Polymer composite materials, methods for producing the same, and polymer compositions

Abstract

To provide: a polymer composite material excellent in mechanical strength; a method for manufacturing the polymer composite material; and a polymer composition suitably usable for manufacturing the polymer composite material.SOLUTION: A polymer composite material of the present invention includes a first polymer containing a cross-linked polymer having a host group, and a second polymer other than the first polymer. The host group is a group obtained by removing one hydrogen atom or hydroxy group from cyclodextrin or cyclodextrin derivative. The polymer composite material is excellent in mechanical strength.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to polymer composite materials, methods for producing the same, and polymer compositions. [Background technology]

[0002] As the applications of polymer materials diversify, the demand for improved performance and other enhancements is increasing. For example, there is a growing need to develop polymer materials that improve both physical properties, such as hardness and elongation, which are typically in a trade-off relationship. Various methods are known for improving the physical properties of polymer materials. One such method is polymer alloying, which involves mixing different polymers (see, for example, Patent Document 1). This polymer alloying method has the advantage of allowing the design of materials that combine the strengths of each different polymer backbone. Polymer alloying can also be achieved by adding compatibilizers or by performing a secondary graft polymerization reaction. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2021-070768 [Overview of the project] [Problems that the invention aims to solve]

[0004] On the other hand, addressing environmental issues in recent years is essential for realizing a sustainable society. From this perspective, developing durable materials to reduce waste is an extremely effective means of improving the functionality of polymer materials and addressing environmental issues. From this perspective, the use of materials compounded with different components, such as the polymer alloys mentioned above, is extremely valuable.

[0005] The present invention has been made in view of the above, and aims to provide a polymer composite material with excellent mechanical strength, a method for producing the same, and a polymer composition that can be suitably used for producing the polymer composite material. [Means for solving the problem]

[0006] The inventors of this invention conducted extensive research to achieve the above objectives and, as a result, discovered that these objectives can be achieved by using a specific cross-linking structure as an essential component, thus completing the present invention.

[0007] In other words, the present invention encompasses, for example, the subject matter described in the following sections. Item 1 A first polymer comprising a crosslinked polymer having a host group, and a second polymer other than the first polymer, The host group is a polymer composite material in which one hydrogen atom or hydroxyl group is removed from a cyclodextrin or cyclodextrin derivative. Section 2 The polymer composite material according to claim 1, wherein the crosslinked polymer further has guest groups, and the host groups and the guest groups form an inclusion complex. Section 3 The polymer composite material according to claim 1, wherein the crosslinked polymer has a structure in which a linear polymer penetrates the host group. Section 4 A polymer composite material according to any one of claims 1 to 3, wherein the crosslinked polymer is dispersed in the material. Section 5 The polymer composite material according to any one of claims 1 to 4, wherein the second polymer penetrates the network of the crosslinked polymer. Section 6 A method for producing polymer composite materials, Step 1 below Step 1: A step to obtain a polymer composite material comprising a first polymer containing a crosslinked polymer having a host group and a second polymer other than the first polymer by a polymerization reaction of a mixture containing a first polymer containing a crosslinked polymer having a host group and a polymerizable monomer. Equipped with, The method for producing a polymer composite material, wherein the host group is a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative. Item 7 The production method according to claim 6, wherein the first polymer used in the step is in a powder form, gel form, slurry form or molded body. Item 8 The production method according to item 6 or 7, wherein the polymerizable monomer is a radically polymerizable monomer. Item 9 A polymer composition containing a slurry in which a first polymer containing a crosslinked polymer having a host group is dissolved or swollen in a solvent. Item 10 The polymer composition according to item 9, which is for producing the polymer composite material according to any one of items 1 to 5.

Advantages of the Invention

[0008] The polymer composite material of the present invention can be produced by a simple method and has excellent mechanical strength. Further, the method for producing the polymer composite material of the present invention is suitable as a method for producing the polymer composite material. Furthermore, the polymer composition of the present invention is suitable as a raw material for producing the polymer composite material.

Brief Description of the Drawings

[0009] [Figure 1] It is a schematic diagram schematically showing the structure of an embodiment of the polymer composite material of the present invention.

Modes for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present invention will be described in detail. In this specification, the expressions "containing" and "comprising" include the concepts of "containing", "comprising", "substantially consisting of" and "consisting only of".

[0011] 1.Polymer composite materials The polymer composite material of the present invention comprises a first polymer containing a crosslinked polymer having a host group, and a second polymer other than the first polymer. In the crosslinked polymer, the host group is a group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative. The polymer composite material of the present invention, by containing a specific crosslinked polymer, has excellent mechanical strength and is a tough material.

[0012] (First polymer) The first polymer includes a crosslinked polymer having a host group. Such a crosslinked polymer is formed from a polymer compound having a host group and has a three-dimensional crosslinked structure. In the polymer compound having a host group, the host group is covalently bonded to the polymer compound and is present, for example, in the side chains. Hereinafter, the crosslinked polymer having a host group included in the first polymer will be referred to as "crosslinked polymer A".

[0013] Crosslinked polymer A includes, for example, host group-containing monomer units as constituent units. A host group-containing monomer unit refers to a constituent unit formed when a polymerizable monomer having a host group (host group-containing polymerizable monomer) is polymerized. A host group-containing monomer unit is a monomer unit having at least one of the aforementioned host groups.

[0014] The host group-containing monomer units contained in the cross-linked structure A may be one or more types.

[0015] As described above, the host group is a group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative. The host group is not limited to a monovalent group; for example, the host group may be a divalent group. Furthermore, a host group-containing monomer unit may contain only one host group, or it may contain two or more.

[0016] Here, the cyclodextrin derivative refers to a molecule having a structure in which at least one of the hydroxyl groups of cyclodextrin has a hydrogen atom substituted with a hydrophobic group. In other words, a cyclodextrin derivative refers to a molecule having a structure in which a cyclodextrin molecule is substituted with another hydrophobic organic group. However, a cyclodextrin derivative has at least one hydrogen atom or at least one hydroxyl group, and preferably at least one hydroxyl group.

[0017] The hydrophobic group is preferably substituted with at least one group selected from the group consisting of hydrocarbon groups, acyl groups, and -CONHR (where R is a methyl group or an ethyl group). Hereinafter, in this specification, the aforementioned "at least one group selected from the group consisting of hydrocarbon groups, acyl groups, and -CONHR (where R is a methyl group or an ethyl group)" may be referred to as "hydrocarbon groups, etc." for convenience.

[0018] Herein, merely as a note for clarity, the term "cyclodextrin" as used herein means at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Therefore, a cyclodextrin derivative is at least one selected from the group consisting of α-cyclodextrin derivatives, β-cyclodextrin derivatives, and γ-cyclodextrin derivatives.

[0019] The host group is a monovalent or greater group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin derivative, but the hydrogen atom or hydroxyl group removed in the cyclodextrin derivative may be any part of the cyclodextrin or cyclodextrin derivative.

