JPWO2016143439A1 - Porous body containing bacterial cellulose and polymer and method for producing the same - Google Patents

Abstract

It is an object of the present invention to provide a porous body containing bacterial cellulose and a polymer and a method for producing the same. Adding a first solvent to the bacterial cellulose hydrogel to prepare a first mixture; adding the polymer to the first mixture and heating; the polymer dissolved in the mixture of the first solvent and water; And preparing the second mixture, cooling the second mixture to obtain a precipitated molded body, and immersing the molded body in a second solvent so that the molded body is contained in the molded body. A step of substituting a first solvent and water with the second solvent to obtain a porous body containing the bacterial cellulose and a polymer, wherein the polymer is a polymer capable of forming a porous body by phase separation; The first solvent provides a method for producing a porous body containing bacterial cellulose and a polymer, which is a solvent miscible with water.

Description

  The present invention relates to a porous body containing bacterial cellulose and a polymer and a method for producing the same.

  Porous materials are often used as a separating agent, an adsorbing agent, and the like in various fields. Inorganic porous materials have been extensively researched on silica-based porous materials. Among the silica-based porous bodies, a technique for creating porous silica particles is common. This porous silica particle has been put to practical use as an analytical material. On the other hand, as a polymer-based porous body, a technique for obtaining porous body particles by adding an appropriate diluent during suspension polymerization of a vinyl monomer is known. This polymer-based porous material has been put into practical use as various adsorbents and separation agents by taking advantage of the light weight of polymer materials.

  A mass of material having a structure in which a continuous skeleton and voids are intertwined with each other is called a monolith. As the polymer porous body, the present inventors have (meth) acrylic acid ester polymer (Patent Document 1), polylactic acid (Patent Document 2), polyvinyl alcohol (Patent Document 3), polycarbonate (Patent Document 4). ), Polyacrylonitrile (Patent Document 5), ethylene vinyl alcohol (Patent Document 6), etc., and a method for producing a polymer porous body (monolith) by heat-induced phase separation or poor solvent-induced phase separation has been reported.

  On the other hand, bacterial cellulose (BC) is a fine cellulose fiber produced by microorganisms. In bacterial cellulose gel, the cellulose fibers form a three-dimensional network structure. The bacterial cellulose hydrogel is a gel in which water is retained in the bacterial cellulose, and the water content is about 99%. An example of the application of bacterial cellulose is Nata de Coco, which has been known for a long time. In recent years, composite materials combining bacterial cellulose and various polymers have been reported. For example, a method of immersing bacterial cellulose gel in a polyvinyl alcohol aqueous solution to make a composite (Non-patent Document 1), a method of adding polyvinyl alcohol to a bacterial cellulose dispersion and making a composite (Non-patent Documents 2 and 3), A method of adding polyvinyl alcohol to a solution of bacterial cellulose to form a complex (Non-patent Document 4), a method of culturing in the presence of polyvinyl alcohol to produce bacterial cellulose, and a complex (Non-patent Document 1), etc. Has been reported.

  In the above method, water-soluble polyvinyl alcohol is combined with bacterial cellulose, but there are not many types of polymers combined with bacterial cellulose.

JP 2009-30017 A JP 2010-260952 A JP 2012-251057 A JP2013-107948A International Publication No. 2011/138937 Pamphlet Japanese Patent Laid-Open No. 2014-23496

Materials Letters 2010, 64, 901-904 Procedia Chemistry, 2012, 4, 73-79 International Journal of Biological Macromolecules, 2011, 48, 50-57 Macromolecules, 1988, 21, 1270-1277

  Then, an object of this invention is to provide the porous body containing bacterial cellulose and a polymer, and its manufacturing method.

The present invention is a method for producing a porous body comprising bacterial cellulose and a polymer,
The method
Adding a first solvent to the bacterial cellulose hydrogel to prepare a first mixture;
Adding the polymer to the first mixture and heating; dissolving the polymer in a mixture of the first solvent and water to prepare a second mixture;
Cooling the second mixture to obtain a precipitated molded body, and immersing the molded body in a second solvent so that the first solvent and water contained in the molded body are Substituting with a solvent to obtain a porous body containing the bacterial cellulose and polymer,
The polymer is a polymer capable of forming a porous body by phase separation,
The first solvent is a solvent miscible with water. In the porous body, the bacterial cellulose is preferably fibrous.

  According to the present invention, it is possible to provide a method for producing a porous body containing bacterial cellulose and a polymer. Moreover, the porous body containing bacterial cellulose and a polymer can be obtained by the production method of the present invention.

FIG. 1 is an SEM photograph of the bacterial cellulose hydrogel obtained in Production Example 1. 2a is a SEM photograph of the BC-PAN porous material obtained in Example 1. FIG. FIG. 2 b is a SEM photograph of the BC-PAN porous material obtained in Example 1. 2c shows the photographing directions of FIGS. 2a and 2b of the SEM photograph of the BC-PAN porous material obtained in Example 1. FIG. 3a is a SEM photograph of the BC-PAN activated carbon obtained in Example 2. FIG. FIG. 3 b is a SEM photograph of BC-PAN activated carbon obtained in Example 2. 3c shows the photographing directions of FIGS. 3a and 3b of SEM photographs of the BC-PAN activated carbon obtained in Example 2. FIG. FIG. 4 is a graph showing the capacity retention ratio of the BC-PAN activated carbon obtained in Example 2 and the PAN activated carbon with respect to the scanning speed using a sulfuric acid aqueous solution (1M). 5a is a cyclic voltammogram of the BC-PAN porous material obtained in Example 1 and the BC-PAN activated carbon obtained in Example 2. FIG. FIG. 5 b is a Nyquist plot (Cole-coll plot) of the PAN activated carbon for comparison with the BC-PAN charcoal obtained in Example 2. 6a is a SEM photograph of the BC-PMMA porous material obtained in Example 3. FIG. FIG. 6 b is an SEM photograph of the BC-PMMA porous material obtained in Example 3. FIG. 7 is an SEM photograph of the BC-CA porous material obtained in Example 4. FIG. 8 is an SEM photograph of the BC-EVOH porous material obtained in Example 5-1. FIG. 9a is a SEM photograph of the BC-EVOH porous material obtained in Example 5-2. FIG. 9b is an SEM photograph of the BC-EVOH porous material obtained in Example 5-2. FIG. 10 a is a SEM photograph of the BC-EVOH porous material obtained in Example 5-3. FIG. 10 b is a SEM photograph of the BC-EVOH porous material obtained in Example 5-3. FIG. 11 is an SEM photograph of the BC-EVOH porous material obtained in Example 5-4. FIG. 12 is an SEM photograph of the BC-EVOH porous material obtained in Example 5-5. FIG. 13a is a SEM photograph of the BC-EVOH porous material obtained in Example 5-6. FIG. 13b is a SEM photograph of the BC-EVOH porous material obtained in Example 5-6.

  When an organic solvent is added to a normal hydrogel, the hydrogel contracts or collapses. The present inventors have found that such a phenomenon is not observed for the hydrogel of bacterial cellulose, and that the water in the hydrogel can be replaced with an organic solvent. Based on such knowledge, the present inventors have found that a porous body containing bacterial cellulose and a polymer can be formed by forming a polymer monolith in a bacterial cellulose hydrogel.

  In the present invention, bacterial cellulose is fine cellulose fibers produced by microorganisms. The microorganism is not limited as long as it is a cellulose-producing bacterium, and examples thereof include bacteria belonging to the genus Acetobacter, Gluconobacter, Agrobacterium, Pseudomonas, Enterobacter, and the like. In bacterial cellulose gel, the cellulose fibers form a three-dimensional network structure. The bacterial cellulose hydrogel is a gel in which water is retained in the bacterial cellulose, and the water content is about 99%. Nata de coco is a kind of bacterial cellulose hydrogel.

  The medium for culturing the microorganism is not particularly limited.For example, glucose, mannitol, sucrose, maltose, starch hydrolyzate, molasses, ethanol, acetic acid, citric acid, etc. as a carbon source, ammonium sulfate, Ammonium salts such as ammonium chloride and ammonium phosphate, nitrates, urea, polypeptone, etc. as inorganic salts, phosphates, calcium salts, iron salts, manganese salts as organic micronutrients, amino acids, vitamins, fatty acids, nucleic acids, etc. Can be used.

  In the present invention, the polymer is a polymer capable of forming a porous body by phase separation. Examples of such polymers include polylactic acid, homopolymers of acrylic esters, copolymers containing acrylic esters, homopolymers of methacrylic esters, copolymers containing methacrylic esters, polyacrylonitrile, and acrylonitrile. Copolymer, polyvinyl alcohol, ethylene vinyl alcohol copolymer, poly (γ-glutamic acid), chitosan, alginic acid, polyethylene oxide, cellulose acetate, and the like, polyacrylonitrile, copolymer containing acrylonitrile, polymethyl methacrylate, polyvinyl alcohol, and Ethylene vinyl alcohol copolymers are preferred, polyacrylonitrile, copolymers containing acrylonitrile, and ethylene vinyl alcohol copolymers are more preferred. .

  The polylactic acid is poly L-lactic acid, poly D-lactic acid or poly DL-lactic acid. The optical purity of polylactic acid is preferably 95% or higher, more preferably 96% or higher, and still more preferably 97% or higher. The weight average molecular weight (Mw) of polylactic acid is preferably 30,000 or more, more preferably 50,000 or more, and further preferably 80,000 or more. As for polylactic acid, commercially available polylactic acid may be obtained, or it may be made in-house according to methods known in the literature.

  Examples of the homopolymers of acrylic acid esters, copolymers containing acrylic acid esters, homopolymers of methacrylic acid esters, and copolymers containing methacrylic acid esters include the following.

