JPS6390501A - Porous fine cellulose particle and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled particle useful as a filler for liquid chromatography, by mixing cellulose xanthate with two kinds of water-soluble polymer compounds, coagulating and neutralizing the mixture and removing one of the polymer compounds from the obtained fine particles. CONSTITUTION:The objective porous fine particle is composed essentially of type-II cellulose and has the following characteristics. The crystallinity of the particle is 5-35% (determined by X-ray diffraction); the particle is composed of spherical or ellipsoidal particle having an average particle diameter of <=300mum; a differentiation curve of pore diameter and pore volume determined by mercury porosimetry has a peak of pore volume in the pore diameter range of 0.02-0.8mum; and the total pore volume in the above range is >=0.025ml/g. The particle can be produced e.g. by mixing cellulose xanthate with an alkaline aqueous solution of a 1st water-soluble polymer other than the xanthate and a 2nd water-soluble anionic polymer compound, coagulating the resultant dispersion of fine particles with an acid, neutralizing the product and removing the 1st polymeric compound from the obtained cellulose-containing fine particle.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to porous microcellulose particles, a method for producing the same, and uses thereof.

More specifically, the present invention relates to porous microcellulose particles consisting essentially of recycled cellulose, a WJI manufacturing method thereof, and uses thereof.

(Prior Art) Particles of cellulose or its various derivatives have recently come to be widely used in various fields as chromatography materials, polymer carriers, cosmetic heating agents, lubricants, and the like.

As a rice-removal, micro-cellulose ladle, American FMC Corporation's 151f:5i! High purity microcrystalline cells U-s are well known. This high-purity microcrystalline cellulose is produced by selecting a particularly high-purity purified bulb, which is hydrolyzed with mineral acid under certain conditions to wash and remove the amorphous regions, and then ground, purified, and dried. (Refer to the pamphlet published by Asahi Kasei Kogyo Co., Ltd. on March 1, 1980, titled 1-Crystalline Cellulose, Avicel ■)
. According to the pamphlet, the above-mentioned high-purity microcrystalline cellulose is chemically known as natural cellulose, that is, I
It can be seen that it is a type of cellulose itself, and that it is commercially available ranging from a small average particle size of about 6 μm to a large average particle size of about 4011 aa or about 120 μm. This high purity microcrystalline cellulose (Grade P
According to the inventor's () 1st study, H-MO6) is 31-3
It was revealed that the crystallinity was relatively good with a degree of crystallinity of about 5%.

JP-A-48-21738 discloses that the heptavalent is 50 or more,
A method is disclosed in which viscose having an average degree of polymerization of 400 or more is dropped in the form of particles into a coagulation regeneration bath having a low acid concentration and a low mirabilite concentration to gradually perform coagulation and regeneration. The examples in the same publication include 30 to 46 meshes (300 to 590 μm).
m) regenerated cellulose granules are described.

Japanese Patent Publication No. 56-21,761 describes a method in which viscose is extruded from a discharge port, the continuous flow is naturally changed into a droplet flow in the air, and the droplets are supplied to a coagulation/regeneration bath as nearly spherical droplets. is disclosed.

In the same publication, 16 to 170 meshes (88
~1168 μl) of cellulose granules are described.

Japanese Patent Publication No. 57-7162 discloses hollow regenerated cellulose fine particles having a large void in the center. The granules are described to have an apparent density of less than 0.4 g/cm' and a mesh size of 16 to 170 mesh.

Japanese Unexamined Patent Publication No. 48-60753 includes the aforementioned Unexamined Japanese Patent Application No. 48-60753.
By using a coagulation regeneration bath with a higher acid concentration and mirabilite concentration than the method disclosed in Publication No. 21738,
A method of making 170 mesh porous regenerated cellulose particles is disclosed.

Japanese Patent Publication No. 49-89,748 discloses that fibrous materials of recycled cellulose are hydrolyzed, dried, and pulverized to produce fibers with a length/diameter ratio of 20/1 to 2/1 and a length of 1. - A method of manufacturing the following cellulose powder is disclosed.

JP-A-57-212,231 discloses a method for producing cellulose powder from fibrous natural cellulose in the same manner as above.

Japanese Patent Publication No. 57-45,254 and the corresponding U.S. Pat. The particle size is reduced to 150-3 by heating to a temperature of
Particles with 50 μ scratches account for 85% by volume (Example 1)
It is disclosed that this can be obtained.

Japanese Patent Publication No. 55-39565 describes a solution of cellulose triacetate in methylene chloride or chloroform, for example, gelatin, polyvinyl alcohol, etc. 1. It is dropped into an aqueous medium in which a dispersant is dissolved, while stirring, and heated to form spherical particles of Sanzuryo cellulose, which are then saponified,
A method of making cellulose spherical particles is disclosed.

In the capsule example of the same publication, cellulose particles with a size of 30 to 500 μm are disclosed.

Japanese Patent Publication No. 55-40618 discloses a method for producing cellulose particles of 50 to 500 .mu.m from cellulose esters other than cellulose triacetate in the same manner as described above.

JP-A No. 55-28,763 states that the boiling point difference is 30°C.
A method for producing microspherical particles by spray-drying a solution of cellulose fatty acid ester dissolved in a mixed solvent of 3M1 or more different solvents is disclosed.

JP-A-56-244429 and the corresponding US Pat. No. 4,312,980 and European Patent Publication M2 S 639 disclose chlorinated hydrocarbons with boiling points lower than the following aqueous medium and carbon atoms. 3ffl in a mixed solvent from 6 or more aliphatic higher alcohols:! A solution of cellulose is suspended in an aqueous medium to form droplets of the solution, then the chlorinated hydrocarbons in the a droplets are evaporated off, and the resulting cellulose triacetate containing aliphatic higher alcohol is A method for producing porous cellulose spherical particles by saponifying spherical particles and removing aliphatic higher alcohol from the spherical particles is disclosed. Examples include particle sizes 10-200.
μm particles are disclosed.

JP-A-56-24430 discloses that triacetate of crystalline cellulose having a degree of chemotactic polymerization is dissolved in a chlorinated hydrocarbon whose boiling point is lower than that of the aqueous medium A described below, and this solution is suspended in the aqueous medium A. Porous cellulose spherical particles characterized in that the solution is made cloudy to form droplets, then the chlorinated hydrocarbons in the drops are removed by evaporation, and the obtained spherical particles of cellulose triacetate are saponified. The manufacturing method is described.

Examples of the publication disclose porous cellulose spherical particles having a particle size of 100 to 200 μm. JP-A-57-3
Publication No. 8801 and corresponding European patent publication tlS47
No. 064 and US Pat. No. 4,390,691 and No. 4,461,892 disclose that a cellulose organic acid ester solution dissolved in a solvent mainly containing chlorinated hydrocarbons is suspended in an aqueous medium, and the solution is In a method for producing porous spherical cellulose particles by forming droplets, evaporating the chlorinated hydrocarbon solvent in the droplets to form cellulose organic acid ester spherical particles, and then saponifying the same, the cellulose A method for producing porous spherical cellulose particles is described, which is characterized by adding and mixing an acid or alkali to an organic acid ester solution and suspending it in an aqueous medium. Examples of the same publication describe porous spherical cellulose particles having a particle size of 50 to 100 μm.