[0020] Here, if we let N be the total number of hydroxyl groups in one cyclodextrin molecule, then α-cyclodextrin has N=18, β-cyclodextrin has N=21, and γ-cyclodextrin has N=24.

[0021] If the host group is a monovalent group obtained by removing one "hydroxyl group" from a cyclodextrin derivative, then the cyclodextrin derivative is formed by substituting up to N-1 hydrogen atoms of hydroxyl groups with hydrocarbon groups or the like per cyclodextrin molecule. On the other hand, if the host group is a monovalent group obtained by removing one "hydrogen atom" from a cyclodextrin derivative, then the cyclodextrin derivative can have up to N hydrogen atoms of hydroxyl groups substituted with hydrocarbon groups or the like per cyclodextrin molecule.

[0022] When the host group is a cyclodextrin derivative from which one hydrogen atom or hydroxyl group has been removed, it is preferable that the structure has such that 70% or more of the hydrogen atoms of the hydroxyl groups present in one cyclodextrin molecule are substituted with the hydrocarbon group or the like, more preferably 80% or more, and particularly preferably 90% or more of the total number of hydroxyl groups.

[0023] When the host group is a group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin derivative, it is preferable that the structure has such that 13 or more hydrogen atoms of the hydroxyl groups present in one α-cyclodextrin molecule are substituted with the hydrocarbon group or the like, more preferably 15 or more, and particularly preferably 17 or more.

[0024] The host group preferably has a structure in which 15 or more hydrogen atoms of the total hydroxyl groups present in one β-cyclodextrin molecule are substituted with the hydrocarbon group or the like, more preferably 17 or more, and particularly preferably 19 or more.

[0025] The host group preferably has a structure in which 17 or more hydrogen atoms of the total hydroxyl groups present in one molecule of γ-cyclodextrin are substituted with the hydrocarbon group or the like, more preferably 19 or more, and particularly preferably 21 or more.

[0026] In cyclodextrin derivatives, the type of hydrocarbon group is not particularly limited. Examples of the hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups.

[0027] The number of carbon atoms in the hydrocarbon group is not particularly limited; for example, the hydrocarbon group preferably has 1 to 4 carbon atoms.

[0028] Specific examples of hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, and butyl groups. When the hydrocarbon group is a propyl or butyl group, it may be in either a linear or branched chain configuration.

[0029] In cyclodextrin derivatives, the acyl group can be an acetyl group, propionyl group, formyl group, etc. The acyl group is preferably an acetyl group because it facilitates the formation of host-guest interactions, allows other polymer chains to easily penetrate the host ring, and makes it easier to obtain polymer materials with excellent toughness and strength.

[0030] In cyclodextrin derivatives, -CONHR (where R is a methyl group or an ethyl group) is a methyl carbamate group or an ethyl carbamate group. -CONHR is preferably an ethyl carbamate group because it facilitates the formation of host-guest interactions, allows other polymer chains to easily penetrate the host ring, and makes it easier to obtain polymer materials with excellent toughness and strength.

[0031] In cyclodextrin derivatives, the hydrocarbon group is preferably an alkyl group or acyl group having 1 to 4 carbon atoms, preferably a methyl group and an acyl group, more preferably a methyl group, an acetyl group and a propionyl group, and particularly preferably a methyl group and an acetyl group.

[0032] The host group-containing monomer unit is not particularly limited as long as it has the host group and is a polymerizable compound; for example, known host group-containing polymerizable monomers can be broadly exemplified. The host group-containing polymerizable monomer preferably has a functional group that exhibits radical polymerizability. Examples of functional groups that exhibit radical polymerizability include groups containing a carbon-carbon double bond, specifically, acryloyl group (CH2=CH(CO)-), methacryloyl group (CH2=CCH3(CO)-), and others such as styryl group, vinyl group, and allyl group. These carbon-carbon double bond-containing groups may have further substituents, provided that radical polymerizability is not inhibited.

[0033] Specific examples of host group-containing polymerizable monomers include vinyl polymerizable monomers having the aforementioned host group. For example, a host group-containing polymerizable monomer can be a compound represented by the following general formula (h1).

[0034] [ka]

[0035] In formula (h1), Ra represents a hydrogen atom or a methyl group, and R H represents the host group, R 1 This represents a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of a hydroxyl group, a thiol group, an optionally substituted alkoxy group, an optionally substituted thioalkoxy group, an optionally substituted alkyl group, an optionally substituted amino group, an optionally substituted amide group, an aldehyde group, and a carboxyl group.

[0036] Alternatively, examples of host group-containing polymerizable monomers include compounds represented by the following general formula (h2).

[0037] [ka]

[0038] In formula (h2), Ra, R H and R 1 are respectively the same as Ra, R H and R 1 in formula (h1).

[0039] Furthermore, examples of the host group-containing polymerizable monomer include compounds represented by the following general formula (h3).

[0040]

Chemical formula

[0041] In formula (h3), Ra, R H and R 1 are respectively the same as Ra, R H and R 1 in formula (h1). n is an integer of 1 to 20, preferably 1 to 10, more preferably 1 to 5. Rb represents hydrogen or an alkyl group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms).

[0042] In addition, the host group R H in the host group-containing polymerizable monomers represented by formulas (h1), (h2) and (h3) is an example when it is a monovalent group obtained by removing one hydroxyl group from cyclodextrin or its derivative.

[0043] <00002​​​​​​If it is a divalent group formed by removing one hydrogen atom from an amino group which may have one substituent, then the nitrogen atom of the amino group can bond with the carbon atom of the C=C double bond.

[0045] In equations (h1) to (h3), R 1 If it is a divalent group formed by removing one hydrogen atom from an amide group which may have one substituent, then the carbon atom of the amide group can bond with the carbon atom of the C=C double bond.

[0046] In equations (h1) to (h3), R 1 If it is a divalent group formed by removing one hydrogen atom from an aldehyde group, then the carbon atom of the aldehyde group can bond with the carbon atom of a C=C double bond.

[0047] In equations (h1) to (h3), R 1 If it is a divalent group formed by removing one hydrogen atom from a carboxyl group, the carbon atom of the carboxyl group can bond with the carbon atom of the C=C double bond.

[0048] The host group-containing polymerizable monomers represented by formulas (h1) to (h3) are, for example, (meth)acrylic acid ester derivatives (i.e., R 1 (-COO-), (meth)acrylamide derivatives (i.e., R 1 It is preferable that the substituent is -CONH- or -CONR-, where R is synonymous with the substituent. As for the R in -CONR-, for example, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 6 carbon atoms is particularly preferred.

[0049] In this specification, "(meth)acrylic" means "acrylic" or "methacrylic," "(meth)acrylate" means "acrylate" or "methacrylate," and "(meth)allyl" means "allyl" or "methallyl."

[0050] The method for producing the host group-containing polymerizable monomer is not particularly limited, and for example, known production methods can be widely employed.

