Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B11/00—Preparation of cellulose ethers
  • C08B11/02—Alkyl or cycloalkyl ethers
  • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
  • C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
  • C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/08—Cellulose derivatives
  • C08L1/26—Cellulose ethers
  • C08L1/28—Alkyl ethers
  • C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]

Definitions

• the present invention relates to a method for producing carboxymethyl cellulose.
• Carboxymethylcellulose (hereinafter also referred to as “CMC”) is widely used as a thickener, a dispersant, an emulsifier, a protective colloid agent, a stabilizer, and the like.
• this CMC is produced by a solvent method in which cellulose is treated with a large amount of alkaline water to activate it as alkali cellulose (arcelerization), and then dispersed in a water-containing organic solvent and reacted with monohaloacetic acid.
• Patent Document 1 discloses a method for producing carboxymethyl cellulose or a salt thereof, which includes a step of reacting cellulose and alkali at a temperature of 20 to 50 ° C.
• Patent Document 2 discloses a method for producing a cellulose derivative, in which a low crystalline powdery cellulose having a crystallinity of 50% or less is reacted with an organic halide compound in the presence of a base.
• the present invention relates to a method for efficiently producing carboxymethyl cellulose having a high aqueous solution viscosity.
• the present invention is a method for producing carboxymethyl cellulose, in which raw pulp is pulverized by a pulverizer, and then cellulose in the obtained pulverized product is reacted with monohaloacetic acid or a salt thereof and an alkali agent at 40 to 100 ° C.
• the present invention relates to a method for producing carboxymethyl cellulose, comprising a step of mixing the monohaloacetic acid or a salt thereof and / or an alkaline agent with the raw material pulp before or during the pulverizing treatment of the raw material pulp.
• carboxymethyl cellulose having a high aqueous solution viscosity can be efficiently produced.
• the present invention is a method for producing carboxymethyl cellulose, in which raw pulp is pulverized by a pulverizer, and then cellulose in the obtained pulverized product is reacted with monohaloacetic acid or a salt thereof and an alkali agent at 40 to 100 ° C.
• monohaloacetic acid or a salt thereof and / or an alkali agent By mixing the monohaloacetic acid or a salt thereof and / or an alkali agent with the raw material pulp before or during the pulverization treatment of the raw material pulp, carboxymethyl cellulose having a high aqueous solution viscosity can be produced efficiently and simply. .
• Step 1 A step of mixing raw pulp with monohaloacetic acid or a salt thereof and pulverizing with a pulverizer (hereinafter also referred to as “pulverizing step”).
• Step 2 A step of reacting the cellulose in the pulverized product obtained in Step 1 with monohaloacetic acid or a salt thereof and an alkali agent at 40 to 100 ° C. to obtain carboxymethyl cellulose (hereinafter also referred to as “reaction step”)
• reaction step A step of reacting the cellulose in the pulverized product obtained in Step 1 with monohaloacetic acid or a salt thereof and an alkali agent at 40 to 100 ° C.
• raw material pulp examples include cotton linter, rice straw pulp, and wood pulp. Specifically, linter pulp, N-wood pulp mainly composed of softwood, and L mainly composed of hardwood. Pulp and the like can be used.
• the shape of the raw material pulp is not particularly limited, but in the production method of the present invention, the higher the degree of polymerization of the raw material pulp, the higher the degree of polymerization of carboxymethyl cellulose can be obtained. On the other hand, the degree of polymerization of the raw material pulp is lowered by processing such as pulverization. Therefore, from the viewpoint of obtaining carboxymethyl cellulose having a high degree of polymerization, the shape of the raw material pulp is preferably a chip shape.
• a shredder for example, manufactured by Meiko Shokai Co., Ltd., trade name: “MSX2000-IVP440F” or a sheet pelletizer (for example, manufactured by Horai Co., Ltd., trade name: “SGG-220-”).
• 3X3 a shredder
• the diameter of the chip is preferably 0.6 to 100 mm, more preferably 0.8 to 30 mm, and more preferably 1 to 10 mm in terms of the number average of 100 long diameters (the longest length of one chip). Further preferred.