JP-A-57-159.801 discloses that cellulose is dissolved in a DMSO solution of rose formaldehyde, the resulting solution is dispersed in a liquid, and mixed with a cellulose coagulant to form dispersed droplets of cellulose. A method for producing granular cellulose dels by delt agglomeration and optional regeneration with hot water is disclosed.

JP-A-57-159802 discloses a method for producing porous cellulose by immersing granular cellulose in a DMSO solution of paraformaldehyde and heating it to make it moist.

~Kaimei No. 57-219,333 discloses that an aqueous medium solution containing an organic solvent solution of cellulose acetate, a dispersant, a surfactant, and a V antifoaming agent is applied to a rotary blade of NTl1450-/win.
The above discloses a method for producing spherical microparticles of cellulose acetate by stirring and mixing at 200 Orpm or more for at least 10 seconds and evaporating the organic solvent.

In JP-A No. 48-30,752, tetrahydro 7
? A method is disclosed for producing cellulose powder by treating cellulose with a mill and then pulverizing it.

JP-A-50-105,758 discloses that a dried cellulose sheet is passed between a pair of rotating rolls under pressure,
Then, by hydrolyzing with mineral acid, fine cellulose powder is produced! Il! The method of leaving is disclosed.

[Problems to be Solved by the Invention] An object of the present invention is to provide porous microcellulose particles consisting essentially of regenerated cellulose or H-type cellulose.

Another object of the present invention is to provide porous microcellulose particles consisting essentially of spherical or oblate particles having an average particle size of 300 μm or less.

Still another object of the present invention is that the pore volume has a maximum value in the pore diameter range of 0.02 to 0.8 μm, and the total pore volume of the pores in the same range is at least 0.025 ml/g. An object of the present invention is to provide porous microcellulose particles.

Still another object of the present invention is to provide a novel method for producing the porous microcellulose particles of the present invention as described above.

Still another object of the present invention is to provide fine cellulose powder.
L A-1 species K, mM 1 j)-ni'
Ltafilrs, ヱ, IRE 8 & tr+ The aqueous flukaline polymer solution is mixed with a second water-soluble anionic commercial molecular compound or a second nonionic polymer compound, and the above-mentioned first The purpose of the present invention is to regularly use the novel manufacturing method described above, which includes a step of producing a fine particle dispersion of the aqueous alkaline polymer solution containing a water-soluble polymer compound.

Still another object of the present invention is to provide the above-mentioned novel manufacturing method, which includes a step of removing the ml of water-soluble polymer compound from the fine particles produced by coagulation or neutralization.

Still another object of the present invention is to provide a useful use of the porous micro cellulose particles of the present invention, in which the porous micro cellulose particles are used as a filler for liquid chromatography. Other objects and advantages will become apparent from the description below.

[Means and Effects for Solving the Problems 1 According to the present invention, the above objects and advantages of the present invention are achieved by: (a) consisting essentially of U-shaped cellulose;
The degree of crystallinity determined by the linear diffraction method is in the range of 5 to 35%, (c) it consists essentially of spherical or prolate particles with an average particle size of 300 μm or less, and (d) the crystallinity is determined by the mercury porosimeter method. In the differential equation of pore diameter and pore volume, the maximum value of pore volume is in the pore diameter section of 0.02 to 0.8μ, and the total pore volume of the pores in the same section is at least 0.025 ml/g. This is achieved by porous microcellulose particles characterized by:

According to the present invention, the porous microcellulose particles of the present invention include: (1) alkaline polymer water solubility of cellulose xanthate and a first water-soluble polymer compound other than cellulose xanthate; (2) Mixing the water-soluble alkaline polymer and a second water-soluble anionic polymer compound to form the alkaline 'f4
producing a fine particle dispersion of an aqueous molecular solution; (3) (i) heating the dispersion or mixing the dispersion with a coagulant of cellulose xanthate; The first water-soluble polymer compound is coagulated as fine particles in a form containing the compound, and then neutralized with an acid to regenerate cellulose to produce cellulose-containing fine particles, or GO
Coagulating and neutralizing the dispersion liquid with an acid to regenerate cellulose to produce cellulose-containing fine particles; (4) during the coagulation and/or neutralization in step (3)(i), 3) during coagulation and neutralization of (ii),
Alternatively, after that, the first water-soluble polymer compound is removed from the fine particles generated in each step, and if necessary, (5) porous, characterized by U sulfur, pickling, water washing, or drying. It can be manufactured by a method for manufacturing microcellulose.

Further, according to the present invention, the porous micro cellulose particles of the present invention are prepared by: (1) preparing water-soluble alkaline polymers of cellulose X xanthate and other mi water-soluble polymer compounds; 2) Made of the above alkaline polymer water-soluble and number-average molecules 1.
G()(i) Mixing 500 or more water-soluble polyethylene glycols or polyethylene glycol derivatives to produce a fine particle dispersion of the alkaline polymer aqueous solution at a temperature of 55°C or higher; Cellulose The dispersion liquid is coagulated as fine particles containing cellulose, and then neutralized with an acid to regenerate cellulose to generate fine particles containing cellulose, or (ii) the dispersion is coagulated and neutralized with an acid to regenerate cellulose. (4) During the coagulation and/or neutralization of the above step (3) (i), during the coagulation and neutralization of the above step (3) (ii), or after each step. The first water-soluble polymer compound is removed from the fine particles produced in step 5, and if necessary, (5) desulfurization, pickling, water washing, or drying.
*a can be similarly achieved by a method for producing porous microcellulose characterized by the following.

As described above, the first method and the second method include the step (1) of preparing an alkaline polymer aqueous solution of cellulose xanthate and a first water-soluble polymer compound, and a fine particle dispersion of an alkaline polymer aqueous solution. The process consists of a step (2) of producing cellulose, a step (3) of producing fine particles containing cellulose, a step (4) of removing the first water-soluble polymer compound, and a post-treatment step (5) carried out as necessary. , are basically composed of the same process.

The first method and the second method differ in that the second high IIP compound used in the above step (2) is a fish that is inflammatory in the first method. First, the first manufacturing method of the present invention will be explained below.

The invention! According to the method of lS1, as described above, the first
An alkaline polymer aqueous solution of Cellulose Zante F and a first water-soluble polymer compound other than that is prepared in the step, a fine particle dispersion of the alkaline polymer aqueous solution is generated in the second step, and a fine particle dispersion of the alkaline polymer aqueous solution is produced in the step tIS3. The fine particles containing the first water-soluble polymer compound are neutralized to produce fine particles containing cellulose, and in the fourth step, the first water-soluble polymer compound is removed from the fine particles.

Iil an alkaline polymer aqueous solution of cellulose xanthate and a first water-soluble polymer compound other than cellulose xanthate! First thing to do
In the process, cellulose xanthate and the other first water-soluble polymer compound are simultaneously dissolved in water or an alkaline aqueous solution, or cellulose xanthate is first dissolved in water or an alkaline aqueous solution, and the resulting viscose is dissolved. This can be carried out by dissolving the first water-soluble polymer compound in water or by dissolving the water-soluble polymer compound Ii in water or an alkaline aqueous solution, and then dissolving cellulose xanthate in the solution.

