JP2017057269A - Production method of porous body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a novel porous body containing a resin having a polyrotaxane compound and having fine pores.SOLUTION: A production method of a porous body includes a step to stretch a resin which has a structural unit derived from a monomer having a carbon-carbon double bond at an end and a structural unit derived from a polyrotaxane compound. In the production method of a porous body, the polyrotaxane compound is a compound in which a hydrogen atom of a hydroxy group included in polyrotaxane is substituted with a (meth)acryloyl group or with a group including the (meth)acryloyl group; and the polyrotaxane is a resin which has an optionally substituted cyclodextrin, a straight-chain molecule including the optionally substituted cyclodextrin in a skewered state, and sealing groups positioned at both ends of the straight chain molecule to prevent the removal of the optionally substituted cyclodextrin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a porous body including a step of stretching a resin having a structural unit derived from a monomer having a carbon-carbon double bond at a terminal and a structural unit derived from a polyrotaxane compound. .

  Since polyrotaxane is derived from the specificity of its molecular structure and has specific functions and properties, its application in various technical fields has been studied in recent years. For example, Patent Document 1 reports an automotive plastic having a hydrophobic polyrotaxane.

Japanese Patent No. 5176086

Recently, the present inventors have found a production method in which a novel porous body containing a resin having a polyrotaxane compound and having fine pores is obtained, and the present invention has been completed.
Therefore, the subject of this invention is providing the manufacturing method of the novel porous body which contains resin which has a polyrotaxane compound, and has a micropore.

The present invention is a method for producing a porous body comprising a step of stretching a resin having a structural unit derived from a monomer having a carbon-carbon double bond at a terminal and a structural unit derived from a polyrotaxane compound,
In the polyrotaxane compound, a hydrogen atom having a hydroxyl group of 4% or more and 10% or less is substituted with a group containing a (meth) acryloyl group or a (meth) acryloyl group out of several hundred% of the hydrogen atoms of the hydroxyl group contained in the polyrotaxane. The compound being
The polyrotaxane is an optionally substituted cyclodextrin;
A linear molecule clathrating the optionally substituted cyclodextrin in a skewered manner;
Having a blocking group that is disposed at the end of a linear molecule clathrating the optionally substituted cyclodextrin and prevents the elimination of the optionally substituted cyclodextrin,
The present invention provides a method for producing a porous body which is a resin having a weight average molecular weight of 21,000 or more and 500,000 or less of a linear molecule that claws the cyclodextrin which may be substituted in a skewered manner.

  According to the present invention, a novel porous body containing a resin having a polyrotaxane compound and having fine pores can be obtained.

It is a schematic diagram which shows notionally the basic structure of a polyrotaxane. The image which image | photographed the cross section of the porous body obtained in Example 1 with the scanning electron microscope The image which image | photographed the cross section of the porous body obtained in Example 4 with the scanning electron microscope An image obtained by photographing a cross section of the porous body obtained in Comparative Example 3 with a scanning electron microscope

In this specification, “(meth) acrylic acid” refers to methacrylic acid or acrylic acid, and “(meth) acryloyl group” refers to a methacryloyl group or acryloyl group. In the present specification, an “ethylenically unsaturated” compound is a compound having a group represented by —CR═CH ₂ (wherein R represents an optionally substituted hydrocarbyl group), For example, the ethylenically unsaturated carboxylic acid refers to a carboxylic acid having a group represented by the above-mentioned —CR═CH ₂ (wherein R represents a hydrocarbyl group).
In the present specification, the “hydrocarbyl group” refers to a monovalent group obtained by removing one hydrogen atom from a hydrocarbon, and the “hydrocarbylene group” refers to a structure obtained by removing two hydrogen atoms from a hydrocarbon. Refers to a divalent group.

  The method for producing a porous body of the present invention includes a step of stretching a resin having a structural unit derived from a monomer having a carbon-carbon double bond at a terminal and a structural unit derived from a polyrotaxane compound. The polyrotaxane compound is a group in which a hydrogen atom having a hydroxyl group of 4% to 10% contains a (meth) acryloyl group or a (meth) acryloyl group out of several hundred% of the hydrogen atoms of the hydroxyl group contained in the polyrotaxane. A substituted compound, wherein the polyrotaxane may be substituted with a cyclodextrin, a linear molecule that includes the optionally substituted cyclodextrin in a skewered manner, and the substituted Cyclodextrin, which is arranged at the end of a linear molecule clathrating cyclodextrin in a skewered manner and may be substituted And a blocking groups to prevent detachment of the emissions, the weight average molecular weight of the packaging contacting the linear molecule may cyclodextrin also the substituted skewered shape is of 21000 to 500,000.

  Examples of the monomer having a carbon-carbon double bond at the terminal in the present invention include, for example, (meth) acrylic acid ester, aromatic vinyl compound, vinyl cyanide compound, ethylenically unsaturated carboxylic acid hydroxyalkyl ester, and ethylenic acid. Unsaturated sulfonic acid ester, ethylenically unsaturated carboxylic acid amide, ethylenically unsaturated carboxylic acid, ethylenically unsaturated sulfonic acid, ethylenically unsaturated alcohol or ester thereof, ethylenically unsaturated ether compound, ethylenically unsaturated amine compound , Ethylenically unsaturated silane compounds, vinyl halides, aliphatic conjugated diene compounds, and the like. Monomers having a carbon-carbon double bond at the end may be used alone or in combination of two or more.

As said (meth) acrylic acid ester, acrylic acid ester or methacrylic acid ester is mentioned, These may be used independently and may use 2 or more types together.
The acrylic ester is at least one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. Those having a group are preferred, and examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, lauryl acrylate, benzyl acrylate, and cyclohexyl acrylate. The said acrylic ester may be used independently and may use 2 or more types together.
The methacrylic acid ester is at least one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. Those having a group are preferred, and examples thereof include methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate, cyclohexyl methacrylate and the like. The said methacrylic acid ester may be used independently and may use 2 or more types together.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, α-chloroslene, p-chloroslene, p-methoxystyrene, Examples include p-aminostyrene, p-acetoxystyrene, sodium styrenesulfonate, α-vinylnaphthalene, sodium 1-vinylnaphthalene-4-sulfonate, 2-vinylfluorene, 2-vinylpyridine, 4-vinylpyridine. The said aromatic vinyl compound may be used independently and may use 2 or more types together.