  Examples of the homopolymers of the acrylate esters include, for example, lower alkyl alcohols having 1 to 6 carbon atoms that may include one or more selected from the group consisting of acrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom. And homopolymers of esters of acrylic acid and an epoxy lower alkyl alcohol having 2 to 6 carbon atoms. Examples of homopolymers of esters of acrylic acid and esters of lower alkyl alcohols having 1 to 6 carbon atoms that may include one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups, and halogen atoms include, for example, poly Examples thereof include methyl acrylate, polyethyl acrylate, polybutyl acrylate, poly (t-butyl acrylate), polybenzyl benzyl, etc., and homoesters of esters of acrylic acid and C2-C6 epoxy lower alkyl alcohols. Examples of the polymer include polyglycidyl acrylate.

  Examples of the copolymer containing acrylic esters include copolymers of acrylic esters and acrylic acids, copolymers of acrylic esters and methacrylic acids, copolymers of acrylic esters and acrylic esters, and acrylic esters. Examples thereof include copolymers of methacrylic acid esters, copolymers of acrylic acid esters and monomers other than those mentioned above, and the like.

  Examples of the homopolymer of the methacrylic acid esters include, for example, a lower alkyl alcohol having 1 to 6 carbon atoms which may include one or more selected from the group consisting of methacrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom. And homopolymers of esters of methacrylic acid and an epoxy lower alkyl alcohol having 2 to 6 carbon atoms. Examples of homopolymers of methacrylic acid and esters of lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms include polymethacrylic acid Examples include methyl, polyethyl methacrylate, polybutyl methacrylate, t-butyl polymethacrylate, polybenzyl methacrylate, 2-hydroxyethyl polymethacrylate, and the like, and methacrylic acid and epoxy lower alkyl alcohol having 2 to 6 carbon atoms. Examples of the homopolymer of esters with polyglycidyl methacrylate and the like.

  Examples of the copolymer containing methacrylic acid esters include, for example, a copolymer of methacrylic acid esters and acrylic acid, a copolymer of methacrylic acid esters and methacrylic acid, a copolymer of methacrylic acid esters and acrylic acid esters, and a methacrylic acid ester. Examples thereof include copolymers of methacrylic acid esters and copolymers of methacrylic acid esters and monomers other than those mentioned above. As the copolymer of the methacrylic acid esters and the other monomers, a copolymer of the methacrylic acid esters and a monomer represented by the following formula (I) is preferable.

In the formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, halogen atom, carbamoyl group, cyano group, lower alkyl group, vinyloxy group, aryl group or halogen atom. A substituted aryl group, or
R ¹ and R ³ together with the double bond to which R ¹ and R ³ are attached form 2,5-dihydrofuran-2,5-dione, and
R ² and R ³ are each independently a hydrogen atom, a halogen atom, a carbamoyl group, a cyano group, a lower alkyl group, a vinyloxy group, an aryl group or an aryl group substituted with a halogen atom.

  Examples of the copolymer of acrylic acid esters and acrylic acid include, for example, lower alkyl having 1 to 6 carbon atoms which may include one or more selected from the group consisting of acrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom. Examples include esters of alcohols and copolymers of acrylic acid; and copolymers of acrylic acid and epoxy lower alkyl alcohols having 2 to 6 carbon atoms and acrylic acid. As a copolymer of acrylic acid and an ester of acrylic acid with an ester of a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom, For example, methyl acrylate and acrylic acid copolymer, ethyl acrylate and acrylic acid copolymer, butyl acrylate and acrylic acid copolymer, t-butyl acrylate and acrylic acid copolymer, benzyl acrylate and acrylic acid copolymer, etc. Examples of the copolymer of acrylic acid and an ester of acrylic acid and an epoxy lower alkyl alcohol having 2 to 6 carbon atoms and acrylic acid include, for example, a copolymer of glycidyl acrylate and acrylic acid.

  Examples of the copolymer of acrylic acid esters and methacrylic acid include, for example, lower alkyl having 1 to 6 carbon atoms which may include one or more selected from the group consisting of acrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom. Mention may be made of esters of alcohols and copolymers of methacrylic acid; and esters of acrylic acid and C 2-6 epoxy lower alkyl alcohols and copolymers of methacrylic acid. As a copolymer of methacrylic acid and esters of acrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom, For example, a copolymer of methyl acrylate and methacrylic acid, a copolymer of ethyl acrylate and methacrylic acid, a copolymer of butyl acrylate and methacrylic acid, a copolymer of t-butyl acrylate and methacrylic acid, a copolymer of benzyl acrylate and methacrylic acid, etc. Examples of the copolymer of acrylic acid and an ester of lower alkyl alcohol having 2 to 6 carbon atoms and methacrylic acid include a copolymer of glycidyl acrylate and methacrylic acid.

  Examples of the copolymer of the acrylate ester and the acrylate ester include, for example, one or more selected from the group consisting of acrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom. Another ester of ester with lower alkyl alcohol and acrylic acid and lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl group, hydroxy group, carboxyl group and halogen atom Copolymers of acrylic acids and esters of acrylic acid with lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms, acrylic acid, Este with C2-C6 epoxy lower alkyl alcohol Kind copolymers; and and esters of epoxy lower alkyl alcohols of acrylic acid and 2 to 6 carbon atoms and another ester of an epoxy-lower alkyl alcohol having 2 to 6 carbon atoms and acrylic acid. Esters of acrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom, and an ester of the lower alkyl alcohol having 1 to 6 carbon atoms that may contain one or more, acrylic acid and an aryl group, hydroxy Examples of the copolymer of another ester with a lower alkyl alcohol having 1 to 6 carbon atoms which may include one or more selected from the group consisting of a group, a carboxyl group and a halogen atom include, for example, methyl acrylate and ethyl acrylate Copolymer, copolymer of methyl acrylate and butyl acrylate, copolymer of methyl acrylate and t-butyl acrylate, copolymer of methyl acrylate and benzyl acrylate, and the like. The acrylic acid and aryl group, hydroxy group, carboxyl group And a group of halogen atoms Examples of a copolymer of an ester of a lower alkyl alcohol having 1 to 6 carbon atoms which may include one or more and an ester of an acrylic acid and an epoxy lower alkyl alcohol having 2 to 6 carbon atoms include, for example, acrylic acid And a copolymer of methyl and glycidyl acrylate.

Examples of the copolymer of acrylic acid esters and methacrylic acid esters may include one or more selected from the group consisting of acrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom. Esters of lower alkyl alcohols and esters of methacrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms Copolymer;
Esters of acrylic acid and an epoxy lower alkyl alcohol having 2 to 6 carbon atoms, and 1 to 1 carbon atoms which may contain one or more selected from the group consisting of methacrylic acid and an aryl group, a hydroxy group, a carboxyl group and a halogen atom 6 copolymers of esters with lower alkyl alcohols;
Esters of acrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms, methacrylic acid and 2 to 6 carbon atoms A copolymer of an ester of an epoxy lower alkyl alcohol with acrylic acid; and an ester of acrylic acid with an epoxy lower alkyl alcohol having 2 to 6 carbon atoms and an ester of methacrylic acid with an epoxy lower alkyl alcohol having 2 to 6 carbon atoms A copolymer;

  Esters of acrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom that may contain one or more lower alkyl alcohols having 1 to 6 carbon atoms, methacrylic acid and an aryl group, hydroxy Examples of the copolymer of esters with a lower alkyl alcohol having 1 to 6 carbon atoms which may include one or more selected from the group consisting of a group, a carboxyl group and a halogen atom include, for example, a copolymer of methyl acrylate and methyl methacrylate, Examples thereof include a copolymer of methyl acrylate and ethyl methacrylate, a copolymer of methyl acrylate and butyl methacrylate, a copolymer of methyl acrylate and t-butyl methacrylate, and a copolymer of methyl acrylate and benzyl methacrylate. Esters of acrylic acid and lower alkyl alcohols having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl groups, hydroxy groups, carboxyl groups and halogen atoms, methacrylic acid and 2 to 2 carbon atoms Examples of the ester copolymer of 6 with an epoxy lower alkyl alcohol include a copolymer of methyl acrylate and glycidyl methacrylate.

  Examples of the copolymer of the acrylate ester and a monomer other than the above include a copolymer of the acrylate ester and a monomer represented by the following formula (I). Examples of the copolymer of the acrylate ester and the monomer represented by the following formula (I) include, for example, one or more selected from the group consisting of acrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom. Good esters of lower alkyl alcohols with 1 to 6 carbon atoms and monomers of the formula (I); and esters of acrylic acid with lower alkyl alcohols of 2 to 6 carbon atoms with the formula (I And a copolymer of monomers represented by

  An ester of acrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom, and represented by formula (I) Examples of monomer copolymers include methyl acrylate and maleic anhydride copolymers, ethyl acrylate and vinyl chloride copolymers, butyl acrylate and vinyl ether copolymers, t-butyl acrylate and maleic anhydride copolymers, and benzyl acrylate. And vinyl chloride copolymer, methyl acrylate and styrene copolymer, methyl acrylate and acrylonitrile copolymer, methyl acrylate and acrylamide copolymer, and the like. Examples of the copolymer of the acrylic acid and the ester of the lower alkyl alcohol having 2 to 6 carbon atoms and the monomer represented by the formula (I) include a copolymer of glycidyl acrylate and vinyl ether.

  Examples of the copolymer of methacrylic acid esters and acrylic acid include, for example, lower alkyl having 1 to 6 carbon atoms which may include one or more selected from the group consisting of methacrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom. Examples include esters of alcohols and acrylic acid copolymers; and esters of methacrylic acid and epoxy lower alkyl alcohols having 2 to 6 carbon atoms and acrylic acid copolymers. As a copolymer of acrylic acid with an ester of methacrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom, For example, a copolymer of methyl methacrylate and acrylic acid, a copolymer of ethyl methacrylate and acrylic acid, a copolymer of butyl methacrylate and acrylic acid, a copolymer of t-butyl methacrylate and acrylic acid, a copolymer of benzyl methacrylate and acrylic acid, etc. Can be mentioned. Examples of the copolymer of methacrylic acid and an ester of lower alkyl alcohol having 2 to 6 carbon atoms and acrylic acid include a copolymer of glycidyl methacrylate and acrylic acid.