The above-mentioned dissolution can be carried out, for example, by mixing with Ni-G or high-viscosity stirring 4'lIR.

Cellulose xanthate may be obtained as an intermediate in the rayon manufacturing process or cellophane manufacturing process, and for example, cellulose concentration is 33% by weight and alkali concentration is 16% by weight.
, cellulose xanthate having a gamma value of about 40 is suitable.

As the first water-soluble polymer compound, for example, a nonionic or anionic polymer compound is preferably used. Examples of the nonionic PjSl water-soluble polymer compound include polyethylene glycol, polyethylene glycol conductor, and polyvinylpyrrolidone.

These polymer compounds have a number average molecular weight of, for example, 400 or more, preferably 600 to 400.0.
It has a number average molecular weight of 0.00.

As a polyethylene glycol conductor, for example, only the hydroxyl group at one end of polyethylene glycol has 1 to 1 carbon atoms.
8 alkyl group, a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms, or a water-soluble compound blocked with an acyl group having 2 to 18 carbon atoms, or an A-B-A' type block copolymer (A , A' are the same or different and represent a polyethylene oxide block, and B represents a polypropylene oxide block) are preferably used. More specifically, for example, polyethylene glycol monomethyl ether,
Polyethylene glycol monolauryl ether, polyethylene glycol monocetylethyl; polyethylene glycol moamethyl 7-enyl ether, polyethylene glycol mono/nylphenyl ether: polyethylene glycol monoacetate, polyethylene glycol monolaurate; and polyoxyethylene block-polyoxy Examples include propylene block-polyoxyethylene block.

In addition, the anionic first water-soluble 116-molecule compound is
For example, anionic L (such as sulfonic acid J, t,
±1 Shiso Pass it V I 16 Ruzeso ｾri 2. (mosquito〕
These anionic groups, preferably C0st1, may be in the form of free acids or salts.

The first water-soluble polymer compound having a sulfonic acid group as an anionic group has a sulfonic acid group such as vinylsulfonestyrenesulfonic acid, 7lylsulfonic acid, methallylsulfonic acid, acrylamide metalpropanesulfonic acid, or a salt thereof. It can be derived from monomers such as. Similarly, water-soluble polymeric compounds of PjSl having phosphonic acid groups as anionic groups can be derived from monomers such as styrenephosphonic acid, vinylphosphonic acid or salts thereof.

Further, the water-soluble polymer compound having a carboxylic acid group as an anionic group can be derived from a monomer such as acrylic acid, methacrylic acid, styrene carboxylic acid, maleic acid, itaconic acid, or a salt thereof.

For example, a water-soluble polymer compound of ttSi having a carboxylic acid group can be prepared by mixing acrylic acid Sorg alone or with other copolymerizable monomers such as methyl acrylate.
Polymerized according to methods known per se, they are supplied as homopolymers or copolymers containing polymerized units of acrylic acid. Furthermore, for example, a styrene homopolymer can be sulfonated to glR a water-soluble polymer compound having a sulfonic acid group.

The same applies to the case where the sulfonic acid group is derived from a monomer other than styrene sulfonic acid, and the case where the phosphonic acid group and the carboxylic acid group are respectively derived from the above monomers.

The first water-soluble anionic polymer compound preferably contains at least 20 mol % of polymerized units of monomers as described above having anionic groups. Such preferred polymeric compounds include copolymers and homopolymers.

The water-soluble anionic polymer compound preferably has a number average molecular weight of at least s, o o o, more preferably 10,000 to 3,000,000.

The water-soluble first anionic polymer compound used in step (1) of the present invention is not limited to the above-mentioned vinyl type polymers, but also includes carboquine methyl cellulose, sulfoethyl cellulose, and others. salt such as N
a salts are included.

According to the first method, as mentioned above, in the first step, an alkaline polymer aqueous solution is prepared! IA is hired. The aqueous polymer solution preferably has a cellulose concentration derived from cellulose xanthate of 3 to 15% by weight, more preferably 5 to 12% by weight.
fifi%, and the alkali concentration is preferably 2 to 15% by weight, more preferably 5 to 10% by weight.
The weight has been adjusted to 11. Further, the amount of the first water-soluble polymer compound is preferably adjusted to 0.03 to 5 parts by weight per 1 part by weight of cellulose.

According to the first method of the present invention, the alkaline polymer aqueous solution adjusted and prepared in the above PtSi step is then tJS
It is mixed with a water-soluble anionic polymer compound of Pt52 in two steps.

For mixing, any means capable of producing a fine particle dispersion of an aqueous alkaline polymer solution can be used. For example, mechanical stirring using a stirring blade or baffle plate, ultrasonic stirring, or mixing using a static mixer may be used alone or Can be implemented in combination.

The second water-soluble anionic polymer compound is preferably used as an aqueous solution, more preferably as an aqueous solution in which the second polymer compound has a concentration of 0.5 to 25% by weight, particularly preferably 2 to 22% by weight. , used. Such an aqueous solution preferably has a viscosity at 20°C of 3 to 50,000 cm, particularly 5 to 30,000 cm.

The alkaline polymer aqueous solution and the water-soluble anionic polymer compound of PtrJ2 are the second polymer compound (), 3 to 1 per 1 part by weight of cellulose in the alkaline molecule aqueous solution.
00 parts by weight, more preferably 1 to 45 parts by weight, particularly preferably 4 to 20 parts by weight, and mixed.

It is advantageous to carry out the mixing at a temperature lower than the boiling point of carbon disulfide contained in the alkaline polymer aqueous solution, and more preferably, according to the research of the present inventor, the above alkaline polymer aqueous solution in the first step When an acid-decomposable inorganic salt such as calcium carbonate is present as a dispersant, for example, by 0.5 to 5 gw, the morphology of the fine particles in the fine particle dispersion produced in the second step is stabilized. It was found that the composition was well maintained.

Examples of the water-soluble anionic polymer compound @2 include the same compounds as the above-mentioned examples of the anionic water-soluble polymer compound fj41.

The water-soluble anionic polymer compound of 1fi2 may be the same as or different from the water-soluble polymer compound of i@1.

According to the method of the present invention, the fine particle dispersion of the alkaline polymer aqueous solution produced in the second step is then coagulated and neutralized in the third step to produce cellulose-containing fine particles. Coagulation and neutralization can be carried out simultaneously or sequentially by heating the dispersion or mixing the dispersion with a coagulant, and then neutralization is carried out by contacting with an acid. It is done by forcing.

The coagulation reaction described above is desirably carried out while adding a mixing operation to the produced dispersion.