  Examples of the vinyl cyanide compound include acrylonitrile, α-chloroacrylonitrile, α-methoxyacrylonitrile, methacrylonitrile, α-chloromethacrylonitrile, α-methoxymethacrylonitrile, vinylidene cyanide, and the like. The said vinyl cyanide compound may be used independently and may use 2 or more types together.

  Examples of the ethylenically unsaturated carboxylic acid hydroxyalkyl ester include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate. The ethylenically unsaturated carboxylic acid hydroxyalkyl ester may be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated sulfonic acid ester include alkyl vinyl sulfonate and alkyl isoprene sulfonate. The said ethylenically unsaturated sulfonic acid ester may be used independently and may use 2 or more types together.

  Examples of the ethylenically unsaturated carboxylic acid amide include acrylamide, methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, N-butoxyethyl acrylamide, N-butoxyethyl methacrylamide, N-methoxymethyl acrylamide, N-methoxymethylmethacrylamide, Nn-propoxymethylacrylamide, Nn-propoxymethylmethacrylamide, N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylate Examples thereof include amide, N, N-diethylacrylamide, N, N-diethylmethacrylamide and the like. The said ethylenically unsaturated carboxylic acid amide may be used independently and may use 2 or more types together.

  Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, and the like. The said ethylenically unsaturated carboxylic acid may be used independently and may use 2 or more types together.

  Examples of the ethylenically unsaturated sulfonic acid include vinyl sulfonic acid and isoprene sulfonic acid. The said ethylenically unsaturated sulfonic acid may be used independently and may use 2 or more types together.

  Examples of the ethylenically unsaturated alcohol or ester thereof include allyl alcohol, methallyl alcohol, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, allyl acetate, methallyl caproate, allyl laurate, Examples include allyl benzoate, vinyl alkyl sulfonate, allyl alkyl sulfonate, vinyl aryl sulfonate, and esters thereof. The said ethylenically unsaturated alcohol or its ester may be used independently, and may use 2 or more types together.

  Examples of the ethylenically unsaturated ether compound include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, methyl allyl ether, and ethyl allyl ether. The said ethylenically unsaturated ether compound may be used independently and may use 2 or more types together.

  Examples of the ethylenically unsaturated amine compound include vinyldimethylamine, vinyldiethylamine, vinyldiphenylamine, allyldimethylamine, and methallyldiethylamine. The said ethylenically unsaturated amine compound may be used independently and may use 2 or more types together.

  Examples of the ethylenically unsaturated silane compound include vinyltriethylsilane, methylvinyldichlorosilane, dimethylallylchlorosilane, vinyltrichlorosilane, and the like. The said ethylenically unsaturated silane compound may be used independently and may use 2 or more types together.

  Examples of the vinyl halide include vinyl chloride, vinylidene chloride, 1,2-dichloroethylene, vinyl bromide, vinylidene bromide, 1,2-dibromoethylene, and the like. The said vinyl halide may be used independently and may use 2 or more types together.

  Examples of the aliphatic conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,2-dichloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 2-bromo-1,3-butadiene, 2-cyano-1, 3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,3-dimethyl-1,3- Pentadiene, 2,4-dimethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 3-methyl-1,3-hexadiene, 4-methyl-1,3-hexa Ene, 5-methyl-1,3-hexadiene, 2,3-dimethyl-1,3-hexadiene, 2,4-dimethyl-1,3-hexadiene, 2,5-dimethyl-1,3-hexadiene, 3, 4-dimethyl-1,3-hexadiene, 3,5-dimethyl-1,3-hexadiene and the like can be mentioned. The said aliphatic conjugated diene type compound may be used independently and may use 2 or more types together.

  As a monomer having a carbon-carbon double bond at the terminal, (meth) acrylic acid ester is preferable.

The polyrotaxane compound in the present invention refers to a hydrogen atom having a hydroxyl group of 4% to 10% containing a (meth) acryloyl group or a (meth) acryloyl group among several hundred% of the hydrogen atoms contained in the polyrotaxane. It is a compound substituted with a group.
The polyrotaxane includes a cyclodextrin which may be substituted, a linear molecule which claws the cyclodextrin which may be substituted in a skewered manner, and a cyclodextrin which may be substituted in a skewered manner. A linear chain that is disposed at the end of a linear molecule and has a blocking group that prevents the elimination of the optionally substituted cyclodextrin, and includes the optionally substituted cyclodextrin molecule in a skewered manner. It is a compound having a weight average molecular weight of 21,000 or more and 500,000 or less.
FIG. 1 is a schematic diagram conceptually showing the basic structure of the polyrotaxane. In FIG. 1, the polyrotaxane 1 has a linear molecule 3, a plurality of optionally substituted cyclodextrins 2, and blocking groups 4 arranged at both ends of the linear molecule 3. The chain molecule 3 penetrates through the opening of the cyclodextrin 2 which may be substituted, and includes the cyclodextrin 2 which may be substituted. The state of the cyclodextrin 2 and the linear molecule 3 which may be substituted in FIG. 1 is defined as “enclosed in a skewered manner” in the present specification.

  The cyclodextrin which may be substituted is cyclodextrin or substituted cyclodextrin. The polyrotaxane may contain both cyclodextrin and substituted cyclodextrin. Further, the polyrotaxane may be one in which optionally substituted cyclodextrins are cross-linked.

  Examples of the cyclodextrin include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, dimethylcyclodextrin, glucosylcyclodextrin, and derivatives or modified products thereof. The polyrotaxane may contain a plurality of the cyclodextrins and may contain two or more types of the cyclodextrins.