  Examples of the copolymer of methacrylic acid esters and methacrylic acid include, for example, lower alkyl having 1 to 6 carbon atoms which may include one or more selected from the group consisting of methacrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom. Mention may be made of esters of alcohols with copolymers of methacrylic acid; and esters of methacrylic acid with C 2-6 epoxy lower alkyl alcohols and copolymers of methacrylic acid. As a copolymer of methacrylic acid and esters of a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom, For example, copolymers of methyl methacrylate and methacrylic acid, copolymers of ethyl methacrylate and methacrylic acid, copolymers of butyl methacrylate and methacrylic acid, copolymers of t-butyl methacrylate and methacrylic acid, copolymers of benzyl methacrylate and methacrylic acid, etc. Can be mentioned. Examples of the copolymer of methacrylic acid and an ester of lower alkyl alcohol having 2 to 6 carbon atoms and methacrylic acid include a copolymer of glycidyl methacrylate and methacrylic acid.

Examples of the copolymer of methacrylic acid esters and methacrylic acid esters include, for example, methacrylic acid and one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group, and a halogen atom. Another ester of methacrylic acid and lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of aryl group, hydroxy group, carboxyl group and halogen atom Types of copolymers;
Esters of methacrylic acid and epoxy lower alkyl alcohols having 2 to 6 carbon atoms, and 1 to 1 carbon atoms which may contain one or more selected from the group consisting of methacrylic acid and aryl groups, hydroxy groups, carboxyl groups and halogen atoms A copolymer of esters of 6 lower alkyl alcohols; and esters of methacrylic acid and epoxy lower alkyl alcohols having 2 to 6 carbon atoms and other esters of methacrylic acid and epoxy lower alkyl alcohols having 2 to 6 carbon atoms. A class of copolymers.

  Esters of the methacrylic acid with an aryl group, a hydroxy group, a carboxyl group and a halogen atom, which may contain one or more, and a lower alkyl alcohol having 1 to 6 carbon atoms, methacrylic acid and an aryl group, hydroxy Examples of the copolymer of another ester with a lower alkyl alcohol having 1 to 6 carbon atoms which may include one or more selected from the group consisting of a group, a carboxyl group and a halogen atom include, for example, methyl methacrylate and ethyl methacrylate Copolymers, copolymers of methyl methacrylate and butyl methacrylate, copolymers of butyl methacrylate and benzyl methacrylate, and the like. Esters of the methacrylic acid with an aryl group, a hydroxy group, a carboxyl group, and one or more selected from the group consisting of a halogen atom and a lower alkyl alcohol having 1 to 6 carbon atoms, methacrylic acid and 2 to 2 carbon atoms Examples of the copolymer of esters of 6 with an epoxy lower alkyl alcohol include a copolymer of methyl methacrylate and glycidyl methacrylate.

  Examples of the copolymer of the methacrylic acid esters and the monomer represented by the formula (I) include carbon that may contain at least one selected from the group consisting of methacrylic acid and an aryl group, a hydroxy group, a carboxyl group, and a halogen atom. A copolymer of an ester with a lower alkyl alcohol of 1 to 6 and a monomer represented by the formula (I); and an ester of a methacrylic acid with an epoxy lower alkyl alcohol of 2 to 6 carbon atoms with the formula (I) Mention may be made of copolymers of the monomers represented.

  An ester of the methacrylic acid and a lower alkyl alcohol having 1 to 6 carbon atoms which may contain one or more selected from the group consisting of an aryl group, a hydroxy group, a carboxyl group and a halogen atom, and is represented by the formula (I) Examples of the copolymer of monomers include, for example, a copolymer of methyl methacrylate and maleic anhydride, a copolymer of ethyl methacrylate and vinyl chloride, a copolymer of butyl methacrylate and vinyl ether, a copolymer of t-butyl methacrylate and maleic anhydride, and benzyl methacrylate. And vinyl chloride copolymer, methyl methacrylate and styrene copolymer, methyl methacrylate and acrylonitrile copolymer, methyl methacrylate and acrylamide copolymer, methyl methacrylate and 4-chloromethyl styrene copolymer And the like. Examples of the copolymer of the ester of methacrylic acid and an epoxy lower alkyl alcohol having 2 to 6 carbon atoms and the monomer represented by the formula (I) include a copolymer of glycidyl methacrylate and vinyl ether.

  In addition, when the said polymer is a copolymer, a monomer composition ratio is not limited, However, The thing with which the solubility with respect to the water of the polymer becomes low is mentioned. The monomer sequence of the polymer may be random, block or the like. Furthermore, although the molecular weight of the polymer is not limited, for example, the number average molecular weight is 1,000 to 100,000,000, preferably 2,000 to 50,000,000, more preferably 3,000 to 20,000,000. For example, the weight average molecular weight is 1,000 to 150,000,000, preferably 2,000 to 80,000,000, and more preferably 3,000 to 40,000,000.

  The molecular weight of the polyacrylonitrile is not limited, but the average molecular weight is, for example, 10,000 to 5,000,000, preferably 20,000 to 4,000,000, and more preferably 30,000 to 3,000,000.

  Examples of the copolymer containing acrylonitrile include a copolymer of vinyl acetate and acrylonitrile, a copolymer of methyl acrylate and acrylonitrile, a copolymer of styrene and acrylonitrile, a copolymer of methacrylic acid and acrylonitrile, a copolymer of butadiene and acrylonitrile, and the like.

  Although the molecular weight is not limited as said polyvinyl alcohol, For example, molecular weight is 5,000-5 million, Preferably it is 10,000-4 million, More preferably, it is 10,000-3 million. The degree of polymerization is, for example, 100 to 100,000, preferably 200 to 80,000, more preferably 200 to 60,000. Polyvinyl alcohol has a saponification degree of, for example, 60 mol% or more, preferably 80 mol% or more, more preferably 85 mol% or more.

  Although molecular weight is not limited as said ethylene vinyl alcohol copolymer, For example, molecular weight is 5,000-5 million, Preferably it is 10,000-4 million, More preferably, it is 10,000-3 million. The degree of polymerization is, for example, 100 to 100,000, preferably 200 to 80,000, more preferably 200 to 60,000.

  The poly (γ-glutamic acid) is a linear water-soluble biodegradable polymer which is produced very efficiently by fermentation of microorganisms belonging to the genus Bacillus and has a carboxyl group in the side chain. is there. The molecular weight of the poly (γ-glutamic acid) is not limited, but is, for example, 3,000 to 10,000,000, preferably 5,000 to 8,000,000, and more preferably 10,000 to 5,000,000. The degree of polymerization is, for example, 100 to 100,000, preferably 200 to 80,000, more preferably 200 to 60,000.

  The chitosan is a natural polysaccharide having an amino group, and is a functional polymer having various uses such as antibacterial properties and metal chelating ability. The porous body containing ethylene vinyl alcohol copolymer and chitosan as main components is a porous body having both the hydroxyl group of ethylene vinyl alcohol copolymer and the amino group of chitosan. The chitosan has a degree of deacetylation of, for example, 60 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more. Moreover, as chitosan, polymerization degree is 30-10,000, for example, Preferably it is 50-5,000.

  The alginic acid is a linear polymer in which two types of blocks, β-D-mannuronic acid and α-L-guluronic acid, which is the C-5 epimer, are bonded (1-4). The molecular weight of the alginic acid is not limited, but is, for example, 3,000 to 10,000,000, preferably 5,000 to 8,000,000, and more preferably 10,000 to 5,000,000.

  Although the molecular weight is not limited as said polyethylene oxide, For example, it is 3,000-10 million, Preferably it is 5,000-8 million, More preferably, it is 10,000-5 million.

  The cellulose acetate is a polymer obtained by esterifying cellulose. The oxidation degree of cellulose acetate is, for example, 50 to 70. Although molecular weight is not limited as cellulose acetate, For example, molecular weight is 3,000-10 million, Preferably it is 5,000-8 million, More preferably, it is 10,000-5 million.

<Step of adding a first solvent to bacterial cellulose hydrogel to prepare a first mixture>
By adding a first solvent to the bacterial cellulose hydrogel, a first mixture containing bacterial cellulose, water and the first solvent is obtained. Bacterial cellulose hydrogel has a water content of about 99%.

  In the present invention, the first solvent is not limited as long as it is miscible with water and is a solvent other than water. Examples of such a first solvent include methanol, ethanol, isopropanol, glycerin, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 2-butanone, nitromethane, Nitroethane, nitrobenzene, benzonitrile, propionitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetone, methyl ethyl ketone, dimethylacetamide (DMAc), N-methylpyrrolidone, 1,4-dioxane, acetonitrile, 1-propanol is exemplified, and dimethyl sulfoxide, ethanol, methanol, isopropanol, DMF, N-methylpyrrolidone, and 1,4-dioxane are preferable, and dimethyl sulfoxide Ethanol, isopropanol, DMF is preferred.

  When the polymer is polylactic acid, the first solvent is preferably DMSO or 1,4-dioxane, more preferably DMSO. When the polymer is any one of a homopolymer of acrylic esters, a copolymer containing acrylic esters, a homopolymer of methacrylic esters, and a copolymer containing methacrylic esters, Is preferably an aliphatic alcohol containing an aliphatic hydrocarbon having 1 to 8 carbon atoms and having 1 or more hydroxyl groups, and more preferably ethanol or isopropanol. When the polymer is polyacrylonitrile, the first solvent is preferably dimethyl sulfoxide, DMF, or DMAc, and more preferably dimethyl sulfoxide, or DMF. When the polymer is polyvinyl alcohol, acetone is preferable as the first solvent. When the polymer is an ethylene vinyl alcohol copolymer, isopropanol is preferable as the first solvent. When the polymer is a copolymer containing acrylonitrile, the first solvent is preferably dimethyl sulfoxide, DMF, or DMAc, and more preferably dimethyl sulfoxide, or DMF. When the polymer is poly (γ-glutamic acid), the first solvent is preferably dimethyl sulfoxide, DMF, or DMAc, and more preferably dimethyl sulfoxide, or DMF. When the polymer is chitosan, the first solvent is preferably dimethyl sulfoxide, DMF or DMAc, more preferably dimethyl sulfoxide or DMF. When the polymer is alginic acid, the first solvent is preferably methanol, ethanol and isopropanol, more preferably methanol and ethanol. When the polymer is polyethylene oxide, the first solvent is preferably dimethyl sulfoxide, DMF or DMAc, more preferably dimethyl sulfoxide or DMF. When the polymer is cellulose acetate, the first solvent is preferably dimethyl sulfoxide, DMF or DMAc, more preferably dimethyl sulfoxide or DMF.