Solidification by heating can be advantageously carried out at a temperature higher than the boiling point of carbon disulfide contained in the alkaline directed molecular water fB liquid, for example at a temperature of 50' to 90°C. In the case of coagulation using a coagulant, it is not necessary to raise the temperature to such a temperature, and coagulation can usually be carried out at a temperature of 0 to 40°C. As a coagulant,
For example, lower aliphatic alcohols, alkali metal salts or alkaline earth metal salts of Wc organic acids, inorganic acids, organic acids, or combinations thereof, and combinations thereof with the third water-soluble polymer compound are preferably used. The lower aliphatic alcohol may be linear or branched, and includes aliphatic alcohols having 1 to 4 carbon atoms such as methanol, ethanol, 1so-propanol, n-propanol, and n-butanol. is preferably used. Examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, and carbon 1'[! etc. Examples of alkali metal salts of inorganic acids include NiCl, Na3SO<
Na salt such as K2S0. Salts such as M II S O4 are preferred, and alkaline earth metal salts include, for example, M II S O4
M, salt, Ca C12f) Ca salt is preferred, 8! The acid is preferably a carboxylic acid or a sulfonic acid, such as formic acid, acetic acid, propionic acid, benzoic acid, benzenesulfonic acid, toluenesulfonic acid, maleic anhydride, malic acid, oxalic acid, etc.

As the water-soluble polymer compound of Pt53, for example, nonionic and anionic polymer compounds are preferably used. It is particularly desirable to use the same third water-soluble polymer compound as the second anionic polymer compound used in the second step. Examples of the third water-soluble polymer compound include the above-mentioned examples. It will be understood from the illustration of the first water-soluble polymer compound.

The coagulant as described above is used in a proportion of, for example, about 20 to 300% based on the cellulose in the viscose.

As the acid used as the neutralizing agent, strong inorganic acids such as sulfuric acid and hydrochloric acid are preferably used.

The neutralizing agent is used in an amount sufficient to neutralize the aqueous alkaline polymer solution, producing fine particles of cellulose. Furthermore, as described above, the third step of coagulation and neutralization can be carried out simultaneously. Effective coagulation and neutralization agents are acids, preferably strong inorganic acids such as hydrochloric acid or sulfuric acid. An acid used in an amount sufficient to neutralize viscose will be an amount sufficient to coagulate and neutralize the viscose. Simultaneous coagulation and neutralization are advantageously carried out at temperatures of, for example, 0 to 40°C.

Although the water-soluble polymer compound is removed during the coagulation, neutralization, or coagulation/neutralization, the cellulose-containing fine particles produced in the third step are further processed to separate the fine particles from the first one. Water-soluble polymer compounds can also be removed.

The water-soluble polymer compound can be removed, for example, using water or meta/-
In order to completely remove the silica, which is carried out by washing with water, hot water washing and methanol washing are carried out, followed by desulfurization, pickling, water washing or drying as necessary in the fifth step. Further, depending on the case, bleaching may be performed after pickling.

Desulfurization can be carried out using an aqueous alkali solution such as caustic soda or sodium sulfide. If necessary, in order to remove the remaining sulfur, it is then pickled with dilute hydrochloric acid, washed with water, and dried.

Next, the method for manufacturing fjS2 of the present invention will be explained.

According to the second method of the present invention, as described above, an alkaline polymer aqueous solution of cellulose xanthate and 11 other water-soluble polymer compounds is prepared in the first step,
In the second step, a fine particle dispersion of the aqueous alkaline polymer solution is produced, in the third step all the particles containing cellulose are produced, and in the step j14, the first water-soluble ('fi molecules) are extracted from the fine particles. The compound is removed.In this respect, it is basically the same as the first production method described above, as described above.

Cell o −: x: Xanthate and other first water) 8
Cultivated money Mueru Δ & Ha type 1 I-Tenhachi-t↓u2 total↓1+J
The requested first step is carried out in the same manner as described in the description of the first manufacturing method above.

For example, the xanthate and other first water-soluble polymer compounds used are the same as those described in the first production method.

A second step for producing a fine particle dispersion of an aqueous alkaline polymer solution.
The process consists of alkaline high carbon water f8 liquid and number average molecular zi
This is carried out by mixing water-soluble polyethylene glycol or a polyethylene glycol derivative of at least so much water.

As mentioned above, the high molecular weight polyethylene glycol or polyethylene glycol derivative used has a number average molecular weight of 1.500 or more, preferably 1.50.
It has a number average molecular weight of 0 to 400.000.

As a polyethylene glycol derivative, for example, only the hydroxyl group at one end of polyethylene glycol has 1 to 1 carbon atoms.
A water-soluble compound or an A-B-A' type block copolymer (A , A' are the same or different and represent a polyethylene oxide block, and B represents a pop-a pyrene oxide block) are preferably used. More specifically, for example, polyethylene glycol monomethyl ether,
Polyethylene glycol monolauryl ether, polyethylene glycol monocetylethyl; polyethylene glycol monomethyl 7-enyl ether, polyethylene glycol monononylphenyl ether; polyethylene glycol monoacetate, polyethylene glycol monolaurate: as-used polyethylene block-polyoxypolymer a Examples include Tsuku-polyoxyethylene block and the like.

Among polyethylene glycol and its derivatives, polyethylene glycol is more preferred, and has a number average molecular weight of 6,
The polyethylene glycol derivatives are more preferably those with a number average molecular weight of 000 to 200,000, particularly preferably those with a number average molecular weight of 5,000 to 100,000, and particularly preferably those with a number average molecular weight of 10,000 to 30,000. Preferably it has a number average molecular weight of 1,500 to 16,000.

According to the second method of the present invention, in the second step,
First, an alkaline polymer aqueous solution and a water-soluble high molecular weight polyethylene glycol or its derivative are mixed. For mixing, any means capable of producing a fine particle dispersion of an alkaline aqueous polymer solution can be used. The specific means are as described in the description of the first manufacturing method above.

The water-soluble high molecular weight polyethylene glycol or its derivative is preferably used as an aqueous solution, and more preferably the concentration of the polyethylene glycol or its derivative is 0.5 to 0.5.
60% by weight, particularly preferably 5-55% by weight, especially 10% by weight
It is used as a ~40% by weight aqueous solution.

The alkaline polymer aqueous solution and polyethylene glycol or polyethylene glycol derivative are Cell A's 1x,
per ft part of polyethylene glycol or more preferably 2
~28 parts by weight, particularly preferably 4 to 24 parts by weight, especially 8
~16 parts by weight are used and mixed. There is no particular restriction on the temperature during mixing, but it is desirable to perform the mixing at a temperature lower than the temperature at which a fine particle dispersion of an alkaline polymer aqueous solution is generated. Generated by temperature → t wetted.

At temperatures lower than 55° C., it is not possible to obtain a fine particle dispersion of an aqueous alkaline polymer solution, which is the basis of the formation of extremely small cellulose particles.

According to the second method, the fine particle dispersion of the alkaline polymer aqueous solution produced in the tIS2 step is then t
The JS3 process produces fine particles that are coagulated and neutralized and contain cellulose. Coagulation and neutralization may be performed simultaneously or sequentially.

When coagulation and neutralization are carried out over time, coagulation is carried out by heating the dispersion or by bringing the dispersion and coagulant into contact with an acid.

It is desirable that the coagulation reaction is carried out while adding agitation to the produced dispersion.

Further, the coagulation reaction is carried out at a temperature equal to or higher than the temperature at which the dispersion is produced.

Both the coagulation by heating and the coagulation using a coagulant are preferably carried out at a temperature of 60°C to 90°C.

The coagulant and the proportion of V used are the same as described in the explanation of the first manufacturing method above.

When using a coagulant with polyethylene glycol or its derivatives as the coagulant, it is possible to prevent the concentration of polyethylene glycol or its derivatives from decreasing in the system by adding the coagulant. This method has the advantage of stably coagulating the liquid.