The substituted cyclodextrin is a compound in which at least one hydrogen atom of a hydroxyl group contained in the cyclodextrin is substituted with a substituent. The polyrotaxane may contain a plurality of the substituted cyclodextrins, and may contain two or more types of the substituted cyclodextrins.
Examples of the substituent include a group containing a hydroxyl group, and examples include a group represented by the following formula (I) and a group containing a group represented by the following formula (I). Since the reactivity with the cyclodextrin is good, the substituent is preferably a group containing a group represented by the following formula (I), such as a group represented by the following formula (II). . In the following formula (I) and the following formula (II), “*” represents a bonding site with another atom, and in the following formula (II), “*” represents a hydroxyl-derived oxygen contained in the cyclodextrin. Represents the bonding site with an atom.

（前記式（Ｉ）中、Ｒ^１およびＲ^３は、それぞれ水素原子または置換されていてもよいヒドロカルビル基を表し、ａは1以上の整数であり、ｂは１以上の整数である。ａまたはｂが２以上である場合、複数あるＲ^１は同じであっても異なっていてもよく、複数あるＲ^３は同じであっても異なっていてもよい。Ｒ^１およびＲ^３は、同じであっても異なっていてもよい。）

（前記式（ＩＩ）中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ水素原子または置換されていてもよいヒドロカルビル基を表し、ａは1以上の整数であり、ｂは１以上の整数であり、ｃは１以上の整数である。複数あるＲ^２は同じであっても異なっていてもよく、ａまたはｂが２以上である場合、複数あるＲ^１は同じであっても異なっていてもよく、複数あるＲ^３は同じであっても異なっていてもよい。Ｒ^１、Ｒ^２およびＲ^３は、同じであっても異なっていてもよい。）

(In the formula (I), R ¹ and R ³ each represent a hydrogen atom or an optionally substituted hydrocarbyl group, a is an integer of 1 or more, and b is an integer of 1 or more. When b is 2 or more, a plurality of R ¹ may be the same or different, and a plurality of R ³ may be the same or different, and R ¹ and R ³ are the same. Or different.)

(In the formula (II), R ¹ , R ² and R ³ each represent a hydrogen atom or an optionally substituted hydrocarbyl group, a is an integer of 1 or more, and b is an integer of 1 or more. , C is an integer greater than or equal to 1. A plurality of R ² may be the same or different, and when a or b is 2 or more, a plurality of R ¹ may be the same or different. And the plurality of R ³ may be the same or different, and R ¹ , R ² and R ³ may be the same or different.)

The optionally substituted hydrocarbyl group in R ¹ , R ² and R ³ may be linear, branched or cyclic.
The optionally substituted hydrocarbyl group in R ¹ , R ² and R ³ is a hydrocarbyl group or a substituted hydrocarbyl group.

Examples of the hydrocarbyl group in R ¹ , R ² and R ³ include methyl group, ethyl group, n-propyl group, cyclopropyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, Alkyl group such as cyclobutyl group; phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 3,4-dimethylphenyl group, 2,3,4- Aryl groups such as trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, ethylphenyl group, isopropylphenyl group, tert-butylphenyl group, naphthyl group, anthracenyl group 1-methyl-1-phenylethyl group, benzyl group, (2-methylphenyl) methyl group, (2,4-di- Aralkyl such as (tilphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (ethylphenyl) methyl group, naphthylmethyl group, etc. Groups and the like.

As the substituted hydrocarbyl group in R ¹ , R ² and R ³ , at least one hydrogen atom contained in the hydrocarbyl group is substituted with a halogen atom such as a chlorine atom or a bromine atom, a hydrocarbyl group, a hydrocarbyloxy group, or the like Is mentioned.
Examples of the hydrocarbyl group include methyl groups, ethyl groups, n-propyl groups, cyclopropyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, and cyclobutyl groups; phenyl groups; Group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 3,4-dimethylphenyl group, 2,3,4-trimethylphenyl group, 3,4, Aryl groups such as 5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, ethylphenyl group, isopropylphenyl group, tert-butylphenyl group, naphthyl group, anthracenyl group; 1-methyl-1-phenyl Ethyl group, benzyl group, (2-methylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2 , 3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (ethylphenyl) methyl group, naphthylmethyl group, and the like.
Examples of the hydrocarbyloxy group include alkyloxy groups such as methoxy group, ethoxy group, isopropoxy group, sec-butoxy group, and tert-butoxy group; phenoxy group, 2-methylphenoxy group, 2,5-dimethylphenoxy group, 2 , 3,6-trimethylphenoxy group, ethylphenoxy group, naphthoxy group and other aryloxy groups; benzyloxy group, (2-methylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (2,4,4) And aralkyloxy groups such as 5-trimethylphenyl) methoxy group, (ethylphenyl) methoxy group, and naphthylmethoxy group.

  a is an integer of 1 or more, preferably 1 or more and 9 or less, more preferably 2 or more and 8 or less, and further preferably 3 or more and 6 or less.

  b is an integer of 1 or more, preferably 1 or more and 12 or less, more preferably 3 or more and 10 or less, and further preferably 5 or more and 9 or less.

  c is an integer of 1 or more, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and further preferably 1 or 2.

  The substituted cyclodextrin may be substituted with a group other than the substituent, and examples thereof include an acyl group, a hydrocarbyl group, a hydroxyalkyl group, an alkylcarbamoyl group, an alkoxysilyl group, and derivatives thereof.

  The linear molecule only needs to be able to be included in a skewered manner in the opening of the optionally substituted cyclodextrin, for example, polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulose series Resin (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, etc. and / or these Copolymers, polyethylene resins, polypropylene, and polyolefin resins such as copolymers with other olefinic monomers, polyester resins, polyvinyl chloride Fat, polystyrene resins such as polystyrene and acrylonitrile-styrene copolymer, (meth) acrylic resins such as polymethyl methacrylate, (meth) acrylic acid ester copolymer, acrylonitrile-methyl acrylate copolymer, polycarbonate resin, polyurethane Resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral resin and derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimide , Polydienes such as polyisoprene and polybutadiene, polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides , Polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof, preferably polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, or polypropylene, more preferably polyethylene glycol. It is.