• the average degree of polymerization of cellulose constituting the raw material pulp is preferably 1000 or more, more preferably 1200 or more, and further preferably 1500 or more, from the viewpoint of developing a high aqueous solution viscosity.
• the upper limit of the average degree of polymerization is not particularly limited, but is preferably 5000 or less from the viewpoint of availability.
• the average degree of polymerization of a cellulose means a viscosity average degree of polymerization, and specifically, it measures by the method as described in an Example.
• crystallinity of cellulose means the crystallinity derived from the type I crystal structure of natural cellulose, and is calculated by the Segal method from the diffraction intensity value by the powder X-ray crystal diffraction spectrum method. , Defined by the following formula (1).
• the crystallinity of the cellulose constituting the raw pulp is preferably more than 50% and 95% or less, more preferably 60 to 95%, still more preferably 70 to 95%, from the viewpoint of maintaining a high degree of polymerization. More preferably, it is 75 to 95%.
• the alkali agent used in the present invention is preferably an alkali metal hydroxide or an alkaline earth metal hydroxide from the viewpoint of efficiently converting the hydroxyl groups of cellulose molecules constituting the raw material pulp into alcoholates.
• Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like, and specific examples of the alkaline earth metal hydroxide include magnesium hydroxide and calcium hydroxide. Among these, an alkali metal hydroxide is preferable, and sodium hydroxide or potassium hydroxide is more preferable. There is no limitation on the form of the alkaline agent.
• an aqueous solution is preferably used from the viewpoint of operation.
• the concentration in the case of adding the alkaline agent in the form of an aqueous solution is not particularly limited, but since the reaction step described below is affected by the amount of water, the amount of water after the addition of the alkaline agent exceeded the suitable amount of water in the reaction step. In some cases, it is desirable to perform operations such as dehydration. Therefore, the concentration of the alkaline agent aqueous solution is preferably 10% by mass or more. On the other hand, from the viewpoint of easy availability, the concentration of the alkaline agent aqueous solution is preferably 75% by mass or less. From the above viewpoint, the concentration of the alkaline agent aqueous solution is preferably 10 to 75% by mass, more preferably 20 to 65% by mass, and still more preferably 30 to 55% by mass.
• the molar equivalent ratio of the alkali agent to the anhydroglucose unit of the cellulose constituting the raw pulp is preferably 0.3 to 3 from the viewpoint of developing a high aqueous solution viscosity. More preferably 0.5 to 2, still more preferably 0.5 to 1.8, still more preferably 0.5 to 1.5, and still more preferably 0.5 to 1.2.
• the number of moles of anhydroglucose units can be determined as a value obtained by dividing the dry weight of cellulose by the molecular weight 162 of anhydroglucose units.
• the alkali agent is consumed for neutralization of monohaloacetic acid, so the molar equivalent ratio of the alkali agent to the anhydroglucose unit of the cellulose constituting the raw pulp (alkali agent / anhydroglucose unit) is high.
• it is preferably 0.6 to 6, more preferably 1.0 to 4, and still more preferably 1 to 3.
• the halogen atom in the monohaloacetic acid used in the present invention is preferably an iodine atom, a bromine atom or a chlorine atom, more preferably a bromine atom or a chlorine atom, still more preferably chlorine, for reasons of reactivity, versatility and ease of handling. Is an atom.
• the metal capable of forming a salt of monohaloacetic acid is preferably lithium, potassium or sodium, more preferably potassium or sodium, and still more preferably sodium, from the viewpoint of expressing the water solubility of the resulting carboxymethyl cellulose and high aqueous solution viscosity. .
• monohaloacetic acid or a salt thereof used in the present invention include monochloroacetic acid, monobromoacetic acid, sodium monochloroacetate, potassium monochloroacetate and the like, and monochloroacetic acid or sodium monochloroacetate is preferable.
• Monohaloacetic acid or a salt thereof may be used in the form of a solid (powder) or may be used after being dissolved in water or a hydrophilic organic solvent described later.
• the molar equivalent ratio of monohaloacetic acid or a salt thereof to anhydroglucose unit of cellulose constituting the raw pulp is preferably 0.3 to 3, from the viewpoint of developing a high aqueous solution viscosity, More preferably, it is 0.5 to 2.0, still more preferably 0.5 to 1.6, and still more preferably 0.6 to 1.0.