[0051] The crosslinked polymer A may contain at least one selected from the group consisting of the host group-containing monomer unit, the guest group-containing monomer unit, and the third monomer unit, in addition to the host group-containing monomer unit. The guest group-containing monomer unit contained in the crosslinked structure A may be one or more types, and the third monomer unit contained in the crosslinked structure A may be one or more types.

[0052] A guest group-containing monomer unit refers to a repeating structural unit formed when a guest group-containing polymerizable monomer is polymerized. A guest group-containing monomer unit is a monomer unit having at least one guest group.

[0053] The type of guest group is not limited as long as it is a group capable of host-guest interaction with the host group, and especially as long as it is a group that can be encapsulated by the host group. The guest group is not limited to a monovalent group; for example, the guest group may be a divalent group. Furthermore, a guest group-containing monomer unit may contain only one guest group, or it may contain two or more guest groups.

[0054] Examples of guest groups include linear or branched hydrocarbon groups having 3 to 30 carbon atoms, cycloalkyl groups, heteroaryl groups, and organometallic complexes, which may have one or more substituents. Examples of substituents are the same as those mentioned above, and include halogen atoms (e.g., fluorine, chlorine, bromine, etc.), hydroxyl groups, carboxyl groups, ester groups, amide groups, and possibly protected hydroxyl groups.

[0055] More specific guest groups include linear or cyclic alkyl groups having 4 to 18 carbon atoms, and groups derived from polycyclic aromatic hydrocarbons. Linear alkyl groups having 4 to 18 carbon atoms may be either linear or branched. Cyclic alkyl groups may have a cage-like structure. Examples of polycyclic aromatic hydrocarbons include π-conjugated compounds formed by at least two aromatic rings, specifically naphthalene, anthracene, tetracene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, and the like.

[0056] Other examples of guest groups include monovalent groups formed by removing one atom (e.g., a hydrogen atom) from a guest molecule, such as at least one selected from the group of guest molecules including alcohol derivatives; aryl compounds; carboxylic acid derivatives; amino derivatives; azobenzene derivatives; azobenzene; naphthalene derivatives; anthracene derivatives; pyrene derivatives; perylene derivatives; carbon atom clusters such as fullerenes; and dansyl compounds.

[0057] Further specific examples of guest groups include t-butyl groups, n-octyl groups, n-dodecyl groups, isobornyl groups, adamantyl groups, pyrene-derived groups, and groups to which the aforementioned substituents are attached.

[0058] The guest group-containing monomer unit is not particularly limited as long as it is a compound that has the guest group and is polymerizable; for example, known guest group-containing polymerizable monomers can be broadly exemplified. The guest group-containing polymerizable monomer preferably has a functional group that exhibits radical polymerizability. Examples of functional groups that exhibit radical polymerizability include groups containing a carbon-carbon double bond, specifically, acryloyl group (CH2=CH(CO)-), methacryloyl group (CH2=CCH3(CO)-), and others such as styryl group, vinyl group, and allyl group. These carbon-carbon double bond-containing groups may have further substituents, provided that radical polymerizability is not inhibited.

[0059] Specific examples of guest group-containing polymerizable monomers include vinyl-based polymerizable monomers having the aforementioned guest group. For example, a guest group-containing polymerizable monomer can be a compound represented by the following general formula (g1).

[0060] [ka]

[0061] In formula (g1), Ra represents a hydrogen atom or a methyl group, and R G R represents the guest group, 2 This is synonymous with R1 in formula (h1). Among the polymerizable monomers represented by formula (g1), (meth)acrylic acid esters or their derivatives (i.e., R 2 (-COO-), (meth)acrylamide or its derivatives (i.e., R 2 It is preferable that the substituent is -CONH- or -CONR-, where R is synonymous with the substituent. In this case, the polymerization reaction proceeds easily, making it easier to produce the crosslinked polymer A.

[0062] Specific examples of guest group-containing polymerizable monomers include n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-dodecyl (meth)acrylate, adamantyl (meth)acrylate, hydroxyadamantyl (meth)acrylate, 1-(meth)acrylamide adamantane, 2-ethyl-2-adamantyl (meth)acrylate, N-dodecyl (meth)acrylamide, t-butyl (meth)acrylate, 1-acrylamide adamantane, N-(1-adamantyl)(meth)acrylamide, N-benzyl (meth)acrylamide, N-1-naphthylmethyl (meth)acrylamide, ethoxylated o-phenylphenol acrylate, phenoxypolyethylene glycol acrylate, isostearyl acrylate, nonylphenol EO adduct acrylate, isobornyl (meth)acrylate, (meth)acrylate having a pyrene moiety, and (meth)acrylamide having a pyrene moiety.

[0063] Guest group-containing polymerizable monomers can be produced by known methods. Alternatively, commercially available guest group-containing polymerizable monomers can also be used.

[0064] The third monomer unit refers to a repeating structural unit formed when the third polymerizable monomer is polymerized. The third monomer unit refers to a repeating structural unit formed when a polymerizable monomer copolymerizable with the host group-containing polymerizable monomer and the guest group-containing polymerizable monomer (hereinafter referred to as the "third polymerizable monomer") is polymerized. The third polymerizable monomer is not identical to the host group-containing polymerizable monomer and the guest group-containing polymerizable monomer, and in particular, does not have the host group.

[0065] Examples of the third polymerizable monomer include various known vinyl polymerizable monomers. Specific examples of the third polymerizable monomer include compounds represented by the following general formula (a1).

[0066] [ka]

[0067] In formula (a1), Ra is a hydrogen atom or a methyl group, R 3 This represents a halogen atom, a hydroxyl group, a thiol group, an amino group or a salt thereof which may have one substituent, a carboxyl group or a salt thereof which may have one substituent, an amide group or a salt thereof which may have one or more substituents, or a phenyl group which may have one or more substituents.

[0068] In formula (a1), R 3When the carboxyl group has one substituent, examples include carboxyl groups (i.e., esters) in which the hydrogen atoms of the carboxyl group are substituted with a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyalkyl group (e.g., hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group), methoxypolyethylene glycol (ethylene glycol has 1 to 20 units, preferably 1 to 10, particularly preferably 2 to 5), ethoxypolyethylene glycol (ethylene glycol has 1 to 20 units, preferably 1 to 10, particularly preferably 2 to 5), etc. The hydrocarbon group having 1 to 20 carbon atoms is preferably 1 to 15 carbon atoms, preferably 1 to 10, and particularly preferably 1 to 3 carbon atoms. The hydrocarbon group may be linear or branched.

[0069] In formula (a1), R 3 When the amide group has one or more substituents, i.e., a secondary or tertiary amide, examples include amide groups in which one or two hydrogen atoms of the primary amide are independently substituted with a hydrocarbon group having 1 to 20 carbon atoms or a hydroxyalkyl group (e.g., a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group). The hydrocarbon group having 1 to 20 carbon atoms is preferably 1 to 15 carbon atoms, and more preferably 2 to 10 carbon atoms. The hydrocarbon group may be linear or branched.