  In the production method of the present invention, the volume ratio [first solvent / (water + first solvent)] of the first solvent and water in the first mixture is preferably 10 to 99.5%, More preferably, it is 20 to 99%. Since the bacterial cellulose hydrogel has a water content of about 99%, the volume of water in the first mixture is substantially the same as the volume of the bacterial cellulose hydrogel.

  When the polymer is polylactic acid, the volume ratio (first solvent / water + first solvent) of the first solvent and water in the first mixture is preferably 75% to 99.5%. Further, when the polymer is any one of a homopolymer of acrylic esters, a copolymer containing acrylic esters, a homopolymer of methacrylic esters, and a copolymer containing methacrylic esters, in the first mixture, The volume ratio of the first solvent and water (first solvent / water + first solvent) is preferably 30 to 99%, more preferably 50 to 97%. Further, when the polymer is polyacrylonitrile, the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is preferably 10 to 95%, 20 to 90% is more preferable. Further, when the polymer is polyvinyl alcohol, the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is preferably 35 to 55%, and 50 -52% is more preferable. Further, when the polymer is an ethylene vinyl alcohol copolymer, the volume ratio of the first solvent and water in the first mixture (first solvent / water + first solvent) is 40 to 90%. Is preferable, and 40 to 80% is more preferable. Further, when the polymer is a copolymer containing acrylonitrile, the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is preferably 10 to 95%. 20 to 90% is more preferable. Further, when the polymer is poly (γ-glutamic acid), the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is 10 to 95%. Is preferable, and 20 to 90% is more preferable. When the polymer is chitosan, the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is preferably 40 to 90%, 80% is more preferable. When the polymer is alginic acid, the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is preferably 35 to 55%, preferably 50 to 52% is more preferable. Further, when the polymer is polyethylene oxide, the volume ratio of the first solvent and water (first solvent / water + first solvent) in the first mixture is preferably 10 to 95%, 20 -90% is more preferable. When the polymer is cellulose acetate, the volume ratio of the first solvent to water (first solvent / water + first solvent) in the first mixture is preferably 10 to 95%, -90% is more preferable.

  In the present invention, examples of the second solvent include water, lower alcohol, acetone, methyl ethyl ketone, dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone, 1,4-dioxane, and acetonitrile. 1 or more selected from the group consisting of lower alcohol, acetone and acetonitrile, more preferably water, methanol, acetone and acetonitrile. Examples of the lower alcohol include lower alcohols having 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, i-propanol, n-butanol, 2-butanol, i-butanol, t-butanol, n -Pentanol, t-amyl alcohol, n-hexanol.

<Step of adding the polymer to the first mixture and heating, and dissolving the polymer in a mixture of the first solvent and water to prepare a second mixture>
The polymer may be subjected to a physical stimulus when dissolved in the first solvent and water mixture. Examples of the physical stimulation include stirring, shaking, ultrasonic treatment, and the like. The temperature at the time of adding and heating the polymer to the first mixture is, for example, 15 ° C to 100 ° C, and preferably 20 ° C to 95 ° C. The second mixture includes the bacterial cellulose, water, the first solvent, and the polymer. The polymer is dissolved in a mixture of water and a first solvent.

  When the polymer is polylactic acid, the heating temperature is preferably 40 ° C to 100 ° C. In addition, when the polymer is any one of a homopolymer of acrylic acid esters, a copolymer containing acrylic acid esters, a homopolymer of methacrylic acid esters, and a copolymer containing methacrylic acid esters, the heating temperature is The temperature is preferably 15 ° C to 65 ° C, more preferably 20 ° C to 60 ° C. Moreover, when the said polymer is polyacrylonitrile, the temperature at the time of heating becomes like this. Preferably it is 70 to 95 degreeC, More preferably, it is 70 to 90 degreeC. Moreover, when the said polymer is polyvinyl alcohol, the temperature at the time of heating becomes like this. Preferably it is 30 to 100 degreeC, More preferably, it is 40 to 100 degreeC. Moreover, when the said polymer is an ethylene vinyl alcohol copolymer, the temperature at the time of heating becomes like this. Preferably it is 30 to 100 degreeC, More preferably, it is 40 to 100 degreeC. Moreover, when the said polymer is a copolymer containing acrylonitrile, the temperature at the time of heating becomes like this. Preferably it is 70 to 95 degreeC, More preferably, it is 70 to 90 degreeC. Moreover, when the said polymer is poly ((gamma) -glutamic acid), the temperature at the time of heating becomes like this. Preferably it is 70 to 95 degreeC, More preferably, it is 70 to 90 degreeC. Moreover, when the said polymer is chitosan, the temperature at the time of heating becomes like this. Preferably it is 30 to 100 degreeC, More preferably, it is 40 to 100 degreeC. Moreover, when the said polymer is alginic acid, the temperature at the time of heating becomes like this. Preferably it is 30 to 100 degreeC, More preferably, it is 40 to 100 degreeC. Moreover, when the said polymer is polyethylene oxide, the temperature at the time of heating becomes like this. Preferably it is 70 to 95 degreeC, More preferably, it is 70 to 90 degreeC. Moreover, when the said polymer is a cellulose acetate, the temperature at the time of heating becomes like this. Preferably it is 70 to 95 degreeC, More preferably, it is 70 to 90 degreeC.

  In the production method of the present invention, the concentration of the polymer in the second mixture is, for example, 5 to 300 mg / ml, preferably 10 to 200 mg / ml, more preferably 15 to 150 mg / ml.

  When the polymer is polylactic acid, the concentration of the polymer in the second mixture is preferably 30 to 150 mg / ml, more preferably 30 to 120 mg / ml. When the polymer is any one of a homopolymer of acrylic esters, a copolymer containing acrylic esters, a homopolymer of methacrylic esters, and a copolymer containing methacrylic esters, in the second mixture, The concentration of the polymer is preferably 5 to 200 mg / ml. When the polymer is polyacrylonitrile, the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 50 to 200 mg / ml. When the polymer is polyvinyl alcohol, the concentration of the polymer in the second mixture is preferably 10 to 300 mg / ml, more preferably 15 to 200 mg / ml. When the polymer is an ethylene vinyl alcohol copolymer, the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 60 to 250 mg / ml. When the polymer is a copolymer containing acrylonitrile, the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 50 to 200 mg / ml. When the polymer is poly (γ-glutamic acid), the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 50 to 200 mg / ml. When the polymer is chitosan, the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 60 to 250 mg / ml. When the polymer is alginic acid, the concentration of the polymer in the second mixture is preferably 10 to 300 mg / ml, more preferably 15 to 200 mg / ml. When the polymer is polyethylene oxide, the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 50 to 200 mg / ml. When the polymer is cellulose acetate, the concentration of the polymer in the second mixture is preferably 40 to 300 mg / ml, more preferably 50 to 200 mg / ml.

<Step of cooling the second mixture to obtain a deposited product>
The temperature for cooling the second mixture is, for example, -200 ° C to 60 ° C, preferably -196 ° C to 45 ° C, more preferably -20 ° C to 40 ° C. The cooling time is preferably 10 seconds to 48 hours, more preferably 30 seconds to 24 hours. In addition, when cooling this 2nd mixture, you may put a 2nd mixture in a container and cool it.

  When the polymer is polylactic acid, the temperature for cooling the second mixture is preferably −20 ° C. to 30 ° C. When the polymer is any one of a homopolymer of acrylic esters, a copolymer containing acrylic esters, a homopolymer of methacrylic esters, and a copolymer containing methacrylic esters, the second mixture is The cooling temperature is preferably -200 ° C to 40 ° C, more preferably 0 ° C to 30 ° C. Moreover, when the said polymer is polyacrylonitrile, the temperature which cools a said 2nd mixture becomes like this. Preferably it is -20 degreeC-60 degreeC, More preferably, it is 15 degreeC-45 degreeC. When the polymer is polyvinyl alcohol, the temperature for cooling the second mixture is preferably -196 ° C to 40 ° C, more preferably -196 ° C to 35 ° C. When the polymer is an ethylene vinyl alcohol copolymer, the temperature for cooling the second mixture is preferably −196 ° C. to 40 ° C., more preferably −196 ° C. to 35 ° C. Moreover, when the said polymer is a copolymer containing acrylonitrile, the temperature which cools a said 2nd mixture becomes like this. Preferably it is -20 degreeC-60 degreeC, More preferably, it is 15 degreeC-45 degreeC. When the polymer is poly (γ-glutamic acid), the temperature for cooling the second mixture is preferably −20 ° C. to 60 ° C., more preferably 15 ° C. to 45 ° C. Moreover, when the said polymer is chitosan, the temperature which cools a said 2nd mixture becomes like this. Preferably it is -196 to 40 degreeC, More preferably, it is -196 to 35 degreeC. When the polymer is alginic acid, the temperature for cooling the second mixture is preferably -196 ° C to 40 ° C, more preferably -196 ° C to 35 ° C. When the polymer is polyethylene oxide, the temperature for cooling the second mixture is preferably −20 ° C. to 60 ° C., more preferably 15 ° C. to 45 ° C. Moreover, when the said polymer is a cellulose acetate, the temperature which cools a said 2nd mixture becomes like this. Preferably it is -20 degreeC-60 degreeC, More preferably, it is 15 degreeC-45 degreeC.