• Said monohaloacetic acid or its salt, and an alkali agent can be used individually or in combination of 2 types or more, respectively.
• the molar equivalent ratio of the alkali agent to the monohaloacetic acid used in the present invention is preferably 2 to 3, more preferably 2 to 2, for the reason that the reaction is carried out efficiently while suppressing side reactions. 0.5, more preferably 2 to 2.2, and even more preferably 2 to 2.1.
• the molar equivalent ratio of the alkaline agent to the monohaloacetic acid salt used in the present invention is because the reaction is carried out efficiently while suppressing side reactions.
• Step 1 Crushing step
• raw pulp and monohaloacetic acid or a salt thereof are mixed and pulverized.
• the raw pulp is pulverized by a pulverizer in the presence of monohaloacetic acid or a salt thereof and an alkali agent. More specifically, monohaloacetic acid or a salt thereof and an alkali agent are mixed before pulverization of the raw pulp or during pulverization, and pulverized.
• Examples of the mixing and pulverizing method include the following (1) to (4).
• Both monohaloacetic acid or a salt thereof and an alkaline agent are used as the raw material pulp.
• Monohaloacetic acid or a salt thereof is mixed before or during pulverization of raw pulp, and an alkali agent can be obtained after the pulverization is completed.
• One of monohaloacetic acid or a salt thereof, or an alkali agent is mixed with raw pulp before the raw pulp is pulverized, and the other is being pulverized during the pulverization How to mix with
• the mixing and pulverizing method may be any of the above methods (1) to (4), but from the viewpoint of obtaining carboxymethyl cellulose having a high aqueous solution viscosity, the methods (1), (2) and (4), That is, a method having a step of pulverizing raw pulp with a pulverizer in the presence of monohaloacetic acid or a salt thereof and an alkali agent is preferable, and the method (4) is more preferable.
• the order of adding the raw materials and the order of pulverization are not particularly limited. Monohaloacetic acid or a salt thereof may be added to the raw pulp and pulverized, then an alkali agent may be added, and further pulverized.
• an alkaline agent may be added to the raw pulp and pulverized, and then the monohaloacetic acid or a salt thereof. And may be further pulverized.
• the raw pulp, monohaloacetic acid or a salt thereof, and an alkali agent may be mixed at the same time and pulverized.
• a method in which raw pulp and monohaloacetic acid or a salt thereof are mixed and pulverized, and then an alkali agent is added and further pulverized is preferable.
• Examples of the pulverizer used in the present invention include those shown in Tables 16 and 4 on page 843 of “Chemical Engineering Handbook, Revised Sixth Edition” edited by the Chemical Engineering Society. More specific examples include roll mills such as high pressure compression roll mills and roll rotating mills; rigid roller mills such as ring roller mills, roller race mills or ball race mills; rolling ball mills, vibration ball mills, vibration rod mills, vibration tube mills, planets Container drive medium mill such as ball mill or centrifugal fluidization mill; medium agitation mill such as tower pulverizer, stirring tank mill, flow tank mill or annular mill; compaction shear mill such as high speed centrifugal roller mill or ang mill; A mortar, a stone mill, etc. are mentioned.
• a container-driven medium mill or a medium agitating mill is preferable, a container-driven medium mill is more preferable, and a vibration ball mill, a vibration rod mill, or a vibration tube mill is more preferable.
• the processing method may be either a batch type or a continuous type.
• a material of a grinder and / or a medium For example, iron, stainless steel, an alumina, a zirconia, a silicon carbide, a silicon nitride, glass etc. are mentioned. Among these, iron, stainless steel, zirconia, silicon carbide, and silicon nitride are preferable from the viewpoint of mixing and grinding efficiency, and iron or stainless steel is more preferable from the viewpoint of industrial use. From the viewpoint of mixing and pulverization efficiency, when the pulverizer used is a vibration mill and the medium is a rod, the outer diameter of the rod is preferably 0.1 to 100 mm, more preferably 0.5 to 50 mm. Range.
