirrer for 12 hours to be dissolved. The same operation was performed to change the amount of powdery cellulose to be added within the range of 20 to 500 mg to prepare measurement solutions having different powdery cellulose concentrations.

(Ii) Measurement of viscosity average degree of polymerization The measurement solution (copper ammonia solution) obtained in (i) above was placed in an Ubbelohde viscometer and allowed to stand for 1 hour in a thermostat (20±0.1°C). After that, the flow rate of the liquid was measured. From the flow-down time (t (seconds)) of the copper-ammonia solution having various powdery cellulose concentrations (g/dL) and the flow-down time (t ₀ (seconds)) of the sample-free copper-ammonium aqueous solution, the following equations were used. The reduced viscosity (η _sp /c) at the concentration was determined by the following formula.
η _sp /c=(t/t ₀ -1)/c
(In the formula, c is the concentration of powdery cellulose (g/dL).)
Furthermore, the reduced viscosity determined intrinsic viscosity [η] (dL / g) and extrapolated to c = 0, was determined viscosity-average molecular weight (M _V) from the following equation.
M _V =2000×[η]×162.14 (g/mol)
(In the formula, 2000 is a coefficient specific to cellulose.)

(6) Measurement of Viscosity (Intrinsic Viscosity Number) A pulp sample was torn, cut into small pieces, shaken in distilled water for disaggregation, and then a thin sheet was prepared with a Buchner funnel, and the sheet was dried at 60°C. Air-dry cellulose corresponding to about 0.04 g by absolute drying is precisely weighed, placed in a 50 mL Erlenmeyer flask, and then 10 mL of ion-exchanged water is added, and when sufficiently permeated, 1 M copper ethylenediamine (CED) solution (commercially available product 10 mL of copper (containing 1.0 mol of copper and 2.0 mol of ethylenediamine) was added and dissolved with stirring. After the standing, the Erlenmeyer flask was tilted, and if there was no swollen gel-like mass on the bottom, it could be judged that the solution was dissolved. After the pulp is dissolved, the pulp is transferred to a capillary viscometer (capillary type), set in a constant temperature water bath at 25° C., and left to stand at 25° C.±0.1° C. The solution was sucked up and the flow time of the solution was measured. From the flow-down time (t ₀ (second)) of the blank solution (0.5 M copper ethylenediamine solution containing no pulp), the flow-down time (t (second)) of the pulp solution, and the pulp concentration (c, g/mL), The intrinsic viscosity [η] was calculated from the relative viscosity (ηr) and the specific viscosity (ηsp) by the following formula. The cellulose concentration was calculated by determining the absolute dry mass from the accurately weighed air-dried cellulose mass and its water content, and setting the volume of the solution to 20 mL.
η _r =η/η ₀ =t/t ₀
ηsp = η _r -1
[Η]=ηsp/(100×c(1+0.28ηsp))

(7) Calculation of average number of moles of alkyleneoxy group added and degree of cation substitution The degree of substitution of the propyleneoxy group and the degree of substitution of the cationic group in the C-HACs obtained in each example are calculated based on the chlorine element amount by elemental analysis. It was determined from the measured value and the value obtained according to the analysis method for hydroxypropyl cellulose described in the 15th revised Japanese Pharmacopoeia, except that the analysis target is C-HPC instead of hydroxypropylcellulose.
Specifically, the aqueous solution of C-HAC obtained in each example was purified by a dialysis membrane (fraction molecular weight 1000), and then the aqueous solution was freeze-dried to obtain purified C-HAC. The chlorine content (%) of the obtained C-HAC was measured by elemental analysis, and the number of cation groups contained in the purified C-HAC and the number of chloride ions as counterions were approximated to be the same. Then, the amount (a (mol/g)) of the cation groups contained in the C-HAC unit mass was determined from the following calculation formula (2).
a (mol/g)
=Chlorine content (%)/(35.5×100) obtained from elemental analysis (2)
Next, except that the analysis target is not purified hydroxypropylcellulose but purified C-HAC, the hydroxypropoxy group-containing content in purified C-HAC is determined according to "Analysis method of hydroxypropylcellulose" described in the 15th revised Japanese Pharmacopoeia. The amount (%) was measured. The hydroxypropoxy group content [formula weight (—OC ₃ H ₆ OH)=75.09] (b (mol/g)) was calculated from the following calculation formula (3).
b (mol/g)
= Hydroxypropoxy group content (%) obtained from gas chromatographic analysis
/(75.09×100) (3)
The cation substitution degree (k) of C-HAC and the average number of moles of propyleneoxy groups added (m) were calculated from the obtained a and b and the following calculation formulas (4) and (5).
a=k/(162+k×151.5+m×58) (4)
b=m/(162+k×151.5+m×58) (5)
[In Formula, k shows the cation substitution degree of C-HAC. m represents the average number of moles of propyleneoxy groups added. ]
When the alkyleneoxy group is an ethyleneoxy group, the hydroxyethyl group content (%) is measured in place of the hydroxypropoxy group content, and the hydroxyethyl group content (mol/g ) Can be obtained and the average number of added moles can be calculated.