  When the polymer is polylactic acid, the cooling time is preferably 5 minutes to 3 hours. In addition, when the polymer is any one of acrylic ester homopolymer, copolymer containing acrylic ester, homopolymer of methacrylic ester, and copolymer containing methacrylic ester, the cooling time is preferably It is 1 minute to 24 hours, and more preferably 1 minute to 1.5 hours. When the polymer is polyacrylonitrile, the cooling time is preferably 1 minute to 24 hours, more preferably 1 minute to 1.5 hours. Moreover, when the said polymer is polyvinyl alcohol, Preferably cooling time is 10 second-48 hours, More preferably, it is 30 second-24 hours. When the polymer is an ethylene vinyl alcohol copolymer, the cooling time is preferably 10 seconds to 48 hours, more preferably 30 seconds to 24 hours. When the polymer is a copolymer containing acrylonitrile, the cooling time is preferably 1 minute to 24 hours, more preferably 1 minute to 1.5 hours. When the polymer is poly (γ-glutamic acid), the cooling time is preferably 1 minute to 24 hours, more preferably 1 minute to 1.5 hours. When the polymer is chitosan, the cooling time is preferably 10 seconds to 48 hours, more preferably 30 seconds to 24 hours. When the polymer is alginic acid, the cooling time is preferably 10 seconds to 48 hours, more preferably 30 seconds to 24 hours. When the polymer is polyethylene oxide, the cooling time is preferably 1 minute to 24 hours, and more preferably 1 minute to 1.5 hours. When the polymer is cellulose acetate, the cooling time is preferably 1 minute to 24 hours, more preferably 1 minute to 1.5 hours.

<Porous body containing the bacterial cellulose and polymer by immersing the molded body in a second solvent and replacing the first solvent and water contained in the molded body with the second solvent Step of obtaining>
After replacing the first solvent and water with the second solvent, the obtained molded body may be dried to obtain a porous body. The drying is performed, for example, at 0 ° C to 90 ° C, preferably 10 ° C to 80 ° C. The drying is performed, for example, under reduced pressure to normal pressure, preferably under reduced pressure. The drying may be freeze drying.

When the polymer is polylactic acid, the drying is preferably performed at 20 ° C to 80 ° C, more preferably 20 ° C to 60 ° C. When the polymer is any one of a homopolymer of acrylic esters, a copolymer containing acrylic esters, a homopolymer of methacrylic esters, and a copolymer containing methacrylic esters, the second mixture is The drying is preferably performed at a temperature of 10 to 40 ° C, more preferably 20 to 30 ° C. Moreover, when the said polymer is polyacrylonitrile, the said drying becomes like this. Preferably it is 0 to 90 degreeC, More preferably, it performs at 0 to 80 degreeC. Moreover, when the said polymer is polyvinyl alcohol, the said drying becomes like this. Preferably it is 0 to 90 degreeC, More preferably, it performs at 10 to 80 degreeC. Moreover, when the said polymer is an ethylene vinyl alcohol copolymer, the said drying becomes like this. Preferably it is 0 to 90 degreeC, More preferably, it performs at 10 to 80 degreeC. When the polymer is a copolymer containing acrylonitrile, the drying is preferably performed at 0 ° C to 90 ° C, more preferably 0 ° C to 80 ° C. When the polymer is poly (γ-glutamic acid), the drying is preferably performed at 0 ° C. to 90 ° C., more preferably 0 ° C. to 80 ° C. Moreover, when the said polymer is chitosan, the said drying becomes like this. Preferably it is 0 to 90 degreeC, More preferably, it performs at 10 to 80 degreeC.
When the polymer is alginic acid, the drying is preferably performed at 0 ° C to 90 ° C, more preferably 10 ° C to 80 ° C. When the polymer is polyethylene oxide, the drying is preferably performed at 0 ° C to 90 ° C, more preferably 0 ° C to 80 ° C. Moreover, when the said polymer is a cellulose acetate, the said drying becomes like this. Preferably it is 0 to 90 degreeC, More preferably, it performs at 0 to 80 degreeC.

  The porous body of the present invention contains bacterial cellulose and a polymer as described above, and the polymer is a porous body that is a polymer that can form a porous body by phase separation. Specifically, the porous body has a structure in which a three-dimensional network structure of the bacterial cellulose (preferably fibrous bacterial cellulose) is entangled with the porous body of the polymer. The porous body of the present invention has, for example, a pore diameter of 0.05 μm to 30 μm, a skeleton diameter of, for example, 0.05 μm to 20 μm, and preferably a pore diameter of 0.1 μm to 10 μm, The diameter is preferably 0.1 μm to 20 μm, more preferably the pore diameter is 0.3 μm to 10 μm, and the skeleton diameter is more preferably 0.3 μm to 8 μm.

  When the polymer is polylactic acid, the pore diameter of the obtained porous body is preferably 0.1 μm to 10 μm, and the skeleton diameter is preferably 0.1 μm to 10 μm. In addition, when the polymer is any one of a homopolymer of acrylic acid esters, a copolymer containing acrylic acid esters, a homopolymer of methacrylic acid esters, and a copolymer containing methacrylic acid esters, The pore diameter is preferably 0.1 μm to 15 μm, and the skeleton diameter is preferably 0.05 μm to 10 μm. Moreover, when the polymer is polyacrylonitrile, the pore diameter of the obtained porous body is preferably 0.1 μm to 15 μm, and the skeleton diameter is preferably 0.05 μm to 10 μm. When the polymer is polyvinyl alcohol, the pore size of the obtained porous body is preferably 0.05 μm to 30 μm, and the skeleton diameter is preferably 0.05 μm to 10 μm. When the polymer is an ethylene vinyl alcohol copolymer, the pore size of the obtained porous material is preferably 0.2 μm to 20 μm, and the skeleton diameter is preferably 0.3 μm to 10 μm. When the polymer is a copolymer containing acrylonitrile, the pore size of the obtained porous body is preferably 0.1 μm to 15 μm, and the skeleton diameter is preferably 0.05 μm to 10 μm. When the polymer is poly (γ-glutamic acid), the pore size of the obtained porous body is preferably 0.1 μm to 15 μm, and the skeleton size is preferably 0.05 μm to 10 μm. When the polymer is chitosan, the pore size of the obtained porous body is preferably 0.2 μm to 20 μm, and the skeleton diameter is preferably 0.3 μm to 10 μm. Moreover, when the polymer is alginic acid, the pore size of the obtained porous body is preferably 0.05 μm to 30 μm, and the skeleton diameter is preferably 0.05 μm to 10 μm. When the polymer is polyethylene oxide, the pore size of the obtained porous body is preferably 0.1 μm to 15 μm, and the skeleton diameter is preferably 0.05 μm to 10 μm. When the polymer is cellulose acetate, the pore size of the obtained porous body is preferably 0.1 μm to 15 μm, and the skeleton diameter is preferably 0.05 μm to 10 μm.

Moreover, the specific surface area of the porous body of this invention is 1-1000 m < ² > / g, for example, Preferably it is 2-500 m < ² > / g. In addition, specific surface area can be specifically measured by the method as described in an Example. Therefore, such a porous body can be used as, for example, a filter or an adsorbent.

When the polymer is polylactic acid, the specific surface area of the porous body is preferably 3 to 900 m ² / g, more preferably 5 to 700 m ² / g. In addition, when the polymer is any one of a homopolymer of acrylic esters, a copolymer containing acrylic esters, a homopolymer of methacrylic esters, and a copolymer containing methacrylic esters, the specific surface area of the porous body Is preferably 3 to 900 m ² / g, more preferably 5 to 700 m ² / g. When the polymer is polyacrylonitrile, the specific surface area of the porous body is preferably 3 to 900 m ² / g, more preferably 5 to 700 m ² / g. Moreover, when the said polymer is polyvinyl alcohol, Preferably the specific surface area of a porous body is 3-900 m < ² > / g, More preferably, it is 5-700 m < ² > / g. Also, if the polymer is an ethylene-vinyl alcohol copolymer, a specific surface area of the porous body is preferably a 5 to 500 m ² / g, more preferably from 10 to 300 m ² / g. In addition, specific surface area can be specifically measured by the method as described in an Example.

In addition, the first porous body of the present invention is
A multilayer structure of the bacterial cellulose;
A porous structure derived from the polymer,
The polymer is a copolymer including one or more selected from the group consisting of polyacrylonitrile, a copolymer including acrylonitrile, a copolymer including methacrylic acid esters, and an ethylene vinyl alcohol copolymer,
The distance between the layers of the multilayer structure is in the range of 0.1 μm to 20 μm,
The layer thickness of the multilayer structure is in the range of 0.2 μm to 30 μm. In the porous body, the bacterial cellulose is preferably fibrous.

  In the first porous body, the distance between the layers of the multilayer structure is in the range of 0.1 μm to 20 μm, preferably in the range of 0.2 μm to 15 μm, more preferably 0.2 μm. It is in the range of -10 μm.

  In the first porous body, the thickness of the multilayer structure layer is in the range of 0.2 μm to 30 μm, preferably in the range of 0.3 μm to 20 μm, and more preferably in the range of 0.3 μm to 10 μm. Range.

The second porous body of the present invention is
A multilayer structure of the bacterial cellulose;
A layer derived from the polymer,
The polymer is an ethylene vinyl alcohol copolymer or a copolymer of cellulose acetate,
The distance between the layers of the multilayer structure is in the range of 0.1 μm to 20 μm,
The layer thickness of the multilayer structure is in the range of 0.2 μm to 30 μm. The polymer-derived layer is preferably on the bacterial cellulose. In the porous body, the bacterial cellulose is preferably fibrous.

  In the second porous body, the distance between the layers of the multilayer structure is in the range of 0.1 μm to 20 μm, preferably in the range of 0.2 μm to 15 μm, more preferably 0.2 μm. It is in the range of -10 μm.

  In the second porous body, the thickness of the multilayer structure layer is in the range of 0.2 μm to 30 μm, preferably in the range of 0.3 μm to 20 μm, and more preferably in the range of 0.3 μm to 10 μm. Range.

  Said 1st porous body and 2nd porous body can be obtained with the manufacturing method of the porous body containing the bacterial cellulose and polymer of this invention.