• the rod filling rate varies depending on the type of vibration mill, but is preferably in the range of 10 to 97%, more preferably 15 to 95%. If the filling rate of the rod is within this range, the contact frequency between the cellulose or the reactant and the rod can be improved, and the grinding efficiency can be improved without hindering the movement of the medium.
• the rod filling rate refers to the apparent volume of the rod relative to the volume of the stirring section of the vibration mill.
• the pulverization time depends on the pulverization conditions such as the size (volume) of the pulverizer, but is preferably about 3 to 3 hours, more preferably 5 to 60 minutes, from the viewpoint of obtaining carboxymethylcellulose having a high aqueous solution viscosity. Minutes are more preferred.
• the temperature during pulverization is preferably 5 ° C. or more and less than 40 ° C., more preferably 5 to 38 ° C., and still more preferably 5 to 35 ° C., from the viewpoint of obtaining carboxymethyl cellulose having a high aqueous solution viscosity. As long as the object of the present invention is not impaired, there may be a portion where the temperature is locally increased during pulverization.
• a step of impregnating the raw pulp with monohaloacetic acid or a salt thereof before the raw pulp is pulverized from the viewpoint of obtaining a carboxymethyl cellulose having a high aqueous solution viscosity by suppressing a decrease in the degree of polymerization.
• a raw pulp and a solution of monohaloacetic acid or a salt thereof are mixed with a commonly used mixing and stirring device such as a Henschel mixer, an anchor blade, etc.
• a method for removing the solvent can be used.
• the solvent can be removed by a general method such as drying under reduced pressure.
• the drying time under reduced pressure is preferably 6 to 48 hours, more preferably 8 to 24 hours.
• the hydrophilic organic solvent those described later can be used.
• the water content in the pulverization treatment step is preferably 10 parts by weight or more with respect to 100 parts by weight of the dry raw material pulp from the viewpoint of suppressing the decrease in the degree of polymerization and obtaining carboxymethyl cellulose having a high aqueous solution viscosity.
• the water content is preferably 100 parts by weight or less with respect to 100 parts by weight of the dry raw material pulp from the viewpoint of pulverization efficiency and the water content in the reaction step described later in a suitable range.
• the water content is preferably 10 to 100 parts by weight, more preferably 10 to 90 parts by weight, further preferably 15 to 80 parts by weight, and more preferably 20 to 60 parts by weight with respect to 100 parts by weight of the dry raw material pulp. Further preferred.
• the water content in the pulverization process within the above range, aggregation of cellulose can be suppressed, and the subsequent reaction process can be performed while maintaining a good powder state, and further, a decrease in the polymerization degree of the raw material can be suppressed. It becomes possible.
• the end point of the pulverization treatment of the raw material pulp is preferably the median diameter of cellulose and / or carboxymethyl cellulose in the pulverized product obtained from the viewpoint of reacting the pulverized product with monohaloacetic acid or a salt thereof and an alkali agent in the next step.
• it can be pulverized to 1 to 800 ⁇ m, more preferably 10 to 500 ⁇ m, still more preferably 10 to 300 ⁇ m, and still more preferably 30 to 250 ⁇ m.
• the method for measuring the median diameter is as described in Examples described later.
• the obtained pulverized product is mainly composed of cellulose, but may partially react to become carboxymethylcellulose.
• Step 2 Reaction step
• the cellulose in the obtained pulverized product is reacted with monohaloacetic acid or a salt thereof and an alkali agent at 40 to 100 ° C. to obtain carboxymethylcellulose.
• the reaction method include the following (i) to (ii).
• an alkali agent is added and mixed to the obtained mixed pulverized product, and additional monohalo is added as necessary.
• reaction When monohaloacetic acid or a salt thereof and an alkali agent are mixed before or during the pulverization treatment of the raw pulp, the reaction may be carried out as it is, but if necessary, additional monohaloacetic acid or a salt thereof. And / or an alkali agent can be added and mixed to carry out the reaction.
• a mixer capable of mixing uniformly.
• a mixer such as a so-called kneader used for kneading high-viscosity substances such as powders and resins as disclosed in paragraph [0016] of JP-A-2002-114801 is used as the reaction apparatus.
• the mixer such as a kneader is not particularly limited as long as it can sufficiently stir.