As the acid used as the neutralizing agent, strong inorganic acids such as sulfuric acid and hydrochloric acid are preferably used.

The neutralizing agent is used in an amount sufficient to neutralize the aqueous alkaline polymer solution, producing fine particles of cellulose. Furthermore, as described above, the third step of coagulation and neutralization can be carried out simultaneously. Agents effective in neutralizing coagulation run-off are acids, preferably strong inorganic acids such as hydrochloric acid or sulfuric acid. A sufficient amount of acid is used to neutralize the aqueous alkaline polymer solution, and the amount of acid used is sufficient to coagulate and neutralize the alkaline polymer aqueous solution. Simultaneous coagulation and neutralization are advantageously carried out at temperatures of, for example, 60°C to 90°C. According to the second method of the present invention, the cellulose fine particles produced in the third step are then subjected to the fourth and fifth steps under the same conditions as described in the description of the first method. The first water-soluble polymer compound is removed and subjected to post-treatment.

Thus, according to the invention, as described above, (a)
It consists essentially of type IIl cellulose, (bJX#i crystallinity determined by diffraction method is in the range of 5 to 35%, and (d) In the differential curve of pore diameter and pore volume measured by the mercury porosimetry method, the maximum value of pore volume is in the pore diameter interval of 0.02 to 0.8μ, and all of the pores in the same interval are There is provided a porous microcellulose particle according to the invention, characterized in that the volume is at least 0.025 ml/g.

The porous microcellulose particles of the present invention include the above (a) to (d).
) is characterized by having the following requirements. Each of these requirements will be explained below.

The porous microcellulose particles of the present invention primarily consist essentially of type II cellulose, that is, regenerated cellulose. Therefore, cellulose fine particles made of natural cellulose, that is, type I cellulose, are completely different from the porous fine particles of the present invention. As is well known, H-type cellulose and L-type cellulose can be distinguished by X-ray diffraction. 11 type cellulose X-
In the line diffraction diagram, there is substantially no diffraction peak at a diffraction angle (2θ) of 15@, which clearly exists in l-type cellulose.

Moreover, secondly, the porous microcellulose particles of the present invention include:
The microcellulose particles of the present invention preferably have a crystallinity of 7 to 33%, more preferably 10 to 30%, as determined by X-ray diffraction. Microcellulose is not amorphous but crystalline as specified by the degree of crystallinity mentioned above.

Thirdly, the porous microcellulose particles of the present invention consist essentially of spherical or oblate particles with an average particle size of 300 μm or less. The porous microcellulose particles of the present invention further have an average particle size of 1 to 200μ,
More preferably, it is substantially defined by spherical to oblate particles of 2 to 150 μm. Honmei #l! The term "long spheroidal" as used in this book includes particles whose projected view or plan view is, for example, an ellipse, an elongated circle, a peanut shape, or an egg shape. The porous microcellulose particles of the present invention are spherical or elongated as described in Section 2, and are therefore different from particles that are rounded or irregularly shaped.

When producing the micro cellulose rotor with 1 type of 1 type 1 drop-off property according to the method of the present invention described above, viscose and If a water-soluble anionic polymer compound is coagulated while being mixed too vigorously, it is likely to be formed.

The porous microcellulose particles of the present invention have #&4 a maximum value of pore volume in the pore diameter range of 0.02 to 0.8 μm in the differential curve of pore diameter and pore volume measured by mercury porosimeter method, and The total pore 'Bm of the pores in the same section is at least 0.025 ml/g. The total pore volume can be calculated from the differential curve of pore diameter and pore volume using the usual method! k can also be easily determined from the integral curve.

The porous microcellulose particles of the present invention have a pore size of 0°02 to
The total pore volume of the pores in the 0.8 μm interval is preferably at least 0.04 ml/g, more preferably at least 0.
, 065 ml/g%, particularly preferably at least 0.15
ml/g. Further, the porous microcellulose particles of the present invention have a total pore volume of at most 1 m in the same area, for example.
l/g can be advantageously used.

The physical properties that characterize the porous microcellulose particles of the present invention include the following.

Many of the cellulose constituting the porous microcellulose particles of the present invention usually exhibit a degree of polymerization in the range of 100 to 700, and many have a copper number of 3 or less as measured and defined by the method described below.

As mentioned above, the porous microcellulose particles of the present invention are fine and porous, and since they are made of cellulose, they are relatively stable against chemicals and are not toxic.
For example, scales are used as diluents for various pharmaceuticals, bulking agents for cosmetics, and food additives, but they are also used, for example, as photochromic agents for liquid chromatography, taking advantage of their porous nature and stability against chemicals. The porous microcellulose particles of the present invention can be suitably used in a wide range of industrial fields.

The present invention will be explained in detail with reference to Examples below.

Before that, methods for measuring various characteristic values in Book #I of the present invention will be described first.

Measuring method of crystallinity〉 M & Magazine Journal Vol. 19, No. 2 (1963) No. 113
It is determined by the method for measuring the crystallinity of cellulose using the XMA diffraction method described on page 119. That is, 2θ is 5
The X-ray diffraction curve from @ to 458 is taken and calculated using the following formula.

With a smile, T'=((a0C) -blXKK =0.8
96 (Incoherent scattering M positive coefficient of cellulose) C=ca a: Diffraction curve of non-grade starch (2θ=5 to 45°)
B: Area of air 6L curve (2θ = 5 to 45°), C: Area of sample diffraction curve (2θ = 5 to 45°), American Instrument Company 5-712
Type 1 mercury porosimeter rDIGITAL READ
Measured with OUT PORO8rMETERJ. The pore diameter was calculated using the following formula.

Here, D: pore diameter (μm), P: pressure (P 5ia), pore volume at this pore diameter is the density of mercury 13.558
Calculated using 5g/am3 (15°C).

V = □ 13.5585 It was determined according to the method.

<Copper price> Therefore, I asked for it.

<Average Particle Size Measuring Method> Approximately 100 g of a sample is taken, poured into 25 ml of pure water, stirred and dispersed, and measured using a light transmission particle size distribution analyzer.

Example 1, Comparative Example 1 500 g of a pipe made of coniferous wood was immersed in 18 weight percent mushroom saug solution 201 at 20° C. for 1 hour, and then compressed to 2.8 times its size. The cellulose was pulverized for 1 hour under external heating from 25°C to 50°C, aged, and then 35% by weight of carbon disulfide (175 bis) was added to the cellulose and sulfurized at 25°C for 1 hour to form cellulose xanthate. did. After dissolving the xanthate in caustic soda water: f# solution, polyethylene glycol (
500 g of 7 resins having a molecular weight of 20,000) were added and dissolved to prepare an aqueous alkaline polymer solution of cellulose xanthate and polyethylene glycol. The alkaline polymer aqueous solution had a cellulose concentration of 9.2%, a caustic soda concentration of 5.9% by weight, a polyethylene glycol concentration of 9.2% by weight, and a viscosity of 83%.
It was 00 centiboise.

60 g of the alkaline polymer aqueous solution prepared above and an aqueous solution of sodium polyacrylate as an anionic second polymer compound (polymer concentration 12%, molecular weight 50,000; manufactured by Nippon Pure Chemical Industries, Ltd.; trade name Noyurimer AC- ION) and 2 g of calcium carbonate as a dispersant were added to 500 so 17 rasf to make the total amount 300 g.