  In the porous material of the present invention, when the polymer is an ethylene vinyl alcohol copolymer, the porous material obtained by changing the solvent composition of the first solvent and water (phase separation) and the composition of the ethylene vinyl alcohol copolymer. The structure of the mass can be adjusted. Specifically, in the case of an ethylene vinyl alcohol copolymer (ethylene content: 27 mol%), the composition of the first solvent and water (mixed solvent used for phase separation) is set to water / first solvent (for example, Isopropanol) = 60/40 to 65/35 vol%, a porous body having a structure including a three-dimensional network structure of nanofibers of bacterial cellulose and a porous structure of a polymer deposited around the network structure can get. Further, the composition of the first solvent and water (mixed solvent used for the phase separation) is water / first solvent (for example, isopropanol) = 35/65 to 55/45 vol%, so that the multilayer structure of bacterial cellulose A porous body having a structure including a porous layer derived from a polymer on the bacterial cellulose can be obtained. In the case of an ethylene vinyl alcohol copolymer (ethylene content: 44 mol%), the composition of the first solvent and water (mixed solvent used for phase separation) is water / first solvent (for example, isopropanol) = By setting it as 30 / 70-40 / 60 vol%, the porous body of the structure containing the multilayer structure of a bacterial cellulose and the porous layer derived from a polymer on the said bacterial cellulose is obtained.

The present invention is activated carbon derived from bacterial cellulose and polymer,
The polymer is polyacrylonitrile or a copolymer containing acrylonitrile,
A multilayer structure derived from the bacterial cellulose;
A porous structure derived from the polymer,
The distance between the layers of the multilayer structure is in the range of 0.1 μm to 20 μm,
The layer thickness of the multilayer structure is in the range of 0.2 μm to 30 μm,
The nitrogen content is in the range of 0.1 to 10% by mass. The porous structure derived from the polymer is porous along the multilayer structure derived from the bacterial cellulose.

  In the activated carbon, the distance between the layers of the multilayer structure is in the range of 0.1 μm to 20 μm, preferably in the range of 0.2 μm to 15 μm, more preferably in the range of 0.2 μm to 10 μm. is there.

  In the activated carbon, the thickness of the multilayer structure layer is in the range of 0.2 to 30 μm, preferably in the range of 0.3 to 20 μm, and more preferably in the range of 0.3 to 10 μm.

  In the activated carbon, the nitrogen content is in the range of 0.1 to 10% by mass, preferably in the range of 0.3 to 10% by mass, more preferably in the range of 0.3 to 8% by mass. .

  The present invention also relates to a method for producing activated carbon derived from bacterial cellulose and a polymer, wherein the polymer is polyacrylonitrile or a copolymer containing acrylonitrile, and the method for producing a porous body containing bacterial cellulose and a polymer according to the present invention. A step of firing the obtained porous body is included.

Before the firing, for example, 150 to 350 ° C., preferably 160
Pre-baking (infusibilization) may be performed at ˜280 ° C. in air, for example, for 0.5 to 20 hours, preferably 1 to 15 hours.

  The calcination is performed at, for example, 500 to 1800 ° C., preferably 600 to 1400 ° C. in an atmosphere of an active gas such as a mixture of argon and carbon dioxide (carbon dioxide / argon (volume ratio) = for example, 0.05 to 2, Preferably it is 0.1 to 3, for example, 0.1 to 24 hours, preferably 0.2 to 12 hours.

  Since the activated carbon is porous and has a high specific surface area, it can be used as an adsorbent such as gas, a deodorizing material, a methane storage material, and the like. Moreover, since the activated carbon has a high carbon content and exhibits conductivity, it can also be used as an electrode material. Examples of the electrode material include electrode materials such as an electric double layer capacitor and a hybrid capacitor.

The present invention will be described more specifically with reference to the following examples. However, the scope of the present invention is not limited by the following examples.
The following abbreviations are used in the description of this specification.
DMSO: dimethyl sulfoxide PAN: polyacrylonitrile IPA: isopropanol DMF: dimethylformamide SEM: scanning electron microscope AC: acetylene black PTFE: polytetrafluoroethylene

In this specification, the following devices were used as measuring devices.
SEM: Hitachi SU3509 (manufactured by Hitachi High-Technologies Corporation)
High-speed / specific surface area / pore distribution analyzer: Quantachrome Nova4200e (manufactured by Cantachrome Instruments Japan GK)
Elemental analysis: CHN corder MT-5 (Yamano)
Cyclic voltammetry: ALS7002E (manufactured by BAS)
AC impedance: Electrochemical Analyzer ALS660A (manufactured by BAS)
In the present specification, the pore diameter and the skeleton diameter describe the minimum and maximum values of the pore diameter and the skeleton diameter measured from an image taken using a scanning electron microscope (SEM).

[Production Example 1]
Manufacture of bacterial cellulose hydrogel 500 mL of pure water, polypeptone (2.5 g, Wako Pure Chemical Industries, Ltd.), yeast extract (“Bacto ™”, 2.5 g, Wako Pure Chemical Industries, Ltd.), glucose (2.5 g ), D-mannitol (2.5 g, Wako Pure Chemical Industries, Ltd.), MgSO ₄ .7H ₂ O (0.5 g) and ethanol (2.5 mL) are mixed well, and the pH is adjusted to about 4 with acetic acid. A liquid medium was prepared. The medium was placed in a heat-resistant plastic container and sterilized using an autoclave, and then Acetobacter xylinus (NBRC13693) was planted and cultured at 30 ° C. for 1 week. The gel produced on the surface of the medium was collected. After replacing the medium components in the obtained gel by impregnating with deionized water over 2 days, the gel was sterilized by autoclaving, and further boiled and sterilized with a 2 wt% aqueous sodium hydroxide solution. After sterilization, the sodium hydroxide aqueous solution in the gel was replaced with deionized water over 2 days to obtain a bacterial cellulose hydrogel. An SEM photograph of the obtained bacterial cellulose hydrogel is shown in FIG.

[Example 1]
Production of porous material containing bacterial cellulose and polyacrylonitrile (hereinafter sometimes referred to as “BC-PAN porous material”) In a sample bowl, the bacterial cellulose hydrogel produced in Production Example 1 was treated with DMSO (Nacalai Tesque Corporation). The solvent contained in the bacterial cellulose was replaced with DMSO. At this time, substitution was performed so that water / DMSO = 15/85 vol%. After solvent substitution, 70 mg / kg of a copolymer containing acrylonitrile (hereinafter referred to as “PAN” for convenience) (a copolymer of acrylonitrile: vinyl acetate = 93: 7, manufactured by Sigma-Aldrich) to the impregnated bacterial cellulose hydrogel. The mixture was added to mL, and the mixture was stirred with a hot stirrer at 90 ° C. overnight. After stirring, the gel-like material is taken out from the mixture, placed in another sample bowl and left in a bioshaker at 25 ° C (“TAOTEC Bioshaker M · BR-022UP”) for 2 hours, and then with a large amount of water for 1 day. The solvent contained in the gel was replaced with water. The obtained gel-like material was freeze-dried (“EYELA FDU 12000”, Tokyo Science Equipment Co., Ltd.) to remove water and obtain a BC-PAN porous material. The SEM photograph of the obtained BC-PAN porous material is shown in FIGS. 2a and 2b. As shown in FIG. 2c, FIG. 2a is a SEM photograph of the BC-PAN porous body observed in the vertical direction and FIG. 2b is observed in the horizontal direction. As shown in FIG. 2a, it was confirmed that the BC-PAN porous body had a structure in which a three-dimensional network structure of nanofibers of bacterial cellulose and a porous structure of polyacrylonitrile were intertwined. Moreover, as shown in FIG. 2b, it was confirmed that the BC-PAN porous body includes a multilayer structure of bacterial cellulose and a porous structure derived from polyacrylonitrile. In addition, the distance between the layer of the said multilayer structure was 1-5 micrometers, and the thickness of the layer of the said multilayer structure was 3-10 micrometers. Moreover, as a result of elemental analysis of the obtained BC-PAN porous body, the ratio (weight ratio) of polyacrylonitrile / bacterial cellulose was 85/15. The BC-PAN body pore diameter was 2 μm to 5 μm, and the skeleton diameter was 1 μm to 2 μm.

[Example 2]
Production of activated carbon derived from bacterial cellulose and polyacrylonitrile (hereinafter sometimes referred to as “BC-PAN activated carbon”) The porous BC-PAN obtained in Example 1 was used in an oven at 230 ° C. for 5 hours. Heat treated (infusibilized). Thereafter, the porous body was activated at 1000 ° C. for 1 hour in an atmosphere of carbon dioxide and argon (carbon dioxide / argon (volume ratio) = 25/75) to obtain BC-PAN activated carbon. The SEM photograph of the obtained BC-PAN activated carbon is shown in FIGS. 3a and 3b. As shown in FIG. 3c, FIG. 3a is a SEM photograph of BC-PAN activated carbon observed in the vertical direction and FIG. 3b in the horizontal direction. As shown in FIG. 3a, it can be confirmed that BC-PAN activated carbon also has a structure in which a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of polyacrylonitrile are intertwined with each other, like the BC-PAN porous body. It was. In addition, as shown in FIG. 3b, it was confirmed that BC-PAN activated carbon includes a multilayer structure derived from bacterial cellulose and a porous coating derived from polyacrylonitrile on the fiber derived from bacterial cellulose. In addition, the distance between the layer of the said multilayer structure was 1-5 micrometers, and the thickness of the layer of the said multilayer structure was 3-10 micrometers. In addition, by using a sample degassing apparatus, the nitrogen adsorption / desorption isotherm of BC-PAN activated carbon is measured, and the pore diameter distribution is calculated therefrom, whereby BC-PAN activated carbon has micropores having a diameter of 2 nm or less. It was also confirmed that there were many holes. Moreover, as a result of elemental analysis of the obtained BC-PAN activated carbon, nitrogen content was 4.0 mass%.