• the chemical engineering manual edited by “Chemical Engineering Handbook” revised 5th edition published by Maruzen Co., Ltd.
• examples of the single-axis kneader include a ribbon mixer, a kneader, a botter, and a screw-type kneader
• examples of the biaxial kneader include a double-arm kneader. It is more preferable that these mixers have a portion where the aqueous base solution can be dropped and dehydrated.
• the reaction temperature is from 40 to 100 ° C., preferably from 40 to 80 ° C., more preferably from the viewpoint of allowing the reaction to proceed efficiently while suppressing side reactions and suppressing a decrease in the degree of polymerization of cellulose. ⁇ 70 ° C.
• the reaction atmosphere in the reaction step is preferably carried out in an inert gas atmosphere from the viewpoint of suppressing a decrease in the degree of polymerization of cellulose and expressing a high aqueous solution viscosity.
• the inert gas is preferably nitrogen, helium or argon, more preferably nitrogen or argon, still more preferably nitrogen.
• stirring is preferably performed at 1 to 500 rpm, more preferably 2 to 200 rpm, and still more preferably 5 to 100 rpm.
• the reaction time is preferably about 1 to 10 hours, more preferably about 2 to 8 hours.
• the end point of the reaction can be taken as a standard when 95% by weight or more of the total amount of monohaloacetic acid or its salt has been consumed, and the progress of the reaction can be confirmed by high performance liquid chromatography (HPLC) or the like. it can.
• HPLC high performance liquid chromatography
• an aqueous solution of a hydrophilic solvent such as methanol is added to the obtained reaction product, and salts such as NaCl can be removed by filtration after stirring.
• Carboxymethylcellulose is obtained as a filter cake, and can be washed with acetone and dehydrated efficiently.
• hydrophilic organic solvent From the viewpoint of improving the mixing property of monohaloacetic acid or a salt thereof and raw pulp, a hydrophilic organic solvent may be used in the pulverization treatment step and / or the reaction step.
• the hydrophilic organic solvent is preferably one that dissolves 100 g or more in 100 g of water at 25 ° C. from the viewpoint of the reactivity between the raw material pulp and monohaloacetic acid or a salt thereof.
• the hydrophilic organic solvent that can be used in the method of the present invention is preferably a secondary or tertiary lower alcohol such as isopropanol or tert-butanol; diglyme such as 1,4-dioxane, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether;
• Examples include ether solvents such as triglyme; hydrophilic polar solvents such as dimethyl sulfoxide, more preferably secondary or tertiary lower alcohols such as isopropanol and tert-butanol, and more preferably isopropanol and tert-butanol.
• Said hydrophilic organic solvent can be used individually or in combination of 2 or more types.
• the amount of the hydrophilic organic solvent used in the reaction in the present invention is preferably 200 parts by weight or less, more preferably 150 parts by weight or less, still more preferably 100 parts by weight or less, and still more preferably with respect to 100 parts by weight of the dry raw material pulp. Is 50 parts by weight or less, more preferably 30 parts by weight or less.
• the water content in the reaction step is preferably 100 with respect to 100 parts by weight of the dry raw material pulp from the viewpoint of efficiently alcoholating the hydroxyl groups of the cellulose molecules with an alkali agent and suppressing the aggregation of the pulverized product.
• the amount is not more than parts by weight, more preferably 10 to 90 parts by weight, still more preferably 15 to 80 parts by weight, still more preferably 20 to 60 parts by weight.
• carboxymethylcellulose having a high aqueous solution viscosity is obtained.
• the obtained carboxymethyl cellulose may be a salt, and the salt is preferably an alkali metal salt such as sodium, potassium or lithium or an alkaline earth metal salt such as magnesium or calcium.
• the viscosity of a 1% by weight aqueous solution of carboxymethylcellulose obtained by the method of the present invention (100 mol% neutralized product with sodium salt) (25 ° C.) is preferably 500 mPa ⁇ s or more, more preferably from the viewpoint of developing high viscosity.
• it is preferably 10,000 mPa ⁇ s or less and more preferably 5000 mPa ⁇ s or less from the viewpoint of handleability.