At a liquid temperature of 30℃, use a laboratory stirrer (manufactured by Yamato Kaisha 1:
MODEL LR-51B, rotating blade 7cm) 60
After stirring at 0 rpm for 10 minutes to generate fine particles of the alkaline polymer aqueous solution, the liquid temperature was raised from 30°C to 70°C in 15 minutes while continuing to stir.
The microparticles containing polyethylene glycol were solidified by maintaining the temperature at 0° C. for 30 minutes. Do not continue stirring 1
00. The mixture was neutralized with 1/2 sulfuric acid and a cellulose particle molecular liquid was obtained. The above fractional liquid was passed through an IG4 type glass filter to separate cellulose fine particles containing polyethylene glycol from the mother liquor, and then heated at 5θ°C and 2g/jt.
After desulfurization with an aqueous sodium chloride solution of about 21 g/2 and neutralization with a 2 g/2 aqueous sulfuric acid solution, the particles were washed with a large excess of water to remove polyethylene glycol from the fine particles to obtain porous cellulose fine particles.

The characteristics of porous cellulose fine particles were measured by the method described above, and the results are shown in Table fjS1.

Next, the results for porous cellulose fine particles obtained by changing the amount of polyethylene glycol (molecules + i20,000) added to 250 g, 750 g, and no addition (Comparative Example 1) are also shown in Table f51. 6 Example 2 Implementation Example 1 except that the molecular weight of the polyethylene glycol used in Example 1 was changed to 2000.4000.6000.
Porous microcell a-s particles were obtained in the same manner as above. Table 2 shows the characteristics of the porous cellulose fine particles. Run No. 1 of Example 1 is also shown.

Example 3 Cellulose xanthate obtained in the same manner as in Example 1 was dissolved in an aqueous caustic soda solution, and then 250 g of an aqueous solution of sodium polystyrene sulfonate (molecular weight 10,000, polymer concentration 20%) was added and dissolved. Then, cellulose fine particles-F
and sodium polystyrene sulfonate, the aqueous alkaline polymer solution contained 9.0% by weight of cellulose fine particles, 5.5% by weight of caustic soda, 0.9% by weight of sodium polystyrene sulfonate, and a viscosity of It was 7,800 centiboise.

60 g of the above-prepared alkaline polymer aqueous solution and an aqueous polyacrylic acid solution as an anionic tlS2 polymer compound (molecules + i50,000, /Ji molecular strength 12ili)
amount%) 240g% 2g of calcium carbonate as a dispersant
Pour 00ml into 7 fusco and make a total volume of 300ml. And so.

Hereinafter, porous microcellmy
Particles were obtained. Obtained Porous Microcellulose 3fi Example 4 Porous microcellulose particles were obtained in the same manner as in Example 1 except that the water-soluble anionic polymer compound of PIS2 was changed as shown in Table 4. Table 4 shows the properties of the obtained porous micro Selmy X particles.

Example 5 In Example 1 *! 60 g of alkaline polymer aqueous solution and an aqueous solution of sodium polyacrylate (molecular weight 50,000, polymer concentration 12% by weight) 2 as anionic second polymer aqueous solution
40g, 500ml of 2g of calcium carbonate as a dispersant
The total amount was 300g.

At a liquid temperature of 30°C, stirring was performed for 10 minutes using a Labo Star Two 600 rpm song to generate fine particles of an alkaline polymer aqueous solution, and then a sulfuric acid concentration of 5 was added to the dispersion of the fine particles.
g/l polyacrylic acid aqueous solution (molecular weight 50,000,
240 g (polymer concentration: 12% by weight) was gradually added to solidify fine particles of the aqueous solution of alkaline molecules. While continuing to stir, the mixture was neutralized and regenerated with 100 g/l sulfuric acid to obtain a fine particle dispersion containing cellulose. The above dispersion I
After separating cellulose-containing fine particles from the mother liquor through a G4 type glass filter, desulfurization was performed at 50°C with a 2 g/l aqueous sodium chloride solution, neutralized with a 2 g/2 aqueous sulfuric acid solution, and then a large excess of water was removed. The particles were washed with water to remove sodium polyacrylate from the particles to obtain porous microcellulose particles.

Table 5 shows the properties of the obtained porous microcellulose particles.

Table 5 Example 6 Cellulose Zanur 10 obtained in the same manner as Example 1
An alkaline polymer aqueous solution of cellulose xanthate and polyethylene glyfur was prepared by dissolving 4.5 kg of a wt% aqueous solution. The aqueous alkaline polymer solution had a cellulose concentration of 8.9% by weight, a caustic soda concentration of 5.4% by weight, a polyweight range 1 fucol of 9.0%, and a viscosity of 7400 centiboise.

60 g of the above-prepared aqueous alkaline polymer solution and 240 g of an aqueous solution of sodium polyacrylate (polymer concentration 12% by weight, molecular weight 50,000) as the anionic second polymer compound.
Then, 2 g of calcium carbonate as a dispersant was put into a 500 ml 7 flask to make the total amount 300 g. Thereafter, porous microscopic cellulose particles were obtained in the same manner as in Example 1. The characteristics of the obtained porous microcellulose particles are shown in the f56 table.

Table 6 Example 7 Cellulose xanthate obtained in the same manner as in Example 1 was dissolved in a caustic soda aqueous solution, and then polyethylene glycol (molecular fi 6000) 500. was added and dissolved to prepare an alkaline polymer aqueous solution of cellulose xanthate and polyethylene glycol. The alkaline polymer aqueous solution has a cellulose X concentration of 8.8% by weight and a caustic soda concentration of 5%.
．． 5% by weight, 4.5% by weight of polyethylene glycol, and a viscosity of 6,800 centiboise.

60 g of the alkaline polymer aqueous solution prepared above and a polyethylene glycol aqueous solution (
240 g (molecular weight 20,000, polymer concentration 30 weight) and 2 g calcium carbonate as a dispersant were placed in a 5001 flask to make the total amount 300 g. At a liquid temperature of 40°C, stir with a lab stirrer at 1000 rpm for 10 minutes, and while continuing to stir, raise the liquid temperature from 40°C to 70°C in 15 minutes to generate fine particles of alkaline polymer aqueous solution. After cooling, the particles were maintained at 70° C. for 30 minutes to solidify the fine particles containing polyethylene glycol (molecules 16,000). Thereafter, porous microscopic cellulose particles were obtained in the same manner as in Example 1.

Table 7 shows the properties of the obtained porous microcellulose particles.

Table 7 Example 8 Porous microcellulose particles No. and 1+2 of Example 1 were packed in a stainless steel column of 8 L fl LI l φ x 25 cm with water at a flow rate of 2.0 ml/min.
It took 0 minutes to fill. Next, using each packed column as a separation column, the relationship between molecular weights and molecular weights was investigated under the following analytical conditions.