[0070] Specific examples of monomers represented by formula (a1) include (meth)acrylic acid, allylamine, maleic anhydride, styrene, as well as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, 2-methoxy(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, 2-phenylethyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 2-methoxy(meth)acrylate, tetrahydrofurfuryl(meth) Examples of (meth)acrylic esters include acrylate, 2-phenylethyl (meth)acrylate, hydroxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ethoxy-diethylene glycol (meth)acrylate, methoxy-triethylene glycol (meth)acrylate, and methoxy-polyethylene glycol (meth)acrylate; and (meth)acrylamide compounds such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethylacrylamide, N-isopropyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylamide, and N-hydroxymethyl (meth)acrylamide. These can be used individually or in combination of two or more.

[0071] In particular, when the host group is a monovalent group obtained by removing one "hydroxyl group" or "hydrogen" from a cyclodextrin, the third polymerizable monomer is preferably highly water-soluble, and is preferably one or more selected from the group consisting of (meth)acrylic acid, (meth)acrylamide, and methyl (meth)acrylate and ethyl (meth)acrylate.

[0072] Alternatively, if the host group is a monovalent group obtained by removing one "hydroxyl group" or "hydrogen" from the cyclodextrin derivative, the third polymerizable monomer is preferably selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, 2-methoxy (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-phenylethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxy (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and phenoxyethyl (meth)acrylate. In this case, the third polymerizable monomer may also contain 1 to 30% by mass of a water-soluble monomer, and examples of water-soluble monomers include (meth)acrylamide and N,N-dimethyl(meth)acrylamide.

[0073] The third monomer unit is preferably (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, or a derivative thereof, among the compounds represented by formula (a1). In this case, the polymerization reaction proceeds easily, making it easier to produce crosslinked polymer A.

[0074] The crosslinked structure A preferably has a host group content of 0.1 mol% or more in its total constituent units, more preferably 0.3 mol% or more, even more preferably 0.5 mol% or more, and particularly preferably 1 mol% or more. Furthermore, the crosslinked structure A preferably has a host group content of 40 mol% or less in its total constituent units, more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0075] The structure of crosslinked polymer A is not particularly limited. For example, crosslinked polymer A may have a structure in which the host group and the guest group form an inclusion complex, or crosslinked polymer A may have a structure in which a linear polymer penetrates the host group.

[0076] If the crosslinked polymer A further has the guest group and the host group and the guest group have a structure in which they form an inclusion complex, then the crosslinked structure A has a crosslinked structure based on so-called host-guest interaction.

[0077] Hereinafter, a crosslinked structure A having a crosslinked structure based on host-guest interactions will be abbreviated as "host-guest type crosslinked structure A," and a crosslinked polymer A having a structure in which a linear polymer penetrates the host group will be abbreviated as "mobile crosslinked type crosslinked structure A."

[0078] The host-guest type crosslinked structure A comprises, for example, the host group-containing monomer unit, the guest group-containing monomer unit, and the third monomer unit. Hereinafter, the host group-containing monomer unit will be abbreviated as "host unit," the guest group-containing monomer unit as simply "guest unit," and the third monomer unit as "third unit."

[0079] In the host-guest crosslinked structure A, the content ratio of the host unit and the guest unit in the total number of constituent units is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, even more preferably 0.5 mol% or more, and particularly preferably 1 mol% or more. Furthermore, in the host-guest crosslinked structure A, the content ratio of the host unit and the guest unit in the total number of constituent units is preferably 40 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less. In this invention, the proportion (molar ratio) of each constituent unit in the host-guest crosslinked structure A can be considered to be the same as the molar ratio of each monomer used in the production of the polymer compound.

[0080] The host-guest type cross-linked structure A can be formed only from the host unit, the guest unit, and the third unit, or it may also include other monomer units.

[0081] The combination of host group and guest group contained in host-guest type crosslinked structure A is not particularly limited, as long as it can form an inclusion complex. When the host group is derived from α-cyclodextrin or a derivative thereof, the guest group is preferably at least one selected from the group of octyl group and dodecyl group. For similar reasons, when the host group is derived from β-cyclodextrin or a derivative thereof, the guest group is preferably at least one selected from the group of adamantyl group, methyl-substituted adamantyl group, ethyl-substituted adamantyl group and isobornyl group. When the host group is derived from γ-cyclodextrin or a derivative thereof, the guest group is preferably at least one selected from the group consisting of octyl group, dodecyl group, cyclododecyl group, adamantyl group, methyl-substituted adamantyl group, ethyl-substituted adamantyl group and isobornyl group.

[0082] On the other hand, the movable crosslinked crosslinked structure A comprises, for example, the host unit and the third monomer unit. Preferably, the movable crosslinked crosslinked structure A does not have the guest unit.

[0083] In the movable crosslinked structure A, a crosslinked structure is formed by a linear polymer penetrating the ring of the host group. Since the penetrating linear polymer can slide and move within the ring of the host group, the crosslinked structure A can have a movable crosslinked structure. The linear polymer penetrating the ring of the host group is a polymer compound formed from the third monomer unit. The linear polymer penetrating the ring of the host group may also have the host unit of the third monomer unit, in which case the host unit acts as a so-called stopper, preventing the linear polymer from detaching from the host group.

[0084] The movable crosslinked cross-linked structure A preferably has a host unit content of 0.1 mol% or more, more preferably 0.3 mol% or more, even more preferably 0.5 mol% or more, and particularly preferably 1 mol% or more in its total constituent units. Furthermore, the movable crosslinked cross-linked structure A preferably has a host unit content of 40 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less in its total constituent units.

[0085] The movable cross-linked cross-linked structure A can be formed solely from the host unit and the third unit, or it may also include other monomer units.

[0086] In the movable crosslinked crosslinked structure A, the type of linear polymer penetrating the host group is not particularly limited as long as it is of a size that can penetrate the host group. In terms of ease of penetrating the host group, it is preferable that it be one or more polymers selected from the group consisting of (meth)acrylic acid, (meth)acrylate, (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylamide, and N,N-dimethyl(meth)acrylamide.

[0087] The method for producing the crosslinked structure A is not particularly limited, and for example, known production methods can be widely employed. For instance, the crosslinked structure A can be obtained by a radical polymerization reaction of a raw material having a host group-containing polymerizable monomer, or by using a polymer compound having a host group unit.

[0088] If the crosslinked structure A is a host-guest type crosslinked structure A, it can be obtained by a polymerization reaction of a monomer mixture (the host group-containing monomer, the guest group-containing monomer, and the third monomer) for obtaining a polymer compound having a host unit, a guest unit, and a third unit. Specifically, as the polymer compound having a host unit, a guest unit, and a third unit grows, an inclusion complex is formed between the host group and the guest group, and as a result, a host-guest type crosslinked structure A can be obtained. The monomer mixture may have the host group-containing monomer and the guest group-containing monomer forming an inclusion compound. The obtained host-guest type crosslinked structure A is a crosslinked body with the inclusion complex as a crosslinking site, and the crosslinking site is based on host-guest interaction.