Moreover, the weight average molecular weight of the linear molecule is 21,000 to 500,000, preferably 25,000 to 100,000.
A novel porous body having fine pores can be obtained by stretching a resin containing a polyrotaxane compound having a linear molecule having a weight average molecular weight within the above range.
The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC), using a linear molecule with a known molecular weight as a standard reagent, and creating a calibration curve from the elution time and molecular weight. . The linear molecule is used after being dissolved in a solvent, and an RI detector is used as a detector.

  The blocking group is not particularly limited as long as it is arranged at the end of the linear molecule and can prevent the elimination of the optionally substituted cyclodextrin. For example, dinitrophenyl groups (2, 4 -Dinitrophenyl group, 3,5-dinitrophenyl group, etc.), dialkylphenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, substituted benzenes (alkylbenzene, alkyloxybenzene, phenol, Halobenzene, cyanobenzene, benzoic acid, aminobenzene, etc.), optionally substituted polynuclear aromatics, steroids, and derivatives or modified forms thereof, preferably dinitrophenyl groups, cyclodextrins, Adamantane group, trityl group, fluorescein Or a pyrenes, more preferably adamantane groups such.

  When the cyclodextrin which may be substituted is included in a skewered manner by the linear molecule, when the amount of inclusion of the cyclodextrin which may be substituted is maximally 1, The linear molecule may be substituted in an amount of 0.001 to 0.6, preferably 0.01 to 0.5, more preferably 0.05 to 0.4. It should be included in a skewered shape.

  The production method of the polyrotaxane is disclosed in, for example, Japanese Patent No. 3475252 and International Publication No. 2009/136618. Among the polyrotaxanes, as a method for producing a polyrotaxane having a substituted cyclodextrin, specifically, using a lactone represented by the following formula (III), the reaction conditions disclosed in International Publication No. 2009/136618 are disclosed. The manufacturing method is mentioned, You may use the oxacycloalkane shown by following formula (IV) as needed. When a lactone represented by the following formula (III) and an oxacycloalkane represented by the following formula (IV) are used, a polyrotaxane having a cyclodextrin is reacted with an oxacycloalkane represented by the following formula (IV). The obtained product is preferably reacted with a lactone represented by the following formula (III) to produce a polyrotaxane having a substituted cyclodextrin.

（前記式（ＩＩＩ）中、Ｒ^１、Ｒ^３およびａは、それぞれ、前記式（Ｉ）および（ＩＩ）におけるＲ^１、Ｒ^３およびａと同義である。）

(Wherein ^(III), R 1, ^{R 3} and a are respectively the same meanings as ^R 1, ^{R 3} and a in the formula (I) and (II).)

（前記式（ＩＶ）中、Ｒ^２およびｃは、それぞれ、前記式（Ｉ）および（ＩＩ）におけるＲ^２およびｃと同義である。）

(Wherein (IV), ^{R 2} and c, respectively, the same meanings as ^{R 2,} and c in the formula (I) and (II).)

  Examples of the group containing the (meth) acryloyl group include a group represented by the following formula (V), a group represented by the following formula (VI), a group represented by the following formula (VII), and the following formula (VIII). And the group shown. In the following formula (V), the following formula (VI), the following formula (VII), and the following formula (VIII), “*” represents a binding site with a hydroxyl group-derived oxygen atom contained in the polyrotaxane.

（前記式（Ｖ）中、Ｒ^５、Ｒ^６、およびＲ^７は水素原子または置換されていてもよいヒドロカルビレン基を表し、Ｒ^４は水素原子またはメチル基を表し、Ａは、酸素原子、−ＮＨ−、−ＮＲ’−（Ｒ’は置換されていてもよいヒドロカルビレン基を表し、その例示は、Ｒ^５、Ｒ^６、およびＲ^７の置換されていてもよいヒドロカルビレン基と同様である。）、−ＣＯ−、−ＣＯＯ−、−ＮＨＣＯ−、または−ＮＨＣＳ−を表す。ｄは1以上の整数であり、ｅは１以上３以下の整数であり、ｆは１以上の整数であり、ｇは０以上の整数であり、ｈは０以上の整数であり、ｉは０以上の整数である。ｄが２以上またはｆが２以上である場合、複数あるＲ^５は同じであっても異なっていてもよく、ｈが２以上またはｆが２以上である場合、複数あるＲ^６は同じであっても異なっていてもよく、ｅが２以上である場合、複数あるＲ^４は同じであっても異なっていてもよく、ｉが２以上またはｅが２以上ある場合、複数あるＲ^７は同じであっても異なっていてもよく、ｇが２以上またはｆが２以上である場合、複数あるＡは同じであっても異なっていてもよい。Ｒ^５、Ｒ^６、およびＲ^７は、同じであっても異なっていてもよい。）

(In the formula (V), R ⁵ , R ⁶ , and R ⁷ represent a hydrogen atom or an optionally substituted hydrocarbylene group, R ⁴ represents a hydrogen atom or a methyl group, and A represents an oxygen atom. , —NH—, —NR ′ — (R ′ represents an optionally substituted hydrocarbylene group, and examples thereof are R ⁵ , R ⁶ , and R ⁷ optionally substituted hydrocarbylene groups. And -CO-, -COO-, -NHCO-, or -NHCS-, d is an integer of 1 or more, e is an integer of 1 to 3, and f is 1 or more. G is an integer greater than or equal to 0, h is an integer greater than or equal to 0, and i is an integer greater than or equal to 0. When d is 2 or more or f is 2 or more, a plurality of R ⁵ are They may be the same or different, and when h is 2 or more or f is 2 or more, R ⁶ may be different even in the same, when e is 2 or more, a plurality of R ⁴ may be different even in the same, if i is 2 or more, or e is 2 or more, A plurality of R ⁷ may be the same or different, and when g is 2 or more or f is 2 or more, a plurality of Rs may be the same or different R ⁵ , R ⁶ , And R ⁷ may be the same or different.)