Production Example 1 (Production of cellulose derivative)
<Step 1>
(1) Cutting treatment As a cellulose-containing raw material, a sheet-shaped wood pulp ("BioflocHV+" manufactured by Tembec, crystallization index: 82%, water content: 7.0%, Viscosity: 1524 mL/g, S18: 5.3%). Was cut into chips of about 3 mm x 1.5 mm x 1 mm using a cutting machine (product name: Super Cutter RK6-800, manufactured by Ogino Seiki Co., Ltd.).
(2) Drying treatment The pulp obtained by the cutting treatment in (1) above was used in a biaxial horizontal stirring dryer (“2-axial paddle dryer, NPD-3W (1/2)” manufactured by Nara Machinery Co., Ltd.). The pulp was dried in a continuous process. The heating medium of the dryer was steam at 150° C., the pulp feed rate was 45 kg/h, and the treatment was performed under atmospheric pressure.
(3) Cellulose coarse crushing treatment The dry pulp obtained by the drying treatment of the above (2) was treated with a continuous vibration mill (“Vibromill, YAMT-200” manufactured by Uras Techno Co., Ltd., capacity of the first and second crushing chambers: 112 L, made of stainless steel). In each of the first and second crushing chambers, 80 round rod-shaped crushing media (rods) made of stainless steel and having a diameter of 30 mm and a length of 1300 mm were accommodated. The continuous vibrating mill was fed with dry pulp at 20.0 kg/h under conditions of a frequency of 16.7 Hz and an amplitude of 13.4 mm. The volume-median particle size (D ₅₀ ) of the obtained coarsely pulverized pulp was 191 μm.
(4) Cellulose size reduction treatment The coarsely pulverized cellulose obtained by the coarse pulverization treatment in (3) above was processed using a high-speed rotary fine pulverizer (Dalton Co., Ltd., product name "Atomizer AIIW-5 type"). The particle size was reduced. A screen with an opening of 1.0 mm was attached, the rotor peripheral speed was driven at 50 m/s (4400 r/min) at a temperature of 55° C., and coarsely pulverized cellulose was supplied from the raw material supply section at the same supply rate as in the coarse pulverization treatment. The powdery cellulose was recovered from the outlet. The water content of the obtained powdery cerose was 1.7%, the crystallization index was -10.7%, and the volume median particle diameter (D ₅₀ ) was 70.6 μm. The processes (1) to (4) were continuously performed.