[0089] If the crosslinked structure A is a movable crosslinked structure A, it can be obtained, for example, by a polymerization reaction to obtain a polymer compound having a host unit and a third unit. Specifically, as the polymer compound having a host unit and a third unit grows, other polymer chains (particularly the growing chain of the third unit) penetrate the host group, a movable crosslinked structure A can be formed.

[0090] The first polymer may be formed solely of crosslinked structure A, or it may contain other components, such as a solvent. If crosslinked structure A contains a solvent, the first polymer may, for example, become a polymer gel. The type of solvent is not particularly limited, and a wide range of solvents used for polymer gels can be employed. As long as a polymer gel can be formed, it may be a hydrophilic or hydrophobic solvent. Examples of hydrophilic solvents include water, C1-C3 alcohol compounds (preferably ethanol and / or isopropanol), glycerin, other aprotic solvents, lipid oils, terpenoids, silicone oils, and various other organic solvents. Examples of aprotic solvents include amides such as N,N-dimethylformamide, N-methylacetamide, and N-methyl-2-pyrrolidone; esters such as methyl acetate and ethyl acetate; ketones such as acetone, methyl ethyl ketone, and γ-butyrolactone (γBL); ethers such as 1,4-dioxane and tetrahydrofuran; sulfur-containing compounds such as dimethyl sulfoxide; and carbonate compounds such as propylene carbonate. In particular, the solvent preferably contains at least one selected from the group consisting of water and glycerin.

[0091] (Second polymer) The second polymer is a component other than the first polymer, and its type is not particularly limited; for example, various known polymer compounds can be cited. Examples of the second polymer include various vinyl polymers, polyurethanes, polyesters, polyamides, polyimides, etc. The second polymer is preferably a vinyl polymer, and among these, (meth)acrylic acid polymers, (meth)acrylic ester polymers, and (meth)acrylamide polymers are preferred, as they facilitate the preparation of polymer composite materials and easily improve compatibility with the first polymer.

[0092] A specific example of the second polymer is a monomer polymer containing one or more compounds represented by the formula (a1) described above.

[0093] When the second polymer is a (meth)acrylic acid-based polymer or a (meth)acrylic ester-based polymer, examples include one or more polymers selected from the group consisting of (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-phenylethyl acrylate, 4-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, and phenoxyethyl (meth)acrylate. In particular, the second polymer is preferably one or more polymers selected from the group consisting of (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.

[0094] When the second polymer is a (meth)acrylamide polymer, examples include one or more polymers selected from the group consisting of (meth)acrylamide, N,N-dimethylacrylamide, N-isopropyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylate, and 2-hydroxyethyl(meth)acrylamide, and among these, one or more polymers selected from the group consisting of (meth)acrylamide and N,N-dimethylacrylamide are preferred.

[0095] The second polymer may have a linear structure or a branched structure. If the second polymer has a linear structure or a branched structure, all monomer units contained in the second polymer may be identical to, partially common to, or entirely different from, the monomer units contained in the first polymer.

[0096] Furthermore, the second polymer may be a crosslinked structure. When the second polymer is a crosslinked structure, an example of such a crosslinked structure is the crosslinked structure A contained in the first polymer mentioned above. When the second polymer is a crosslinked structure A, its type is not particularly limited as long as it is not identical to the crosslinked structure A contained in the first polymer. For example, the second polymer can be a crosslinked structure A that has the same composition (constituent units) as the crosslinked structure A contained in the first polymer but with a different composition ratio, or the second polymer can be a crosslinked structure A that has different (constituent units) from the crosslinked structure A contained in the first polymer.

[0097] In other words, when the second polymer is a crosslinked structure, the polymer composite material contains at least two types of crosslinked structures A. When the second polymer is a crosslinked structure A, such crosslinked structure A may be either the host-guest type crosslinked structure A or the mobile crosslinked structure A described above, and preferably both the first polymer and the second polymer are mobile crosslinked structures A.

[0098] (Polymer composite material) The polymer composite material of the present invention may contain components other than the first polymer and the second polymer, as long as the effects of the present invention are not hindered. The polymer composite material of the present invention may also be formed from only the first polymer and the second polymer. When the polymer composite material of the present invention contains components other than the first polymer and the second polymer, the content ratio is not particularly limited, and for example, it may be 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, relative to the total mass of the first polymer and the second polymer.

[0099] In the polymer composite material of the present invention, the content ratio of the first polymer and the second polymer is not particularly limited. For example, in terms of the polymer composite material having excellent mechanical strength and being a tough material, it is preferable that the content ratio of the crosslinked structure A in the first polymer is 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more, relative to the total mass of the crosslinked structure A and the second polymer in the first polymer. Furthermore, it is preferable that the content ratio of the crosslinked structure A is 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less.

[0100] The polymer composite material of the present invention is not particularly limited in its state of existence, as long as it contains the first polymer and the second polymer. For example, in the polymer composite material of the present invention, the crosslinked structure (crosslinked structure A) contained in the first polymer can exist in a dispersed state. This makes the polymer composite material more mechanically strong and prone to becoming a tough material. The crosslinked structure A can exist in the polymer composite material as a dispersed domain structure such as a spherical structure.

[0101] Furthermore, in the polymer composite material of the present invention, the second polymer may penetrate the network of the crosslinked polymer. This increases the compatibility between the first polymer and the second polymer, and the polymer composite material exhibits particularly excellent mechanical strength and tends to become a tougher material. When the second polymer penetrates the network of the crosslinked polymer, it is preferable that the second polymer is linear.

[0102] Figure 1 schematically shows one embodiment of the polymer composite material of the present invention, in which the second polymer penetrates the network of the crosslinked polymer A.

[0103] The shape of the polymer composite material of the present invention is not particularly limited and may be a molded body such as a film, sheet, plate, or block, or it may be particulate, fibrous, granular, or pelletized. Furthermore, the polymer composite material may be a gel, or a cellogel obtained by drying a gel, and can be appropriately selected depending on the application. Examples of applications as a gel include gel ink, buffer material, dielectric, conductor, and bioelectrode.

[0104] The polymer composite material of the present invention, by containing the first polymer and the second polymer, exhibits excellent mechanical strength and tends to be a tough material. Specifically, the polymer composite material of the present invention tends to have high fracture energy and Young's modulus, and the good balance between the two results in a tough material.

[0105] Furthermore, the polymer composite material of the present invention can have self-healing properties, and in particular, if it includes a crosslinked structure A having the aforementioned host-guest type crosslinked structure, the polymer composite material of the present invention can have good self-healing properties.

[0106] 2. Method for manufacturing polymer composite materials The method for producing the polymer composite material of the present invention is not particularly limited. For example, the polymer composite material of the present invention can be produced by a method comprising the following step 1. Step 1: A step to obtain a polymer composite material comprising a first polymer containing a crosslinked polymer having a host group and a second polymer other than the first polymer, by a polymerization reaction of a mixture containing a first polymer containing a crosslinked polymer having a host group and a polymerizable monomer.