（前記式（ＶＩ）中、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ａ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉは、前記式（Ｖ）におけるＲ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ａ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉと同義であり、Ｄは酸素原子または硫黄原子を表す。）

(In the formula (VI), R ⁴ , R ⁵ , R ⁶ , R ⁷ , A, d, e, f, g, h, and i are R ⁴ , R ⁵ , R ⁶ , R ⁷ is synonymous with A, d, e, f, g, h and i, and D represents an oxygen atom or a sulfur atom.)

（前記式（ＶＩＩ）中、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ａ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉは、前記式（Ｖ）におけるＲ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ａ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉと同義である。）

(In the formula (VII), R ⁴ , R ⁵ , R ⁶ , R ⁷ , A, d, e, f, g, h and i are the same as R ⁴ , R ⁵ , R ⁶ , R ⁷ is synonymous with A, d, e, f, g, h and i.)

（前記式（ＶＩＩＩ）中、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ａ、ｄ、ｅ、ｆ、ｇ、ｈ、およびｉは、前記式（Ｖ）におけるＲ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ａ、ｄ、ｅ、ｆ、ｇ、ｈ、およびｉと同義であり、Ｄは酸素原子または硫黄原子を表す。）

(In said formula (VIII), R < ⁴ >, R < ⁵ >, R < ⁶ >, R < ⁷ >, A, d, e, f, g, h, and i are R < ⁴ >, R < ⁵ >, R < ⁶ > in said formula (V). , R ⁷ , A, d, e, f, g, h, and i, and D represents an oxygen atom or a sulfur atom.)

The optionally substituted hydrocarbylene group in R ⁵ , R ⁶ , and R ⁷ may be any of linear, branched, or cyclic.
The optionally substituted hydrocarbylene group in R ⁵ , R ⁶ , and R ⁷ is a hydrocarbylene group or a substituted hydrocarbylene group.
Examples of the hydrocarbylene group in R ⁵ , R ⁶ , and R ⁷ include methylene group, ethylene group, n-propylene group, cyclopropylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, tert -Alkylene group such as butylene group and cyclobutylene group; phenylene group, 2-methylphenylene group, 3-methylphenylene group, 4-methylphenylene group, 2,3-dimethylphenylene group, 3,4-dimethylphenylene group, 2 , 3,4-trimethylphenylene group, 3,4,5-trimethylphenylene group, 2,3,4,5-tetramethylphenylene group, ethylphenylene group, isopropylphenylene group, tert-butylphenylene group, naphthylene group, anthracenylene Arylene groups such as 1-methyl-1-phenylethylene , Benzylene group, (2-methylphenyl) methylene group, (2,4-dimethylphenyl) methylene group, (2,3,4,5-tetramethylphenyl) methylene group, (2,3,4,6-tetra And aralkylene groups such as a methylphenyl) methylene group, an (ethylphenyl) methylene group, and a naphthylmethylene group.
As the substituted hydrocarbylene group in R ⁵ , R ⁶ and R ^7, at least one hydrogen atom contained in the hydrocarbylene group is a halogen atom such as a chlorine atom or a bromine atom, a hydrocarbyl group, a hydrocarbyloxy group, etc. And those substituted with.
Examples of the hydrocarbyl group include methyl groups, ethyl groups, n-propyl groups, cyclopropyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, and cyclobutyl groups; phenyl groups; Group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 3,4-dimethylphenyl group, 2,3,4-trimethylphenyl group, 3,4, Aryl groups such as 5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, ethylphenyl group, isopropylphenyl group, tert-butylphenyl group, naphthyl group, anthracenyl group; 1-methyl-1-phenyl Ethyl group, benzyl group, (2-methylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2 , 3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (ethylphenyl) methyl group, naphthylmethyl group, and the like.
Examples of the hydrocarbyloxy group include alkyloxy groups such as methoxy group, ethoxy group, isopropoxy group, sec-butoxy group, and tert-butoxy group; phenoxy group, 2-methylphenoxy group, 2,5-dimethylphenoxy group, 2 , 3,6-trimethylphenoxy group, ethylphenoxy group, naphthoxy group and other aryloxy groups; benzyloxy group, (2-methylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (2,4,4) And aralkyloxy groups such as 5-trimethylphenyl) methoxy group, (ethylphenyl) methoxy group, and naphthylmethoxy group.

The optionally substituted hydrocarbylene group in R ⁵ , R ⁶ and R ⁷ is preferably a hydrocarbylene group, more preferably an alkylene group.

  d is an integer greater than or equal to 1, Preferably it is 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less, More preferably, it is 1 or 2.

  f is an integer of 1 or more, preferably 1 or more, 4 more preferably 1 or more and 3 or less, and further preferably 1 or 2.

  g is an integer of 0 or more, preferably 0 or more and 4 or less, more preferably 0 or more and 2 or less, and still more preferably 0 or 1.

  h is an integer of 0 or more, preferably 0 or more and 8 or less, more preferably 0 or more and 4 or less, and even more preferably 0 or 2.

  i is an integer of 0 or more, preferably 0 or more and 8 or less, more preferably 0 or more and 4 or less, and still more preferably 0 or more and 2 or less.

  A is preferably —NHCO—, and D is preferably an oxygen atom.

  The group containing a (meth) acryloyl group or a (meth) acryloyl group is preferably a group containing a (meth) acryloyl group, and more preferably a group represented by the above formula (VI).

In the polyrotaxane compound, a hydrogen atom having a hydroxyl group of 4% or more and 10% or less is substituted with a group containing a (meth) acryloyl group or a (meth) acryloyl group out of several hundred% of the hydrogen atoms contained in the polyrotaxane. Has been. The number of hydrogen atoms contained in the hydroxyl group contained in the polyrotaxane (that is, the hydroxyl value) can be measured based on JIS K 0070.
By stretching a resin containing a polyrotaxane compound in which the ratio of the hydrogen atom of the hydroxyl group contained in the polyrotaxane is replaced with a (meth) acryloyl group or a group containing a (meth) acryloyl group is in the above range, A novel porous body having pores can be obtained.