• the measuring method of the aqueous solution viscosity is as described in Examples described later.
• Carboxymethyl cellulose obtained by the method of the present invention is useful as a thickener for cosmetics and the like.
• the crystallinity of cellulose in raw pulp or pulverized material is measured using the raw pulp or pulverized material as a sample, and the X-ray diffraction intensity of the sample is determined by “Rigaku RINT 2500VC X” manufactured by Rigaku Corporation. -RAY diffractometer "(trade name) was measured under the following conditions and calculated based on the formula (1).
• the measurement sample was prepared by compressing a pellet having an area of 320 mm 2 ⁇ thickness of 1 mm.
• the X-ray scan speed was measured at 10 ° / min.
• aqueous solution viscosity A 1% aqueous solution of carboxymethyl cellulose (100 mol% neutralized with sodium salt) was prepared, and a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., trade name: “TVB-10M”) was used. 25 ° C., rotor: No. 3 (for measurement of 200 to 2000 mPa ⁇ s), 30 rpm, and 3 minutes. In addition, No. When the viscosity is less than 200 mPa ⁇ s when measured in No. 3, rotor: No. 1 and exceeding 2000 mPa ⁇ s, rotor: No. 4 is used.
• Production Example 1 Manufacture of chip-like pulp
• a commercially available cotton linter pulp sheet (manufactured by Shandong Takamitsu Chemical Co., Ltd., trade name: “PCS2400”, crystallinity 94%, water content 7.5% by weight) is used as a sheet pelletizer (manufactured by Horai Co., Ltd., trade name: “SGG- 220-3X3 ”) to form 3 mm square chips (average number of 100 pieces of long diameter (longest length of one chip)), and chip-like pulp (crystallinity 94%, average polymerization degree 2358, A water content of 7.3% by weight) was obtained.
• Production Example 2 Manufacture of chip-like pulp
• a commercially available wood pulp sheet (manufactured by Tenbeck, trade name: “Biofloc HV +”, crystallinity 74%, water content 6.7% by weight) is a sheet pelletizer (manufactured by Horai Co., Ltd., trade name: “SGG-220-3X3”). )
• chips of 3 mm square average number of 100 pieces of long diameter (the longest length of one piece)
• chip-like pulp crystallinity 74%, average polymerization degree 1506, water content 6) 0.7% by weight
• Example 1 In a mortar, 100.0 g of pulp chips obtained in Production Example 1 as a dry weight (0.617Mol, anhydroglucose unit conversion) were charged, to which 30% sodium monochloroacetate (ClCH 2 CO 2 Na, hereinafter "SMCA Also, 167.8 g (0.432 mol) of an aqueous solution was added and mixed with stirring. After the mixture was dried at 60 ° C. under a nitrogen stream under reduced pressure conditions (about 70 kPa) for 12 hours, 20.0 g of ion-exchanged water was added and mixed to adjust the water content.
• SMCA sodium monochloroacetate
• the mixed pulverized product obtained above was charged into a 1 L kneader (trade name: “PNV-1 type” manufactured by Irie Shokai Co., Ltd.), the inside of the kneader was decompressed (about 50 kPa), and then returned to normal pressure with nitrogen. Performed 3 times and replaced with nitrogen. Then, it heated up at 60 degreeC and stirred for 3 hours.
• the total amount of water derived from cellulose and other raw materials was 40 parts by weight with respect to 100 parts by weight of the dry raw material pulp. After confirming that 98% by weight or more of the added SMCA had been consumed, the product was cooled to room temperature and the product was removed from the kneader.
• Example 2 Thirteen round rods with a diameter of 30 mm are placed in a pot of a vibrating rod mill (manufactured by Chuo Kako Co., Ltd., trade name: “MB-1”), and the chip-like pulp obtained in Production Example 1 is dried by weight. 100.0 g (0.617 mol, anhydroglucose unit conversion), ion-exchanged water 12.2 g, and SMCA powder 50.3 g (0.432 mol) were added under the conditions of a frequency of 1200 cpm, an amplitude of 8 mm, and a grinding time of 6 minutes. Mixed and pulverized.