[0107] Here, the host group is a group from which one hydrogen atom or hydroxyl group has been removed from cyclodextrin or a cyclodextrin derivative, and is equivalent to the host group in the polymer composite material of the present invention.

[0108] Step 1 uses a raw material containing a first polymer which includes a crosslinked polymer having a host group. The first polymer contained in the raw material used in Step 1 is synonymous with the first polymer in the polymer composite material of the present invention. That is, the first polymer used in Step 1 is a raw material for forming the first polymer in the polymer composite material.

[0109] The raw material containing the first polymer used in step 1 is, for example, in the form of a powder, gel, slurry, or molded article.

[0110] When the raw material containing the first polymer is in gel form, for example, the raw material containing the first polymer can be a hydrogel in which the crosslinked structure A is swollen with a solvent. Examples of solvents include hydrophilic solvents, specifically, water, C1-C3 alcohol compounds (preferably ethanol and / or isopropanol), glycerin, other aprotic solvents, lipid oils, terpenoids, silicone oils, and various other organic solvents. Examples of aprotic solvents include amides such as N,N-dimethylformamide, N-methylacetamide, and N-methyl-2-pyrrolidone; esters such as methyl acetate and ethyl acetate; ketones such as acetone, methyl ethyl ketone, and γ-butyrolactone (γBL); ethers such as 1,4-dioxane and tetrahydrofuran; sulfur-containing compounds such as dimethyl sulfoxide; carbonate compounds such as propylene carbonate; and aromatic hydrocarbons such as toluene. In particular, it is preferable that the solvent contains at least one selected from the group consisting of water and glycerin.

[0111] If the raw material containing the first polymer used in step 1 is in slurry form, the crosslinked structure A in the first polymer is, for example, dissolved, swollen, or dispersed in a solvent. The solvent can be, for example, the same type as the solvent used to form the hydrogel described above, and among these, water, glycerin, toluene, N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, acetone, etc. are preferred.

[0112] When the raw material containing the first polymer used in step 1 is in slurry form, the solid content concentration in such slurry is not particularly limited. For example, the content ratio of the crosslinked structure A to the total mass of the crosslinked structure A and the solvent is preferably 1 to 40% by mass, and preferably 5 to 30% by mass. When the raw material containing the first polymer used in step 1 is in slurry form, the slurry can be pulverized beforehand. This pulverization can be carried out using, for example, a bead mill.

[0113] If the raw material containing the first polymer used in step 1 is in slurry form, the method for preparing such slurry is not particularly limited. For example, the slurry can be prepared by mixing a pre-fabricated crosslinked structure A with a solvent. Alternatively, the slurry can be prepared by mixing the aforementioned hydrogel with a solvent.

[0114] If the raw material containing the first polymer used in step 1 is a powder, the method for preparing such a powder is not particularly limited, and a wide range of known methods can be employed. For example, methods such as grinding the crosslinked structure A, or removing the solvent from the slurry in an appropriate manner to produce a powder can be cited.

[0115] When the raw material containing the first polymer used in step 1 is a molded article, the shape of such a molded article is not particularly limited and can be, for example, a sheet, a block, a film, etc.

[0116] In step 1, a mixture is prepared containing a raw material comprising a first polymer in powder, gel, slurry, or molded form, and at least one polymerizable monomer, and a polymerization reaction is carried out on the mixture. The polymerizable monomer in the mixture is a raw material for producing a second polymer in the polymer composite material. The polymerizable monomer in the mixture may be a single type or two or more types.

[0117] The polymerizable monomer is preferably a radical polymerizable monomer. Examples of radical polymerizable monomers include the compound represented by formula (a1) above. Therefore, for example, the polymerizable monomer can be (meth)acrylic acid or (meth)acrylic ester, and specifically, one or more selected from the group consisting of (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-phenylethyl acrylate, 4-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, and 2-phenylethyl acrylate. In particular, it is preferable that it be one or more selected from the group consisting of (meth)acrylic acid, (meth)acrylate, (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.

[0118] Furthermore, for example, the polymerizable monomer can be a (meth)acrylamide compound, and can be one or more selected from the group consisting of (meth)acrylamide, N,N-dimethylacrylamide, N-isopropyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylate, and 2-hydroxyethyl(meth)acrylamide. Among these, one or more selected from the group consisting of (meth)acrylamide and N,N-dimethylacrylamide are preferred.

[0119] If the first polymer used in step 1 contains a hydrogel, the polymerizable monomer is preferably a (meth)acrylamide compound. In this case, the resulting second polymer is easily compatible with the first polymer. If the first polymer used in step 1 is not a hydrogel, the polymerizable monomer is preferably a (meth)acrylic acid or a (meth)acrylic ester, or a mixture of a (meth)acrylic ester and a (meth)acrylamide compound. In a mixture of a (meth)acrylic ester and a (meth)acrylamide compound, the content of the (meth)acrylamide compound is, for example, 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less.

[0120] The polymerizable monomer may also be a mixture of the aforementioned host group-containing polymerizable monomer and the compound represented by formula (a1) above. In this case, the resulting second polymer can form a crosslinked structure similar to the crosslinked structure A of the first polymer. However, the crosslinked structure of the second polymer differs from the crosslinked structure A of the first polymer in terms of the proportion of constituent units or the types of constituent units.

[0121] The method for preparing the mixture used in step 1 is not particularly limited. For example, the mixture can be prepared by mixing a first polymer in the form of a powder, gel, slurry, or molded body with at least one polymerizable monomer in an appropriate manner.

[0122] In the mixture used in step 1, the content ratio of the first polymer to the polymerizable monomer is not particularly limited. For example, in terms of the ease with which the polymer composite material can be made into a tough material, it is preferable that the content ratio of the crosslinked structure A in relation to the total mass of the crosslinked structure A and polymerizable monomer contained in the first polymer is 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more. Furthermore, it is preferable that the content ratio of the crosslinked structure A is 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less.

[0123] The mixture used in step 1 may include, in addition to the first polymer and polymerizable monomer, a polymerization initiator, a polymerization accelerator, a crosslinking agent, etc. The type of polymerization initiator is not particularly limited, and for example, known polymerization initiators can be widely used. Examples of polymerization initiators include persulfate compounds such as ammonium persulfate; azo compounds such as azobisisobutyronitrile; peroxides such as di-tert-butyl peroxide, tert-butyl hydroperoxide, and benzoyl peroxide; and photopolymerization initiators such as the Omnirad series from IGM Resins BV. The concentration of the polymerization initiator can be, for example, 0.01 to 10% by mass, preferably 0.05 to 5% by mass, and more preferably 0.1 to 3% by mass, based on the total amount of polymerizable monomer. Examples of polymerization accelerators include N,N,N',N'-tetramethylethylenediamine.