As a method for producing the polyrotaxane compound, for example,
(I) a method of reacting the polyrotaxane with a chloride containing a (meth) acryloyl group in the presence of a basic compound;
(Ii) a method of reacting the polyrotaxane with an isocyanate compound containing a (meth) acryloyl group or an isothiocyanate compound containing a (meth) acryloyl group in the presence of a catalyst;
(Iii) In the presence of a catalyst, the polyrotaxane is reacted with a compound having two or more isocyanate groups or a compound having two or more isothiocyanate groups, and the resulting product, hydroxyalkyl (meth) acrylate, And the like, and the method (ii) is preferred.
The number of the (meth) acryloyl group or the group containing the (meth) acryloyl group contained in the polyrotaxane compound can be adjusted by the amount of the raw material containing the (meth) acryloyl group.

  Examples of the basic compound used in (i) include triethylamine, pyridine, N, N-dimethyl-4-aminopyridine, and the like. Examples of the catalyst used in (ii) and (iii) include dibutyltin dilaurate, tin octylate, bismuth octylate, zinc octylate, lead octylate, bismuth decanoate, triethylamine, triethylenediamine, N, N , N ′, N′-tetramethylethylenediamine and the like.

  Examples of the chloride containing the (meth) acryloyl group include acryloyl chloride, 2-chloroethyl acrylate, and methacryloyl chloride. These may be used alone or in combination of two or more.

  Examples of the isocyanate compound containing a (meth) acryloyl group include 2-methacryloyloxyethyl isocyanate, 3-methacryloyloxy-n-propyl isocyanate, 2-methacryloyloxyisopropyl isocyanate, 4-methacryloyloxy-n-butyl isocyanate, 2 -Methacryloyloxy-tert-butyl isocyanate, 2-methacryloyloxybutyl-4-isocyanate, 2-methacryloyloxybutyl-3-isocyanate, 2-methacryloyloxybutyl-2-isocyanate, 2-methacryloyloxybutyl-1-isocyanate, 5 -Methacryloyloxy-n-pentyl isocyanate, 6-methacryloyloxy-n-hexyl isocyanate, 7-methacryloyl Xy-n-heptyl isocyanate, 2- (isocyanatoethyloxy) ethyl methacrylate, 3-methacryloyloxyphenyl isocyanate, 4-methacryloyloxyphenyl isocyanate, 2-acryloyloxyethyl isocyanate, 3-acryloyloxy-n-propyl isocyanate, 2 -Acryloyloxyisopropyl isocyanate, 4-acryloyloxy-n-butyl isocyanate, 2-acryloyloxy-tert-butyl isocyanate, 2-acryloyloxybutyl-4-isocyanate, 2-acryloyloxybutyl-3-isocyanate, 2-acryloyloxy Butyl-2-isocyanate, 2-acryloyloxybutyl-1-isocyanate, 5-acryloyloxy-n- Nthyl isocyanate, 6-acryloyloxy-n-hexyl isocyanate, 7-acryloyloxy-n-heptyl isocyanate, 2- (isocyanatoethyloxy) ethyl acrylate, 3-acryloyloxyphenyl isocyanate, 4-acryloyloxyphenyl isocyanate, 1 , 1-bis (methacryloyloxymethyl) methyl isocyanate, 1,1-bis (methacryloyloxymethyl) ethyl isocyanate, 1,1-bis (acryloyloxymethyl) methyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate Examples include 2'-pentenoyl-4-oxyphenyl isocyanate and compounds in which hydrogen atoms contained in these compounds are substituted with halogen atoms. . These may be used alone or in combination of two or more.

  Examples of the isothiocyanate compound containing the (meth) acryloyl group include 2-methacryloyloxyethyl isothiocyanate, 3-methacryloyloxy-n-propyl isothiocyanate, 2-methacryloyloxyisopropyl isothiocyanate, 4-methacryloyloxy-n- Butyl isothiocyanate, 2-methacryloyloxy-tert-butyl isothiocyanate, 2-methacryloyloxybutyl-4-isothiocyanate, 2-methacryloyloxybutyl-3-isothiocyanate, 2-methacryloyloxybutyl-2-isothiocyanate, 2- Methacryloyloxybutyl-1-isothiocyanate, 5-methacryloyloxy-n-pentylisothiocyanate, 6-methacryloyloxy-n Hexyl isothiocyanate, 7-methacryloyloxy-n-heptyl isothiocyanate, 2- (isocyanatoethyloxy) ethyl methacrylate, 3-methacryloyloxyphenyl isothiocyanate, 4-methacryloyloxyphenyl isothiocyanate, 2-acryloyloxyethyl isothiocyanate, 3-acryloyloxy-n-propyl isothiocyanate, 2-acryloyloxyisopropyl isothiocyanate, 4-acryloyloxy-n-butyl isothiocyanate, 2-acryloyloxy-tert-butyl isothiocyanate, 2-acryloyloxybutyl-4-iso Thiocyanate, 2-acryloyloxybutyl-3-isothiocyanate, 2-acryloyloxybutyl-2-isothiocyanate Cyanate, 2-acryloyloxybutyl-1-isothiocyanate, 5-acryloyloxy-n-pentyl isothiocyanate, 6-acryloyloxy-n-hexyl isothiocyanate, 7-acryloyloxy-n-heptyl isothiocyanate, 2- (isocyanate) Natoethyloxy) ethyl acrylate, 3-acryloyloxyphenyl isothiocyanate, 4-acryloyloxyphenyl isothiocyanate, 1,1-bis (methacryloyloxymethyl) methyl isothiocyanate, 1,1-bis (methacryloyloxymethyl) ethyl isothiocyanate 1,1-bis (acryloyloxymethyl) methyl isothiocyanate, 1,1-bis (acryloyloxymethyl) ethyl isothiocyanate, 2′-pente Examples include noyl-4-oxyphenyl isothiocyanate and compounds in which a hydrogen atom contained in these compounds is substituted with a halogen atom. These may be used alone or in combination of two or more.

  Examples of the compound having two or more isocyanate groups include aliphatic isocyanate, alicyclic isocyanate, araliphatic isocyanate, and aromatic isocyanate. These may be used alone or in combination of two or more.