• MB-1 vibrating rod mill
• Example 3 Carboxymethylcellulose was obtained in the same manner as in Example 2 except that the pulverization time after addition of the SMCA powder was 12 minutes and that pulverization was not performed after the addition of the aqueous sodium hydroxide solution.
• the degree of substitution per unit of anhydroglucose of the obtained carboxymethyl cellulose was 0.46, and the 1% aqueous solution viscosity (25 ° C.) was 539 mPa ⁇ s.
• Table 1 The results are shown in Table 1.
• Example 4 40 weights with respect to 100 parts by weight of dry raw material pulp, using the chip-like pulp obtained in Production Example 2 as the chip-like pulp, and the total amount of water derived from cellulose and other raw materials in the pulverized product after mixing and pulverization
• carboxymethylcellulose was obtained in the same manner as in Example 2 except that the amount of ion-exchanged water added before mixing and grinding was changed to 13.2 g.
• the degree of substitution of the obtained carboxymethylcellulose per anhydroglucose unit was 0.50, and the 1% aqueous solution viscosity (25 ° C.) was 801 mPa ⁇ s.
• Table 1 The results are shown in Table 1.
• Example 5 12.1 g of ion-exchanged water, 107.8 g (0.926 mol) of SMCA powder, 39.4 g (0.486 mol) of 49.3% sodium hydroxide aqueous solution as an alkali agent, and beaded sodium hydroxide (Tosoh Corporation)
• Carboxymethylcellulose was obtained in the same manner as in Example 2 except that 21.4 g (0.535 mol) manufactured by the company and trade name “Tosoh Pearl” was used.
• the degree of substitution of the obtained carboxymethyl cellulose per anhydroglucose unit was 0.79, and the viscosity of a 1% aqueous solution (25 ° C.) was 750 mPa ⁇ s.
• Table 1 The results are shown in Table 1.
• Example 6 Thirteen round rods with a diameter of 30 mm are placed in a pot of a vibrating rod mill (manufactured by Chuo Kako Co., Ltd., trade name: “MB-1”), and the chip-like pulp obtained in Production Example 1 is dried by weight. 100.0 g (0.617 mol, converted to anhydroglucose unit) and 49.3% sodium hydroxide aqueous solution 38.6 g (0.475 mol) were added and mixed under conditions of a vibration frequency of 1200 cpm, an amplitude of 8 mm, and a pulverization time of 6 minutes. Crushed.
• MB-1 vibrating rod mill
• Comparative Example 1 Thirteen round rods with a diameter of 30 mm are placed in a pot of a vibrating rod mill (manufactured by Chuo Kako Co., Ltd., trade name: “MB-1”), and the chip-like pulp obtained in Production Example 1 is dried by weight. 100.0 g (0.617 mol, converted into anhydroglucose unit) was added, and the mixture was pulverized under conditions of a vibration frequency of 1200 cpm, an amplitude of 8 mm, and a pulverization time of 12 minutes, and powdered cellulose (crystallinity 78%, average polymerization degree 1216, The amount of water was 7.3% by weight and the particle size was 100 ⁇ m).
• the total amount of water derived from cellulose and other raw materials was 40 parts by weight with respect to 100 parts by weight of dry powdered cellulose. Subsequent operations were carried out in the same manner as in Example 1, such as neutralization and washing, to obtain carboxymethylcellulose.
• the degree of substitution of the obtained carboxymethylcellulose per anhydroglucose unit was 0.44, and the 1% aqueous solution viscosity (25 ° C.) was 343 mPa ⁇ s.
• Table 1 The results are shown in Table 1.
• the carboxymethyl cellulose of Comparative Example 1 obtained by adding monohaloacetic acid or a salt thereof and an alkali agent to the powdered cellulose obtained by pulverizing the raw material pulp and reacting it had a low aqueous solution viscosity.
• the carboxymethyl cellulose of Examples 1 to 6 obtained by reacting a pulverized product obtained by adding monohaloacetic acid or a salt thereof and an alkaline agent before or during pulverization of the raw pulp was an aqueous solution. It has a high viscosity and is useful as a thickener.
• the carboxymethyl cellulose having a high aqueous solution viscosity obtained by the method of the present invention is useful as a thickener for cosmetics and the like.

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