[0124] The polymerization reaction method carried out in step 1 is not particularly limited, and a wide range of known polymerization reactions can be employed. For example, depending on the type of polymerization initiator used, methods such as thermal polymerization and photopolymerization can be widely employed. When photopolymerization is employed, ultraviolet light (for example, UV light with a wavelength of 200 to 405 nm) can be used as the light source. The temperature of the polymerization reaction is also not limited, and can be, for example, 0 to 100°C, preferably 20 to 25°C. The time of the polymerization reaction is also not particularly limited, and can be 1 minute to 24 hours, preferably 1 minute to 5 hours.

[0125] By carrying out a polymerization reaction of the mixture prepared in step 1, a second polymer is produced, and the polymer composite material of the present invention described above can be obtained. This polymer composite material contains a first polymer containing a crosslinked structure A and a second polymer. The polymerization reaction of the mixture can be carried out, for example, with the mixture contained in a suitable container, or with a coating film of the mixture formed.

[0126] In particular, when the first polymer used in step 1 is in powder, gel, or slurry form, the mixture prepared in step 1 is a liquid, such as a solution or dispersion. Therefore, such a mixture can be subjected to a polymerization reaction while contained in a sheet-like mold, or it can be subjected to a polymerization reaction while a film has been formed by methods such as casting it onto a substrate. In the former case, the resulting polymer composite material is a molded article such as a sheet, and in the latter case, the resulting polymer composite material is a film.

[0127] If the first polymer used in step 1 is a molded article, the mixture prepared in step 1 may, for example, be a molded article impregnated with the polymerizable monomer. In this case, the polymerization reaction proceeds in which the polymerizable monomer polymerizes within the molded article, which is the first polymer, to produce a second polymer. As a result, the resulting polymer composite material is also a molded article, just like the first polymer.

[0128] As described above, polymer composite materials in various shapes, such as sheets and films, can be obtained through step 1.

[0129] 3. Polymer composition The present invention also includes polymer compositions. The polymer composition of the present invention contains a slurry in which a first polymer, which includes a crosslinked polymer having a host group, is dissolved, dispersed, or swollen in a solvent. Such a slurry corresponds to a slurry that can be used in step 1 of the manufacturing method described above.

[0130] Therefore, the crosslinked polymer having a host group in the polymer composition of the present invention is synonymous with the aforementioned crosslinked structure A, and the solvent in the polymer composition of the present invention is synonymous with the solvent in the slurry that can be used in step 1. Accordingly, similar to the slurry used in step 1, water, glycerin, toluene, N,N-dimethylformamide, acetone, etc. are preferred as the solvent in the polymer composition of the present invention.

[0131] In the polymer composition of the present invention, the solid content concentration in the slurry is not particularly limited. For example, the content ratio of the crosslinked structure A to the total mass of the crosslinked structure A and the solvent is preferably 1 to 40% by mass, and preferably 5 to 30% by mass.

[0132] In the polymer composition of the present invention, the method for preparing the slurry is not particularly limited. For example, the slurry can be prepared by mixing a pre-fabricated crosslinked structure A with a solvent. Alternatively, the slurry can be prepared by mixing the aforementioned hydrogel with a solvent.

[0133] The polymer composition of the present invention can be formed solely from a slurry, or it may contain components other than the slurry as needed. Furthermore, in the polymer composition of the present invention, the slurry may consist only of the crosslinked structure A and the solvent, or it may contain other components.

[0134] Since the polymer composition of the present invention contains a slurry containing a crosslinked structure A, the polymer composition of the present invention is suitable for the production of the polymer composite material of the present invention as described above, and is particularly suitable for use as a raw material for the production of the polymer composite material of the present invention. Specifically, the polymer composition of the present invention is suitable for use as a first polymer used in step 1. [Examples]

[0135] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to the embodiments of these examples.

[0136] [Production of the first polymer] (Production example 1: Crosslinked structure A1) A mixture of 6-acrylamide-β-cyclodextrin (βCD-AAm) as a host group-containing polymerizable monomer, N-(1-adamantyl)acrylamide (Ad-AAm) as a guest group-containing polymerizable monomer, and acrylamide (AAm) (manufactured by Wako Pure Chemical Industries, Ltd.) as a third polymerizable monomer was mixed in a molar ratio of 3:3:94. This mixture was stirred for 5 minutes while being irradiated with ultrasound. After filtering, ammonium persulfate (0.25 mol% of the total monomers) and N,N,N',N'-tetramethylethylenediamine (5 mol% of the total monomers) and water were added as polymerization initiators to prepare the mixture. The amount of water was 69.64% by mass of the total mixture. Polymerization was carried out by leaving this mixture at room temperature for 1 hour. The resulting polymer was washed to a depth of approximately 4 cm. 3 A hydrogel in the shape of a nearly rectangular parallelepiped was obtained. This hydrogel contains repeating structural units derived from βCD-AAm and repeating structural units derived from Ad-AAm, each at a ratio of 3 mol% in the polymer.

[0137] Next, 80 ml of glycerin was placed in a 100 ml beaker, and the hydrogel was completely immersed in it. In this state, the mixture was left to stand at room temperature (25°C) for 12 hours, thereby replacing the water in the hydrogel with glycerin (G). This yielded a host-guest type gel-like crosslinked structure (denoted as crosslinked structure A1). In the gel-like crosslinked structure A1, water accounted for 22.16% by mass and glycerin for 37% by mass.

[0138] (Production example 2: Crosslinked structure A2) 0.95 mmol of the compound (βCDAAm) represented by the following formula (1-1), prepared by a known method, was weighed into a Schlenk tube and purged with nitrogen. 20 g of this βCDAAm was dissolved in 300 mL of pyridine, 170.133 g of acetic anhydride was added, and the mixture was stirred at 55°C for at least 12 hours. Then, 50 mL of methanol was added to quench the mixture, and the solution was concentrated in an evaporator until the volume was 200 mL. The resulting concentrate was added dropwise to 2000 mL of water, and the resulting precipitate was collected. The precipitate was dissolved in 200 mL of acetone, added dropwise to 2000 mL of water, and the resulting precipitate was collected. The target product, Ac-CDAA, was isolated by drying under reduced pressure. Mass spectroscopy and NMR spectroscopy confirmed that the target Ac-CDAA had been formed. It was confirmed that 100% of the total hydroxyl groups present in one molecule of the cyclodextrin derivative in Ac-CDAA were substituted with acetyl groups. Therefore, it was found that Ac-CDAA is a compound in which the hydrogen atom of the hydroxyl group in formula (1-1) is replaced by an acetyl group.

[0139] [ka]

[0140] Next, Ac-CDAA was used as the host group-containing polymerizable monomer, N-(1-adamantyl)acrylamide (hereinafter referred to as "ADAA," manufactured by Yushiro Chemical Industry Co., Ltd.) as the guest group-containing polymerizable monomer, and a mixture of 4-hydroxybutyl acrylate (hereinafter referred to as "4HBA," manufactured by Tokyo Chemical Industry Co., Ltd.) and N,N-dimethylacrylamide was used as the third polymerizable monomer, all mixed in a molar ratio of 0.5:0.5:79:20 (mass ratio of 7.0:0.7:78.6:13.7) to prepare a monomer mixture. To this monomer mixture, Omnirad184 (registered trademark) was added as a photopolymerization initiator in the amounts (weight %) shown in Table 1, and the monomer mixture was polymerized by irradiation with ultraviolet light. This polymerization reaction involves placing a monomer mixture in a 70 x 10 x 3 mm mold made from a silicone sheet, and using an ultraviolet irradiation device (AS ONE "SLUV-8") at an ultraviolet wavelength of 366 nm and an irradiation intensity of 1.6-1.7 mW / cm². 2 The polymerization reaction was carried out by irradiation for 5 minutes at (measured values). This polymerization reaction yielded a host-guest type crosslinked structure (crosslinked structure A2).