  <Pore Properties of BC-PAN Porous Material Obtained in Example 1 and BC-PAN Activated Carbon Obtained in Example 2>

[BET specific surface area measurement]
Using a sample degasser, after deaeration for 40 minutes at 60 ° C. under a nitrogen stream, the specific surface area was measured by the BET three-point method. The specific surface area obtained by the BET method is shown in Table 1 below. From this value, it was confirmed that the BC-PAN activated carbon obtained in Example 2 was a porous body having a sufficiently large specific surface area.

<Electrochemical measurement of activated carbon derived from bacterial cellulose and polyacrylonitrile (BC-PAN charcoal)>
The BC-PAN charcoal obtained in Example 2 was pulverized and classified to 45 μm or less using a JIS-Z-8801 JIS standard test sieve. The obtained BC-PAN charcoal powder was added to 1-propanol (Nacalai Tesque, Inc.) solution of 0.8% Nafion (trademark) (De521 CS type, Wako Pure Chemical Industries, Ltd.) so as to be 20 mg / mL By sonicating for 15 minutes, a BC-PAN charcoal dispersion was obtained. This dispersion is applied to a glassy carbon electrode, and the dried one is used as a working electrode, the Pt electrode is used as a counter electrode, the Ag / AgCl electrode is used as a reference electrode, and evaluated by cyclic voltammetry (CV) using a tripolar cell. did. As the electrolytic solution, three kinds of sulfuric acid aqueous solution (1M), sodium sulfate aqueous solution (1M) and potassium hydroxide aqueous solution (1M) were used for comparison. The potential window was set according to the liquidity of the electrolytic solution, and the scanning speed was changed from 200 mV to 1 mV. FIG. 4 is a graph showing the capacity retention ratio of the BC-PAN activated carbon obtained in Example 2 and the PAN activated carbon with respect to the scanning speed using a sulfuric acid aqueous solution (1M). FIG. 5 is a cyclic voltammogram of BC-PAN activated carbon and PAN activated carbon obtained in Example 2.

In addition, PAN activated carbon was manufactured with the following method.
Copolymer containing acrylonitrile (copolymer of acrylonitrile: vinyl acetate = 93: 7, manufactured by Sigma-Aldrich) (0.140 g), water (0.30 g, 0.30 mL) and dimethyl sulfoxide (DMSO) (1.87 g 1.7 mL) (DMSO / H ₂ O (volume ratio) = 85/15) was placed in a sample tube, stirred with heating at 90 ° C. using a hot stirrer, and dissolved at a PAN concentration of 70 mg / mL. After the mixture was heated and stirred for 24 hours, the precipitate was phase-separated from the mixture by allowing it to stand for 1 hour with a bioshaker set to 20 ° C. The solvent contained in the precipitate was replaced with methanol over 24 hours, and then the precipitate was vacuum-dried with a desiccator to obtain a PAN porous material.

  The PAN porous body was heat-treated at 230 ° C. for 6 hours in the air using an oven (infusibilization). Thereafter, activation was performed at 1000 ° C. for 1 hour in an atmosphere of carbon dioxide and argon (carbon dioxide / argon (volume ratio) = 25/75) to obtain PAN activated carbon.

  As shown in FIG. 4, as a result of measuring at different scanning speeds, the capacity was reduced when the scanning speed was increased with PAN activated carbon, whereas the capacity was maintained with BC-PAN activated carbon even at a high scanning speed. Was confirmed. Further, as shown in FIG. 5a, it was confirmed that the shape of the cyclic voltammogram of BC-PAN activated carbon at a high scanning speed was close to an ideal rectangular shape.

  These results are thought to be due to the unique structure of BC-PAN activated carbon. The PAN porous body portion having a large surface area increases the electric double layer area, and further, carbon nanofibers derived from bacterial cellulose entangled with PAN It is considered that good high-speed response was exhibited by contributing to the improvement of the conductive path.

<Resistance measurement by AC impedance method of activated carbon (BC-PAN charcoal) derived from bacterial cellulose and polyacrylonitrile>
Using the BC-PAN charcoal obtained in Example 2, the resistance value by the AC impedance method was measured.
After thoroughly kneading 19 mg of activated carbon powder (classified to 45 μm or less) and 1 mg of PTFE fine particles (AC: PTFE = 95: 5 wt%) using a mortar and pestle, the glass plate and glass rod were stretched to obtain a thickness. The sheet was molded so as to be 100 ± 5 μm. The obtained AC sheet electrode was cut into a disk shape having a diameter of 5 mm, dried at 120 ° C. overnight and used for measurement.
Using a hand press (SSP-10A, SHIMAZU), the AC sheet electrode was pressure-bonded onto a SUS304 current collector mesh (Niraco) having a size of 7 mm × 7 mm at 30 kN to produce a working electrode. In addition to the working electrode, a platinum mesh (Niraco) is used for the counter electrode, a silver / silver chloride (Ag / AgCl) electrode (intercheme) with a Lugin tube is used for the reference electrode, and a 1 mol / L sulfuric acid aqueous solution is used for the electrolyte. Configured. Measurement was performed after the electrode was impregnated with an electrolyte under reduced pressure. The amplitude was measured at 10 mV, and the AC frequency was changed from 0.01 to 10000 Hz. The obtained Nyquist plot (Cole-coll plot) is shown in FIG. 5b. In FIG. 5b, the vertical axis represents imaginary impedance (Z ″), and the horizontal axis represents real impedance (Z ′). Moreover, as activated carbon, the BC-PAN charcoal obtained in Example 2 or the PAN activated carbon was used.

  As shown in FIG. 5b, it was confirmed that BC-PAN charcoal had a lower intergranular resistance than PAN activated carbon.

[Example 3]
Production of porous body containing bacterial cellulose and polymethylmethacrylic acid (PMMA) (hereinafter sometimes referred to as “BC-PMMA porous body”) In a sample basket, the bacterial cellulose hydrogel produced in Production Example 1 was prepared. It was impregnated with ethanol, and the solvent contained in the bacterial cellulose hydrogel was replaced with ethanol. At this time, substitution was performed so that water / ethanol = 20/80 vol%. After solvent substitution, polymethylmethacrylic acid (PMMA) (weight molecular weight 95,000) was added to the impregnated bacterial cellulose to a concentration of 80 mg / mL, and the mixture was stirred with a hot stirrer at 60 ° C. for 5 hours. After stirring, the gel-like material is taken out from the mixture, placed in another sample bowl and left in a bioshaker at 25 ° C. for 2 hours, and then with a large amount of water for one day with the solvent contained in the gel-like material. Replacement was performed. The obtained gel-like material was freeze-dried to remove water, and a BC-PMMA porous material was obtained. The SEM photograph of the obtained BC-PMMA porous body is shown in FIGS. 6a and 6b. As shown in FIGS. 6a and 6b, it was confirmed that the BC-PMMA porous body had a structure in which a three-dimensional network structure of nanofibers of bacterial cellulose and a porous structure of polymethylmethacrylic acid were intertwined. In addition, the distance between the layer of the said multilayer structure was 1-5 micrometers, and the thickness of the layer of the said multilayer structure was 3-10 micrometers.

[Example 4]
Production of porous body containing bacterial cellulose and cellulose acetate (CA) (hereinafter sometimes referred to as “BC-CA porous body”) In a sample bowl, Nata de Coco (manufactured by Tengu Canning Co., Ltd.) is a mixture of DMSO and water. (Water / DMSO = 30/70 vol%) was impregnated, and the solvent contained in Nata de Coco was replaced with DMSO. After solvent substitution, cellulose acetate (CA) (molecular weight 50,000) was added to the impregnated nata de coco to 100 mg / mL, and this mixture was stirred overnight with a hot stirrer at 85 ° C. to dissolve the cellulose acetate. . After stirring, methanol was added to the mixture, and the mixture was further stirred overnight. The gel-like material is taken out from the mixture, placed in another sample bowl, left in a bioshaker at 20 ° C. for 3 hours, and then replaced with a solvent contained in the gel-like material over a day with a large amount of water. It was. The obtained gel-like material was freeze-dried to remove water, and a BC-CA porous material was obtained. The SEM photograph of the obtained BC-CA porous material is shown in FIG. As shown in FIG. 7, it is confirmed that the BC-CA porous body has a structure including a three-dimensional network structure of nanofibers of bacterial cellulose and a porous structure of cellulose acetate deposited around the network structure. did it. The BC-CA body pore diameter was 1.0 μm to 1.5 μm, and the skeleton diameter was 0.2 μm to 0.3 μm. As a result of elemental analysis of the obtained BC-CA porous body, the ratio (weight ratio) of cellulose acetate / bacterial cellulose was 80/20.

[Example 5-1]
Production of porous body containing bacterial cellulose and ethylene vinyl alcohol copolymer (EVOH) (hereinafter sometimes referred to as “BC-EVOH porous body”) Bacterial cellulose hydro produced in Production Example 1 in a sample basket The gel was impregnated with isopropanol, and the solvent contained in the bacterial cellulose hydrogel was replaced with isopropanol. At this time, substitution was performed so that water / isopropanol = 50/50 vol%. After solvent substitution, ethylene vinyl alcohol copolymer (EVOH) (ethylene content 27 mol%) was added to the impregnated bacterial cellulose to a concentration of 100 mg / mL%, and this mixture was stirred with a hot stirrer at 75 ° C. overnight. did. After stirring, the gel-like material is taken out from the mixture, placed in another sample basket, left in a bioshaker at 4 ° C. for 24 hours, and then with a large amount of acetone over one day with the solvent contained in the gel-like material. Replacement was performed. The obtained gel-like material was freeze-dried to remove water, and a BC-EVOH porous material was obtained. An SEM photograph of the obtained BC-EVOH porous material is shown in FIG. As shown in FIG. 8, the BC-EVOH porous body has a structure including a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of an ethylene vinyl alcohol copolymer deposited around the network structure. It was confirmed that it had. Moreover, the pore diameter of the obtained BC-EVOH porous body was 0.2 μm to 0.5 μm, and the skeleton diameter was 0.1 μm to 0.3 μm. Moreover, as a result of elemental analysis of the obtained BC-EVOH porous material, the ratio (weight ratio) of ethylene vinyl alcohol / bacterial cellulose was 94/6.