<Step 2>
100 parts by mass of the powdery cellulose obtained in step 1 was added to a jacketed reaction tank (WB-300PV manufactured by Taiheiyo Kiko Co., Ltd.) equipped with a main blade and a chopper blade as a stirrer. I put it in. After substituting the gas phase in the tank with nitrogen, 24.5 parts by mass of sodium hydroxide as a basic compound (1 mol of AGU of powdery cellulose) was stirred with a main blade peripheral speed of 3 m/s and a chopper blade of 16 m/s. 1.0 mol) and water were spray-injected. The amount of water used to prepare the aqueous sodium hydroxide solution was adjusted such that the total amount of the amount of water and the water content of the powdery cellulose was 49.8 parts by weight as the water content in the reaction system. .. Further, the inner temperature was adjusted to 50° C.±5° C. with jacket warm water, and mixing was continued for 2 hours. Next, 142.9 parts by mass of propylene oxide (PO) (4.0 mol per 1 mol of AGU of the powdery cellulose) was adjusted to an internal pressure of 0.07 to 0. It was charged for about 8 hours so as to keep it at 10 MPa (gauge pressure). After all the propylene oxide was added, stirring and temperature control were continued for about 3 hours until the internal pressure was sufficiently stabilized. The water content in the reaction at this time was 49.8% by mass with respect to the cellulose. Subsequently, a 70 mass% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride (HAC) which is a cationizing agent (water content 30%, purity 90% or more, manufactured by Yokkaichi Gosei Co., Ltd., product name "CTA-65". )) 112.0 parts by mass (0.68 mol of HAC for 1 mol of AGU of powdery cellulose) was sprayed in, and stirring was continued for 2 hours while adjusting the internal temperature to 50°C ± 5°C. The water content in the reaction at this time was 83.4 mass% with respect to the cellulose. Then, the internal temperature was cooled to 40° C. to obtain cationized hydroxypropyl cellulose which is a cellulose derivative. The total amount charged per unit volume of the reaction tank was 174 kg/m ³ . The average number of moles of PO added in the cationized hydroxypropyl cellulose was 2.41, and the degree of cation substitution was 0.18.

Production Examples 2 to 6, Comparative Production Example 1
From the sheet-like wood pulp shown in Table 1, in the same manner as in Production Example 1, (1) cutting treatment, (2) drying treatment, (3) cellulose coarse pulverization treatment, and (4) cellulose particle size reduction treatment, The powdery cellulose having the water content, the crystallization index, and the volume median particle diameter (D ₅₀ ) shown in Table 1 was obtained. Cationized hydroxypropyl cellulose was obtained in the same manner as in Example 1 except that this powdery cellulose was used in Step 2. The results are shown in Table 1.

*1: The molar equivalent of cellulose to 1 mol of anhydrous glucose (AGU)

[Evaluation of hair cosmetics]
Examples 1 to 6 and Comparative Example 1 (manufacture and evaluation of shampoo)
A hair shampoo having the following composition was manufactured as follows. C-HACs (1) to (7) obtained in Production Examples 1 to 6 and Comparative Production Example 1, cationic polymer, cationized guar gum, and sodium polyoxyethylene alkyl sulfate as a surfactant (manufactured by Kao Corporation, product Name: Emal 170S-A (70% aqueous solution)), lauryl hydroxysulfobetaine (Kao Corporation, trade name: Amphitol 20HD (30% aqueous solution)), silicone (Toray Dow Corning Co., Ltd., silicone BY22-050A ( Using an effective content of 55%)), a shampoo having an effective content of each component having the composition shown in Table 2 was prepared by a conventional method.
Purified water, methylparaben, and a surfactant were placed in a beaker and heated to 80°C with stirring. After confirming the uniform dissolution, C-HAC and a cationic polymer aqueous solution previously diluted to 2% with water were added. After cooling to 60°C or lower, the silicone was cooled to 45°C or lower, and then a fragrance was added and stirred until uniform. The mixture was cooled to room temperature, supplemented with water evaporated by heating, and further stirred for 30 minutes or more.
The composition of the hair shampoo for evaluation is shown in Table 2 below.

Each component used in Table 2 is as follows.
*1: 17.1% of Emal 170S-A (effective 70%) manufactured by Kao Corporation is added.
*2: 2.6% addition of Amhitol 20HD (effective content 30%) manufactured by Kao Corporation
*3: Sofcare KG101E manufactured by Kao Corporation (effective content 40%) added at 0.05%
*4: Jaguar C-13S manufactured by Rhodia
*5: Silicone BY22-050A manufactured by Toray Dow Corning Co., Ltd. (effective 55
%) added 0.91%

(Evaluation method)
Each component having the composition shown in Table 3 below was placed in a beaker, heated to 80° C., mixed, confirmed to be uniformly dissolved, and then cooled to obtain a plain shampoo. After washing the hair bundle with the obtained plain shampoo and thoroughly moistening it with warm water at 35 to 40°C, wash it with a shampoo having the composition shown in Table 2, rinse with warm water, remove water with a towel, and comb with hair. I arranged the bunch. Then, it was dried with warm air from a dryer, and the hair bundle was trimmed with a comb for finishing. Using the hair bundle thus treated as a tress for evaluation, four panelists evaluated after washing, rinsing and drying according to the following evaluation criteria and evaluation methods. The results are shown in Table 4.