Analysis conditions 1. Pump HLC- manufactured by Toyo Soda Kogyo Co., Ltd.
803D 2, Eluent: Pure water 3, Flow rate: 1, 0 ml 7 minutes 4, Temperature: Room temperature 5, Detector: Class M RI detector Figure 1 shows the relationship between the molecular weight of polyethylene glycol and elution time. This shows that the porous microcellulose particles of the present invention have good separation performance as a liquid chromatography packing material.

Incidentally, FIG. 1 shows the micro cellulose particles of Comparative Example 1 as a comparative example.

[Brief explanation of the drawing]

Figure 1 shows the molecular weight and elution time of the porous microcellulose particles of the present invention (obtained in Run No. 1 and Run No. 2 of Example 1) as a packing material for liquid chromatography. FIG. IYC2FFI 10-Kudoriguchi H's Winter Go (Zet Notification) 1) Se
4 (Run No. of Example 1,
Scanning electron micrograph (obtained in step 2) (X100
O).

Claims (1)

[Claims] 1. (1) consists essentially of type II cellulose (d) In the differential curve of pore diameter and pore volume measured by the mercury porosimeter method, the maximum pore volume is in the pore diameter range of 0.02 to 0.8 μm. Porous microcellulose particles having a total pore volume of at least 0.025 ml/g. 2. The porous microcellulose particles according to claim 1, having a crystallinity in the range of 7 to 33%. 3. The porous microcellulose particles according to claim 1, having a crystallinity in the range of 10 to 30%. 4. The porous microcellulose particles according to claim 1, which essentially consist of spherical or oblong spherical particles having an average particle diameter of 1 to 200 μm. 5. The porous microcellulose particles according to claim 1, which essentially consist of spherical or oblong spherical particles having an average particle diameter of 2 to 150 μm. 6. The projection of a long spheroidal particle is an ellipse, an elongated circle,
The porous microcellulose particles according to claim 1, which are peanut-shaped or oval-shaped. 7. The porous microcellulose particles according to claim 1, wherein the total pore volume of the pores in the pore diameter range of 0.02 to 0.8 μm is at least 0.04 ml/g. 8. The porous microcellulose particles according to claim 1, wherein the total pore volume of the pores in the pore diameter range of 0.02 to 0.8 μm is at least 0.065 ml/g. 9. The porous microcellulose particles according to claim 1, wherein the total pore volume of the pores in the pore size range of 0.02 to 0.8 μm is at least 0.15 ml/g. 10. Claim 1, wherein the total pore volume of the pores in the pore diameter range of 0.02 to 0.8 μml/g is at most 1 ml/g.
The porous microcellulose particles described in . 11. The porous microcellulose particles according to claim 1, wherein the degree of polymerization of cellulose is in the range of 100 to 700. 12. The porous microcellulose particles according to claim 1, wherein the cellulose has a copper value of 3 or less. 13. (1) Prepare a water-soluble alkaline polymer of cellulose xanthate and a first water-soluble polymer compound other than cellulose xanthate, (2) Prepare the water-soluble alkaline polymer and a second water-soluble anionic polymer. (3) (i) dispersion by heating the dispersion or mixing the dispersion with a coagulant of cellulose xanthate; Cellulose xanthate in the liquid is coagulated as fine particles containing the first water-soluble polymer compound, and then neutralized with an acid to regenerate cellulose to produce cellulose-containing fine particles, or (ii) coagulating and neutralizing the dispersion liquid with an acid to regenerate cellulose to produce cellulose-containing fine particles; (4) during coagulation and/or neutralization in step (3) (i) above; 3) During or after the coagulation and neutralization in (ii), the first water-soluble polymer compound is removed from the fine particles generated in each step, and if necessary, (5) desulfurization, pickling, and water washing are carried out. , or drying. A method for producing porous microcellulose. 14. The alkaline polymer aqueous solution of the above step (1) contains 0.00 parts by weight of cellulose xanthate in terms of cellulose.
14. The method according to claim 13, comprising 0.3 to 5 parts by weight of the first water-soluble polymer compound. 15. The method according to claim 13 or 14, wherein the first water-soluble polymer compound is nonionic or anionic. 16. The method according to claim 15, wherein the nonionic first water-soluble polymer compound is polyethylene glycol, a polyethylene glycol derivative, or polyvinylpyrrolidone having a number average molecular weight of 400 or more. 17. The method according to claim 16, wherein the polyethylene glycol or polyethylene glycol derivative has a number average molecular weight of 600 to 400,000. 18. Claim 15, wherein the anionic first water-soluble polymer compound has a sulfonic acid group, phosphonic acid group, or carboxylic acid group in the form of a free acid or salt as an anionic group. The method described in. 19. The anionic first water-soluble polymer compound is selected from the group consisting of vinylsulfonic acid, styrenesulfonic acid, methylstyrenesulfonic acid, allylsulfonic acid, methallylsulfonic acid, acrylamide methylpropanesulfonic acid, and salts thereof. 16. A method according to claim 15, containing polymerized units of at least one monomer. 20. The anionic first water-soluble polymer compound is a polymerized unit of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, styrene carboxylic acid, maleic acid, itaconic acid, and salts thereof. 16. The method according to claim 15, comprising: 21. Claim No. 2, wherein the anionic first water-soluble polymer compound contains polymerized units of at least one monomer selected from the group consisting of styrenephosphonic acid, vinylphosphonic acid, and salts thereof. The method described in Section 15. 22. The method according to claim 15, wherein the anionic first water-soluble polymer compound is a homopolymer or copolymer containing at least 20 mol % of polymerized units of the above monomers. 23. Claim 1, wherein the anionic first water-soluble polymer compound has a number average molecular weight of at least 5,000.
The method described in Section 5. 24. The method according to claim 15, wherein the anionic first water-soluble polymer compound has a number average molecular weight of 10,000 to 3,000,000. 25. The method according to claim 13, wherein the alkaline polymer aqueous solution in step (1) contains cellulose derived from cellulose xanthate in a concentration of 3 to 15% by weight. 26. The method according to claim 13, wherein the alkali concentration of the aqueous alkaline polymer solution in step (1) is 2 to 15% by weight as caustic soda. 27. A patent in which the anionic second water-soluble polymer compound in step (2) above has a sulfonic acid group, phosphonic acid group, or carboxylic acid group in the form of a free acid or salt as an anionic group. The method according to claim 13. 28. The anionic second water-soluble polymer compound is selected from the group consisting of vinylsulfonic acid, styrenesulfonic acid, methylstyrenesulfonic acid, allylsulfonic acid, methallylsulfonic acid, acrylamide methylpropanesulfonic acid, and salts thereof. 14. A method according to claim 13, containing polymerized units of at least one monomer. 29. The anionic second water-soluble polymer compound is a polymerized unit of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, styrene carboxylic acid, maleic acid, itaconic acid, and salts thereof. 14. The method according to claim 13, comprising: 30. Claim No. 3, wherein the anionic second water-soluble polymer compound contains polymerized units of at least one monomer selected from the group consisting of styrenephosphonic acid, vinylphosphonic acid, and salts thereof. The method described in Section 13. 31. The method according to claim 13, wherein the anionic second water-soluble polymer compound is a homopolymer or copolymer containing at least 20 mol% of polymerized units of the above monomers. 32. Claim 1, wherein the anionic second water-soluble polymer compound has a number average molecular weight of at least 5,000.