[Example 5-2]
Production of porous body containing bacterial cellulose and ethylene vinyl alcohol copolymer (EVOH) (hereinafter sometimes referred to as “BC-EVOH porous body”) The ratio of water / isopropanol was 65/35 vol%, and EVOH ( (Ethylene content 27 mol%) A BC-EVOH porous material was obtained in the same manner as in Example 5-1, except that the concentration was 150 mg / mL. The SEM photograph of the obtained BC-EVOH porous body is shown in FIGS. 9a and 9b. FIG. 9a is a SEM photograph of the BC-EVOH porous body observed in the vertical direction, and FIG. 9b is a horizontal direction observed. As shown in FIGS. 9a and 9b, the BC-EVOH porous body has a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of an ethylene vinyl alcohol copolymer deposited around the network structure. It was confirmed to have a structure including. Moreover, the pore diameter of the obtained BC-EVOH porous body was 0.5 μm to 1.0 μm, and the skeleton diameter was 0.2 μm to 0.4 μm. Moreover, as a result of elemental analysis of the obtained BC-EVOH porous material, the ratio (weight ratio) of ethylene vinyl alcohol / bacterial cellulose was 95/5.

[Example 5-3]
Production of porous body containing bacterial cellulose and ethylene vinyl alcohol copolymer (EVOH) (hereinafter sometimes referred to as “BC-EVOH porous body”) The ratio of water / isopropanol is 60/40 vol%, and EVOH ( (Ethylene content 27 mol%) A BC-EVOH porous material was obtained in the same manner as in Example 5-1, except that the concentration was 150 mg / mL. The SEM photograph of the obtained BC-EVOH porous body is shown in FIGS. 10a and 10b. Fig. 10a is a SEM photograph of the BC-EVOH porous body observed in the vertical direction and Fig. 10b is observed in the horizontal direction. As shown in FIGS. 10a and 10b, the BC-EVOH porous body has a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of an ethylene vinyl alcohol copolymer deposited around the network structure. It was confirmed to have a structure including. Moreover, the pore diameter of the obtained BC-EVOH porous body was 0.5 μm to 1.0 μm, and the skeleton diameter was 0.05 μm to 0.2 μm. Moreover, as a result of elemental analysis of the obtained BC-EVOH porous body, the ratio (weight ratio) of ethylene vinyl alcohol / bacterial cellulose was 93/7.

[Example 5-4]
Production of porous body containing bacterial cellulose and ethylene vinyl alcohol copolymer (EVOH) (hereinafter sometimes referred to as “BC-EVOH porous body”) The ratio of water / isopropanol is 45/55 vol%, EVOH concentration BC-EVOH in the same manner as in Example 5-1, except that ethylene vinyl alcohol copolymer (EVOH) (ethylene content 44 mol%) (molecular weight 14,000) was used for bacterial cellulose. A porous body was obtained. An SEM photograph of the obtained BC-EVOH porous material is shown in FIG. As shown in FIG. 11, the BC-EVOH porous body has a structure including a multilayer structure of bacterial cellulose nanofibers and a porous coating of ethylene vinyl alcohol copolymer deposited on the bacterial cellulose nanofibers. It was confirmed that it had. In addition, the distance between the layers of the multilayer structure was 1 μm to 5 μm, and the thickness of the layers of the multilayer structure was 3 μm to 10 μm. Moreover, the pore diameter of the obtained BC-EVOH porous body was 0.2 μm to 0.5 μm, and the skeleton diameter was 0.2 μm to 0.3 μm. Moreover, as a result of elemental analysis of the obtained BC-EVOH porous material, the ratio (weight ratio) of ethylene vinyl alcohol / bacterial cellulose was 94/6.

[Example 5-5]
Production of porous body containing bacterial cellulose and ethylene vinyl alcohol copolymer (EVOH) (hereinafter sometimes referred to as “BC-EVOH porous body”) The ratio of water / isopropanol is 60/40 vol%, and EVOH ( A BC-EVOH porous material was obtained in the same manner as in Example 5-4 except that the ethylene content was 44 mol% and the concentration was 150 mg / mL (44 mol%). An SEM photograph of the obtained BC-EVOH porous material is shown in FIG. As shown in FIG. 12, the BC-EVOH porous body has a structure including a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of an ethylene vinyl alcohol copolymer deposited around the network structure. It was confirmed that it had. Moreover, the pore diameter of the obtained BC-EVOH porous body was 0.2 μm to 1.0 μm, and the skeleton diameter was 0.1 μm to 0.3 μm. Moreover, as a result of elemental analysis of the obtained BC-EVOH porous material, the ratio (weight ratio) of ethylene vinyl alcohol / bacterial cellulose was 95/5.

[Example 5-6]
Production of porous body containing bacterial cellulose and ethylene vinyl alcohol copolymer (EVOH) (hereinafter sometimes referred to as “BC-EVOH porous body”) The ratio of water / isopropanol is 50/50 vol%, and EVOH ( (Ethylene content 27 mol%) A BC-EVOH porous material was obtained in the same manner as in Example 5-1, except that the concentration was 150 mg / mL. The SEM photograph of the obtained BC-EVOH porous body is shown in FIGS. 13a and 13b. FIG. 13a is a SEM photograph of the BC-EVOH porous body observed in the vertical direction, and FIG. 13b a horizontal direction. As shown in FIGS. 13a and 13b, the BC-EVOH porous body has a three-dimensional network structure of bacterial cellulose nanofibers and a porous structure of an ethylene vinyl alcohol copolymer deposited around the network structure. It was confirmed to have a structure including. Moreover, the pore diameter of the obtained BC-EVOH porous body was 0.2 μm to 0.5 μm, and the skeleton diameter was 0.1 μm to 0.3 μm. Moreover, as a result of elemental analysis of the obtained BC-EVOH porous body, the ratio (weight ratio) of ethylene vinyl alcohol / bacterial cellulose was 93/7.

  The porous body containing bacterial cellulose and polymer obtained by the method of the present invention is expected to be used for filters, adsorbents, electrodes and the like.

Claims (13)

A method for producing a porous body containing bacterial cellulose and a polymer,
The method
Adding a first solvent to the bacterial cellulose hydrogel to prepare a first mixture;
Adding the polymer to the first mixture and heating; dissolving the polymer in a mixture of the first solvent and water to prepare a second mixture;
Cooling the second mixture to obtain a precipitated molded body, and immersing the molded body in a second solvent so that the first solvent and water contained in the molded body are Substituting with a solvent to obtain a porous body containing the bacterial cellulose and polymer,
The polymer is a polymer capable of forming a porous body by phase separation,
The manufacturing method in which the first solvent is a solvent miscible with water.   The first solvent is methanol, ethanol, isopropanol, glycerin, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 2-butanone, nitromethane, nitroethane, nitrobenzene, benzo Nitrile, propionitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetone, methyl ethyl ketone, dimethylacetamide (DMAc), N-methylpyrrolidone, 1,4-dioxane, acetonitrile, 1-propanol The production method according to claim 1, wherein the production method is one or more selected from the group.   The production method according to claim 1 or 2, wherein the second solvent is selected from the group consisting of water, a lower alcohol, acetone, and acetonitrile.   In the step of preparing the second mixture, the volume ratio of the first solvent and water (first solvent / water) is 10 to 99.5%. The manufacturing method as described.   The polymer includes polylactic acid, homopolymers of acrylic esters, copolymers containing acrylic esters, homopolymers of methacrylic esters, copolymers containing methacrylic esters, polyacrylonitrile, copolymers containing acrylonitrile, polyvinyl alcohol, The production according to any one of claims 1 to 4, which is at least one selected from the group consisting of ethylene vinyl alcohol copolymer, poly (γ-glutamic acid), chitosan, alginic acid, polyethylene oxide, and cellulose acetate. Method.   The manufacturing method according to claim 1, wherein the concentration of the polymer in the second mixture is 5 to 300 mg / ml. A method for producing activated carbon derived from bacterial cellulose and polymer,
The polymer is polyacrylonitrile or a copolymer containing acrylonitrile,
The manufacturing method including the process of baking the porous body containing the bacterial cellulose and polymer which were obtained by the manufacturing method of Claim 5 or 6.   A porous body comprising bacterial cellulose and a polymer, wherein the polymer is a polymer capable of forming a porous body by phase separation.   The porous body according to claim 8, which has a structure in which a three-dimensional network structure of the bacterial cellulose is intertwined with the porous body of the polymer. Activated carbon derived from bacterial cellulose and polymer,
The polymer is polyacrylonitrile or a copolymer containing acrylonitrile,
A multilayer structure derived from the bacterial cellulose;
A porous structure derived from the polymer,
The distance between the layers of the multilayer structure is in the range of 0.1 μm to 20 μm,
The layer thickness of the multilayer structure is in the range of 0.2 μm to 30 μm,
The activated carbon whose nitrogen content is in the range of 0.1 to 10% by mass. A multilayer structure of the bacterial cellulose;
A porous structure derived from the polymer,
The polymer is a copolymer including one or more selected from the group consisting of polyacrylonitrile, a copolymer including acrylonitrile, a copolymer including methacrylic acid esters, and an ethylene vinyl alcohol copolymer,
The distance between the layers of the multilayer structure is in the range of 0.1 μm to 20 μm,
10. The porous body according to claim 8, wherein a thickness of the multilayer structure layer is in a range of 0.2 μm to 30 μm. A multilayer structure of the bacterial cellulose;
A layer derived from the polymer,
The polymer is an ethylene vinyl alcohol copolymer or a copolymer of cellulose acetate,
The distance between the layers of the multilayer structure is in the range of 0.1 μm to 20 μm,
10. The porous body according to claim 8, wherein a thickness of the multilayer structure layer is in a range of 0.2 μm to 30 μm.   The porous body according to claim 12, wherein the polymer-derived layer is on the bacterial cellulose.