(Evaluation criteria)
Based on the standard hair shampoo that does not contain C-HAC of the product of the present invention, the following items have the same performance as 1, slightly good as 2, and good as 3 and the average of four professional panelists is shown in Table 4. Described in.
The following items were judged according to the following criteria.
・Amount of foam during cleaning, foaming speed, foam retention, foam slippage ・Smoothness of hair during rinsing and its duration (length of time until a squeaky feeling is felt), softness of hair, creaking of hair Less feeling, finger passage of hair (less tangling of hair), less residual feeling, finger passage of hair after drying, smoothness of hair, cohesion of hair, smoothness of hair 3: Good 2 : Fairly good 1: Equivalent

As is clear from Table 4, in step 1, when C-HAC was obtained using pulp having a 18% by mass sodium hydroxide-soluble content of 5.6% by mass or less as a raw material, the C-HAC A hair cleansing agent containing HAC (hair shampoo) has good foam slippage during cleaning, and has excellent foam volume, foaminess, smoothness of hair during rinsing and its durability, and smoothness of hair after drying. It was excellent in passing, fingering, cohesiveness and dryness.
On the other hand, in Comparative Example 1 in which pulp with S18 exceeding 5.6% by mass was used as a raw material, foam slip and foam retention were not sufficient, and the foam collapsed during cleaning, resulting in poor usability during cleaning. It was Further, the smoothness of the hair during rinsing and the lasting of the smoothness were particularly poor. Furthermore, after drying, the hair was inferior in smoothness, good finger feel and smoothness.
Thus, by using a pulp having a specific content of 18% by mass of sodium hydroxide as a raw material, a cationized hydroxyalkyl cellulose having an extremely excellent effect can be obtained when blended in a hair cosmetic composition. Became clear.

The cationized hydroxyalkyl cellulose obtained by the production method of the present invention can provide a high-quality product, especially when blended in a hair cosmetic composition.

Claims (7)

A method for producing a cationized hydroxyalkyl cellulose, which comprises the following step 1 and step 2 in this order.
Step 1: Step of crushing pulp having 18% by mass of sodium hydroxide soluble content of 5.6% by mass or less to obtain powdery cellulose Step 2: The powdery cellulose obtained in Step 1 is added with alkylene oxide and cation Step of reacting with an agent The method for producing cationized hydroxyalkyl cellulose according to claim 1, wherein the cellulose obtained in step 1 has a viscosity average molecular weight of 100,000 or more and 180,000 or less. The method for producing a cationized hydroxyalkyl cellulose according to claim 1 or 2, wherein the cationizing agent is represented by the following formula 1 or 2.

In formulas (1) and (2), R ^{21 to} R ²³ each independently represent a hydrocarbon group having 1 to 24 carbon atoms, A represents a halogen atom, X ⁻ represents an anion, and t is 0. An integer of 3 or less is shown. The method for producing a cationized hydroxyalkyl cellulose according to claim 1, wherein the cellulose obtained in step 1 is an amorphous cellulose having a crystallization index of 30% or less. The cationized hydroxy according to any one of claims 1 to 4, further comprising a step of confirming that the 18% by mass sodium hydroxide-soluble content of the pulp is 5.6% by mass or less before the step 1. Method for producing alkyl cellulose. The method for producing a cationized hydroxyalkyl cellulose according to claim 1, wherein the alkylene oxide contains an alkylene oxide compound having 2 to 4 carbon atoms. A method for producing a hair cosmetic, comprising mixing a cationized hydroxyalkyl cellulose obtained by the method according to any one of claims 1 to 6 with a surfactant.