  Examples of the aliphatic isocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3- Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, methyl 2,6-diisocyanatohexanoate (common name: lysine diisocyanate); 6-diisocyanatohexanoic acid 2-isocyanatoethyl, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11 Triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. And aliphatic triisocyanate. These may be used alone or in combination of two or more.

  Examples of the alicyclic isocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name: Isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) ) Cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, alicyclic diisocyanate such as methylenebis (4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI), norbornane diisocyanate 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2) .1) Heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5- Di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) ) Heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanato Til) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3 -Isocyanatopropyl) -bicyclo (2.2.1) heptane and other alicyclic triisocyanates. These may be used alone or in combination of two or more.

  Examples of the araliphatic isocyanate include methylenebis (4,1-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω′-diisocyanato-1. Araliphatic diisocyanates such as 1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof; Examples thereof include araliphatic triisocyanates such as 5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

Examples of the aromatic isocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate (common name: 2,4-TDI). ) Or 2,6-tolylene diisocyanate (common name: 2,6-TDI) or a mixture thereof, aromatic diisocyanate such as 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate; triphenylmethane-4, Aromatic triisocyanates such as 4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene; 4,4′-diphenylmethane-2,2 ′, Aromatic Tetrie such as 5,5'-tetraisocyanate Or the like can be mentioned cyanate. These may be used alone or in combination of two or more.
Examples of the compound having two or more isothiocyanate groups include monomethylene diisothiocyanate, dimethylene diisothiocyanate, trimethylene diisothiocyanate, tetramethylene diisothiocyanate, pentamethylene diisothiocyanate. And hexamethylene diisothiocyanate, toluene diisothiocyanate, xylene diisothiocyanate, tolylene dithiocyanate, 1,3-bis (isothiocyanatomethyl) cyclohexane, and the like. These may be used alone or in combination of two or more. Moreover, you may use together with the compound which has the said 2 or more isocyanate group.

  Examples of the hydroxyalkyl (meth) acrylate include hydroxymethyl methacrylate, hydroxyethyl methacrylate, and hydroxymethyl acrylate. These may be used alone or in combination of two or more.

Examples of the method for producing the resin include a monomer having a carbon-carbon double bond at the terminal and a monomer derived from the polyrotaxane compound, such as an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, Examples of the polymerization method include a liquid polymerization method (cast polymerization method), and a liquid injection polymerization method (cast polymerization method) is preferable.
By the above method, the carbon-carbon double bond derived from the (meth) acryloyl group contained in the polyrotaxane compound, and the carbon-carbon double bond derived from the monomer having the carbon-carbon double bond at the terminal. React with each other to obtain the resin.

The polymerization is performed using light irradiation or a polymerization initiator. Examples of the polymerization initiator include azo initiators (eg, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile)), peroxide initiators. (Lauroyl peroxide, benzoyl peroxide, etc.), redox initiators in which organic peroxides and amines are combined, and the like.
When the polymerization initiator is added at the time of polymerization, the addition amount of the polymerization initiator is 100 parts by mass with respect to a total amount of the monomer having a carbon-carbon double bond at the terminal and the polyrotaxane compound added at the time of polymerization. Preferably, it is 0.01 part by mass or more and 1 part by mass or less, and more preferably 0.01 part by mass or more and 0.5 part by mass or less.

The content of the structural unit derived from the polyrotaxane compound in the resin is 100 parts by mass of the total amount of the structural unit derived from the monomer having a carbon-carbon double bond at the terminal and the structural unit derived from the polyrotaxane compound. 5 parts by mass or more, preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less.
The content of the structural unit derived from the monomer having a carbon-carbon double bond at the terminal in the resin is derived from the structural unit derived from the monomer having a carbon-carbon double bond at the terminal and the polyrotaxane compound. 95 mass parts or less are preferable with respect to 100 mass parts of total amounts with a structural unit, 50 mass parts or more and 95 mass parts or less are more preferable, and 50 mass parts or more and 90 mass parts or less are more preferable.
By stretching the resin in which the content of the structural unit derived from the monomer having a carbon-carbon double bond at the terminal in the resin and the content of the structural unit derived from the polyrotaxane compound are in the above range, A novel porous body having fine pores can be obtained. In addition, the content of the structural unit derived from the monomer having a carbon-carbon double bond at the terminal in the resin and the content of the structural unit derived from the polyrotaxane compound are respectively the terminal when the resin is produced. It can adjust with the addition amount of the monomer which has a carbon-carbon double bond, and a polyrotaxane compound.

  A known additive may be added to the resin as long as the effects of the present invention are not impaired. Examples of the additives include UV absorbers (hindered amine compounds, etc.) for improving weather resistance, antioxidants (phenolic compounds, phosphorus compounds, etc.) for preventing discoloration and yellowing, and molecular weight control. Chain transfer agents (such as linear or branched alkyl mercaptan compounds such as methyl mercaptan, n-butyl mercaptan, and t-butyl mercaptan), flame retardants for imparting flame retardancy, and colorants.

  The porous body of the present invention can be obtained by stretching the resin.

The stretching process may be uniaxial stretching or biaxial stretching. The stretching method may be a method using a general apparatus such as roll stretching, tenter stretching, or rolling.
In the present embodiment, for example, in the case of uniaxial stretching, the stretching ratio is 1.05 times or more, preferably 1.07 times or more and 1.30 times or less.
Here, the stretching ratio is a pair of grips in which a porous membrane sample cut so as to have a length of 10 mm and a thickness of 4 mm in a direction perpendicular to the measurement direction is arranged so that the distance between them is 115 mm. The tool is held so that the direction defining the interval coincides with the measurement direction, and the sample is stretched at a rate of 5 mm / min along the measurement direction by the pair of gripping tools until the sample is broken. When the distance between the pair of grips when the sample breaks is L1 (mm), the value is calculated by the following equation.
Stretch ratio (%) = {(L1-115) / 115} × 100
The stretching temperature is not particularly limited, but stretching is preferably performed at room temperature to 80 ° C. or less.