The method described in Section 3. 33. The method according to claim 13, wherein the anionic second water-soluble polymer compound has a number average molecular weight of 10,000 to 3,000,000. 34. The method according to claim 13, wherein the anionic second water-soluble polymer compound is used as an aqueous solution. 35, the anionic second water-soluble polymer compound is 0.5
14. The method according to claim 13, used as a ~25% by weight aqueous solution. 36, the anionic second water-soluble polymer compound is 2-2
Claim 1 used as a 2% by weight aqueous solution
The method described in Section 3. 37. Claim 13, wherein an alkaline polymer aqueous solution and an anionic second water-soluble polymer compound are mixed at a temperature lower than the boiling point of carbon disulfide to produce a fine particle dispersion of the alkaline polymer aqueous solution. The method described in section. 38. The method according to claim 13, wherein the alkaline polymer aqueous solution and the anionic second water-soluble polymer compound are mixed at a temperature of 0 to 40°C. 39. The method according to claim 13, wherein the aqueous alkaline polymer solution and the anionic second water-soluble polymer compound are mixed by mechanical stirring. 40. A patent claim in which an aqueous alkaline polymer solution and an anionic second water-soluble polymer compound are mixed in a ratio of 0.3 to 100 parts by weight of the second water-soluble polymer compound per 1 part by weight of cellulose. The method according to item 13. 41. Claim No. 41, wherein an alkaline polymer aqueous solution and an anionic second water-soluble polymer compound are mixed in a ratio of 1 to 45 parts by weight of the second water-soluble polymer compound per 1 part by weight of cellulose. The method described in Section 13. 42. Claim No. 42, wherein an alkaline polymer aqueous solution and an anionic second water-soluble polymer compound are mixed in a ratio of 4 to 20 parts by weight of the second water-soluble polymer compound per 1 part by weight of cellulose. The method described in Section 13. 43. Claim 13, wherein the coagulation reaction in step (3) is carried out while adding a mixing operation to the produced dispersion.
The method described in section. 44. Claim 13, wherein the solidification by heating in step (3)(i) is carried out at a temperature equal to or higher than the boiling point of carbon disulfide.
The method described in section. 45. Solidification by heating in step (3) (i) above at 50°
14. A method according to claim 13, carried out at a temperature of -90<0>C. 46. Coagulation with coagulant in step (3) (i) above from 0 to
14. The method according to claim 13, carried out at a temperature of 40<0>C. 47. The coagulant used in step (3) (i) above is a lower aliphatic alcohol, an alkali metal salt or alkaline earth metal salt of an inorganic acid, an inorganic acid, an organic acid, or a combination thereof, or a third aqueous solution thereof. 14. The method according to claim 13, wherein the method is a combination with an anionic polymer compound. 48. The method according to claim 13, wherein the acid used for neutralization in step (3)(i) is a strong inorganic acid. 49. Coagulation and neutralization in step (3) (ii) above from 0 to
14. The method according to claim 13, carried out at a temperature of 40<0>C. 50. The method according to claim 13, wherein the acid used for coagulation and neutralization in step (3) (ii) is a strong inorganic acid. 51. The method according to claim 50, wherein the strong inorganic acid is hydrochloric acid or sulfuric acid. 52, (1) Prepare an alkaline polymer aqueous solution of cellulose xanthate and a first water-soluble polymer compound other than that, (2) The water solubility of the alkaline polymer and the number average molecular weight 1,
500 or more water-soluble polyethylene glycols or polyethylene glycol derivatives are mixed to form a fine particle dispersion of the alkaline polymer aqueous solution at a temperature of 55°C or higher; (3) (i) the above dispersion is used to form the above dispersion The cellulose xanthate in the dispersion is converted into the first water-soluble highly water-soluble material by further heating at a temperature equal to or higher than the temperature at which the cellulose xanthate in the dispersion is heated or by mixing the dispersion with a coagulant for cellulose xanthate. Cellulose is coagulated as fine particles containing a molecular compound and then neutralized with an acid to regenerate the cellulose to produce cellulose-containing fine particles, or (ii) the dispersion is coagulated and neutralized with an acid to produce cellulose. (4) during coagulation and/or neutralization in step (3)(i) above, during coagulation and neutralization in step (3)(ii) above, or After that, the first water-soluble polymer compound is removed from the fine particles generated in each step, and if necessary, (5) the porous microcellulose is desulfurized, pickled, washed with water, or dried. manufacturing method. 53, the number average molecular weight of the polyethylene glycol or polyethylene glycol derivative in step (2) above is 1,50
53. The method of claim 52, wherein the number is between 0 and 400,000. 54. The method according to claim 52, wherein the polyethylene glycol in step (2) has a number average molecular weight of 6,000 to 200,000. 55. The method according to claim 52, wherein the polyethylene glycol derivative in step (2) has a number average molecular weight of 1,500 to 16,000. 56. The polyethylene glycol derivative of step (2) above is a phenyl group in which only the hydroxyl group at one end of the polyethylene glycol is substituted with an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, or a phenyl group having 2 to 18 carbon atoms. is a water-soluble compound capped with an acyl group of
53. The method according to claim 52, which is a block copolymer of type A' (A and A' are the same or different and represent a polyethylene oxide block, and B represents a polypropylene oxide block). 57. The method according to claim 52, wherein the water-soluble polyethylene glycol or polyethylene glycol derivative in step (2) is used as an aqueous solution. 58. The method according to claim 52, wherein the water-soluble polyethylene glycol or polyethylene glycol derivative in step (2) is used as a 0.5 to 60% by weight aqueous solution. 59. Water-soluble polyethylene glycol or polyethylene glycol derivative in step (2) above is 5 to 55% by weight
53. The method according to claim 52, wherein the method is used as an aqueous solution of. 60. According to claim 52, the aqueous alkaline polymer solution and water-soluble polyethylene glycol or polyethylene glycol derivative are mixed in a ratio of 1 to 30 parts by weight of polyethylene glycol or polyethylene glycol derivative per 1 part by weight of cellulose. the method of. 61. Claim 52, wherein the coagulation reaction in step (3) is carried out while adding a mixing operation to the produced dispersion.
The method described in section. 62. Solidification by heating in step (3) (i) above at 60°C
53. A method according to claim 52, carried out at a temperature of -90<0>C. 63. Coagulation with coagulant in step (3) (i) above at 60
53. A method according to claim 52, carried out at a temperature between 90<0>C and 90<0>C. 64. The coagulant used in step (3) (i) above is an alkali metal salt or alkaline earth metal salt of an inorganic acid, an inorganic acid, an organic acid, or a combination thereof, or a polyethylene glycol or polyethylene glycol derivative that is water-soluble with them. 53. The method of claim 52 in combination with. 65, (a) consisting essentially of type II cellulose; (b)
The degree of crystallinity as determined by X-ray diffraction is in the range of 5 to 35%, (c) it consists essentially of spherical or prolate particles with an average particle size of 300 μm or less, and (d) as determined by mercury porosimeter method. In the measured differential curve of pore diameter and pore volume, the maximum value of pore volume is in the pore diameter section of 0.02 to 0.8 μm, and the total pore volume of the pores in the same section is at least 0.025 ml/g. , A packing material for liquid chromatography characterized by consisting of porous microcellulose particles■