  The manufacturing method of the porous body of this invention may include processes other than the process of manufacturing the said resin, and the process of extending | stretching obtained resin. Examples of the other steps include a step of molding the resin into a predetermined size and shape.

  The porous body obtained by the above production method using the above compound has fine pores, and is apparently whitened.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples. The degree of whitening of the porous bodies obtained in Examples and Comparative Examples was evaluated by the following method.
<Method for evaluating porous body>
A 4 mm thick porous sample was placed on a piece of paper printed with black pigment ink on white paper, and through the sample, it was visually evaluated whether the printed character could be identified. Classified. As the character cannot be identified through the sample, it is whitened and is a porous body having fine pores.
A: Characters are not visible at all and cannot be identified.
B: Black shadows of characters are visible but cannot be identified.
C: Characters can be clearly identified.

<Hydroxyl value>
The hydroxyl value (unit: mgKOH / g) of polyrotaxane was measured based on JIS K0070.

Example 1
A polyrotaxane substituted with ε-caprolactone, the linear molecule is polyethylene glycol (PEG) having a weight average molecular weight of 35000, and a weight average molecular weight of 700,000 Celm (registered trademark) superpolymer SH3400P (advanced soft material 340 g of a hydroxyl value of 72 mg KOH / g (manufactured by Co., Ltd.) was dissolved in 1300 mL of dehydrated methyl methacrylate at room temperature. 3.4 mL of methacryloyloxyethyl isocyanate was added, and 1 part by mass of dibutyltin dilaurate as a catalyst was added to methacryloyloxyethyl isocyanate. Thereafter, the mixture was stirred at room temperature for 5 days to obtain a polyrotaxane compound.
10 parts by mass of the polyrotaxane compound, 89.9 parts by mass of methyl methacrylate, and 0.1 parts by mass of 2,2′-azobisisobutyronitrile were added and mixed. Next, the obtained mixture was poured into a cell having a gap of 4 mm composed of two glass plates and a soft polyvinyl chloride gasket, and in a polymerization tank using air as a heat medium at 70 ° C. After polymerizing by heating for 3 hours and then at 120 ° C. for 40 minutes to obtain a resin, a porous body was obtained by uniaxial stretching at 1.30 times at room temperature.
The obtained porous body was visually evaluated. The results are shown in Table 1. Moreover, when the cross section of the porous body obtained with the scanning electron microscope was observed, as shown in FIG. 2, the micropore was seen.

(Example 2)
A resin was obtained in the same manner as in Example 1 except that 5.1 mL of methacryloyloxyethyl isocyaninate was added. The obtained porous body was visually evaluated. The results are shown in Table 1.

(Comparative Example 1)
A resin was obtained in the same manner as in Example 1 except that 1.7 mL of methacryloyloxyethyl isocyanate was added, and then uniaxially stretched 1.02 times at room temperature to obtain a porous body.
The obtained porous body was visually evaluated. The results are shown in Table 1.

(Comparative Example 2)
A resin was obtained in the same manner as in Example 1 except that 6.8 mL of methacryloyloxyethyl isocyanate was added, and then uniaxially stretched 1.23 times at room temperature to obtain a porous body.
The obtained porous body was visually evaluated. The results are shown in Table 1.

(Comparative Example 3)
Instead of the above-mentioned Serum (registered trademark) superpolymer SH3400P, the linear molecule is polyethylene glycol (PEG) having a weight average molecular weight of 20000, and the Serum (registered trademark) superpolymer SH2400P (Advanced A resin was obtained in the same manner as in Example 1 except that Soft Material Co., Ltd., hydroxyl value 76 mgKOH / g) was used, and then a porous body was obtained by uniaxial stretching at 1.09 times at room temperature.
The obtained porous body was visually evaluated. The results are shown in Table 1. Moreover, when the cross section of the porous body obtained with the scanning electron microscope was observed, as shown in FIG. 4, the micropore was not seen.

(Comparative Example 4)
A resin containing only methyl methacrylate was obtained in the same manner as in Example 1 without adding the polyrotaxane compound, and then uniaxially stretched 1.02 times at room temperature.
The appearance of the obtained porous body was visually evaluated. The results are shown in Table 1.

(Example 3)
A porous body was obtained in the same manner as in Example 1 except that 20 parts by mass of the polyrotaxane compound and 79.9 parts by mass of methyl methacrylate were used. The obtained porous body was visually evaluated. The results are shown in Table 1.

Example 4
A porous material was obtained in the same manner as in Example 1 except that 5 parts by mass of the polyrotaxane compound and 94.9 parts by mass of methyl methacrylate were used. The obtained porous body was visually evaluated. The results are shown in Table 1. Moreover, when the cross section of the porous body was observed with a scanning electron microscope, fine pores were seen as shown in FIG.

1 Polyrotaxane 2 Cyclodextrin which may be substituted 3 Linear molecule 4 Blocking group

Claims (2)

It is a method for producing a porous body comprising a step of stretching a resin having a structural unit derived from a monomer having a carbon-carbon double bond at a terminal and a structural unit derived from a polyrotaxane compound,
In the polyrotaxane compound, a hydrogen atom having a hydroxyl group of 4% or more and 10% or less is substituted with a group containing a (meth) acryloyl group or a (meth) acryloyl group out of several hundred% of the hydrogen atoms of the hydroxyl group contained in the polyrotaxane. The compound being
The polyrotaxane is an optionally substituted cyclodextrin;
A linear molecule clathrating the optionally substituted cyclodextrin in a skewered manner;
Having a blocking group that is disposed at the end of a linear molecule clathrating the optionally substituted cyclodextrin and prevents the elimination of the optionally substituted cyclodextrin,
A method for producing a porous body, which is a resin having a weight average molecular weight of 21,000 or more and 500,000 or less of linear molecules clathrating the optionally substituted cyclodextrin.   The method for producing a porous body according to claim 1, wherein the content of the structural unit derived from the polyrotaxane compound is 5 parts by mass or more.

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