[0141] (Production example 3: Crosslinked structure A3) A crosslinked structure (crosslinked structure A3) was obtained in the same manner as in Production Example 2, except that the above Ac-CDAA was used as a host group-containing polymerizable monomer, ADAA as a guest group-containing polymerizable monomer, and phenoxyethyl acrylate as a third polymerizable monomer were mixed in a molar ratio of 1:1:98 to prepare a monomer mixture.

[0142] (Production example 4: Crosslinked structure A4) A crosslinked structure (crosslinked structure A4) was obtained in the same manner as in Production Example 2, except that the above Ac-CDAA was used as a host group-containing polymerizable monomer, ADAA as a guest group-containing polymerizable monomer, and ethyl acrylate as a third polymerizable monomer were mixed in a molar ratio of 1:1:98 to prepare a monomer mixture.

[0143] (Production example 5: Crosslinked structure A5) A crosslinked structure (crosslinked structure A5) was obtained in the same manner as in Production Example 2, except that the above Ac-CDAA was used as a host group-containing polymerizable monomer, ADAA as a guest group-containing polymerizable monomer, and methyl acrylate as a third polymerizable monomer, all mixed in a molar ratio of 1:1:98 to prepare a monomer mixture.

[0144] (Production example 6: Crosslinked structure A6) A crosslinked structure (crosslinked structure A6) was obtained in the same manner as in Production Example 2, except that the monomer mixture was prepared by mixing the above Ac-CDAA as a host group-containing polymerizable monomer, ADAA as a guest group-containing polymerizable monomer, and butyl acrylate as a third polymerizable monomer in a molar ratio of 1:1:98.

[0145] [Manufacturing of polymer composite materials] (Example 1-1) Powder preparation from slurry As a crosslinked structure, crosslinked structure A1 obtained in Production Example 1 was mixed with N,N-dimethylformamide or N-methylpyrrolidone as a solvent, and a slurry with a solid content of 10% by mass was prepared by grinding in a ball mill. The solvent was removed by heating this slurry to 150°C and air-drying to obtain powder 1 of crosslinked structure A1. Synthesis of polymer composite materials A mixture was prepared by mixing the aforementioned powder 1 as the first polymer and methyl methacrylate as the polymerizable monomer in a mass ratio of 0.5:99.5. To this mixture, 0.2% by mass of Omnirad184 (registered trademark) was added relative to the polymerizable monomer as a polymerization initiator. Next, the mixture was placed in a mold measuring 70 × 10 × 3 mm made from a silicone sheet, and an ultraviolet irradiation device (AS ONE "SLUV-8") was used to irradiate it at an ultraviolet wavelength of 366 nm and an irradiation intensity of 1.6~1.7 mW / cm². 2 The polymerization reaction was carried out by irradiation for 5 minutes at (measured values). A polymer composite was obtained by this polymerization reaction.

[0146] (Examples 1-2) A polymer composite was obtained in the same manner as in Example 1-1, except that the powder 1 was used as the first polymer and methyl methacrylate was used as the polymerizable monomer, mixed in a mass ratio of 60:40.

[0147] (Examples 1-3) A polymer composite was obtained in the same manner as in Example 1-1, except that the powder 1 was used as the first polymer and methyl methacrylate was used as the polymerizable monomer, mixed in a mass ratio of 50:50.

[0148] (Examples 1-4) A polymer composite was obtained in the same manner as in Example 1-1, except that the powder 1 was mixed as the first polymer and methyl methacrylate as the polymerizable monomer in a mass ratio of 40:60.

[0149] (Examples 1-5) A polymer composite was obtained in the same manner as in Example 1-1, except that the powder 1 was used as the first polymer and methyl methacrylate was used as the polymerizable monomer, mixed in a mass ratio of 10:90.

[0150] (Examples 1-6) A polymeric composite was obtained in the same manner as in Example 1-1, except that the polymerizable monomer was changed to acrylic acid.

[0151] (Examples 1-7) A polymeric composite was obtained in the same manner as in Examples 1-2, except that the polymerizable monomer was changed to acrylic acid.

[0152] (Examples 1-8) A polymeric composite was obtained using the same method as in Examples 1-3, except that the polymerizable monomer was changed to acrylic acid.

[0153] (Examples 1-9) A polymeric composite was obtained in the same manner as in Examples 1-4, except that the polymerizable monomer was changed to acrylic acid.

[0154] (Examples 1-10) A polymeric composite was obtained using the same method as in Examples 1-5, except that the polymerizable monomer was changed to acrylic acid.

[0155] (Examples 1-11) A polymeric composite was obtained in the same manner as in Example 1-1, except that the polymerizable monomer was changed to methacrylic acid.

[0156] (Examples 1-12) A polymeric composite was obtained in the same manner as in Examples 1-2, except that the polymerizable monomer was changed to methacrylic acid.

[0157] (Examples 1-13) A polymeric composite was obtained in the same manner as in Examples 1-3, except that the polymerizable monomer was changed to methacrylic acid.

[0158] (Examples 1-14) A polymeric composite was obtained in the same manner as in Examples 1-4, except that the polymerizable monomer was changed to methacrylic acid.

[0159] (Examples 1-15) A polymeric composite was obtained in the same manner as in Examples 1-5, except that the polymerizable monomer was changed to methacrylic acid.

[0160] (Example 2-1) Slurry preparation As a crosslinked structure, crosslinked structure A3 obtained in Production Example 3 was mixed with N,N-dimethylformamide or tetrahydrofuran as a solvent, and slurry 1 with a solid content of 10% by mass was prepared by grinding in a ball mill. Synthesis of polymer composite materials A mixture was prepared by mixing slurry 1 as the first polymer and methyl methacrylate as the polymerizable monomer in a mass ratio (where slurry 1 is calculated on a solid content basis) of 60:40. To this mixture, 0.2% by mass of Omnirad184 (registered trademark) was added relative to the polymerizable monomer as a polymerization initiator. Next, the mixture was placed in a mold measuring 70 × 10 × 3 mm made from a silicone sheet, and an ultraviolet irradiation device (AS ONE "SLUV-8") was used to irradiate it at an ultraviolet wavelength of 366 nm and an irradiation intensity of 1.6~1.7 mW / cm². 2 The polymerization reaction was carried out by irradiation for 5 minutes at (measured values). A polymer composite was obtained by this polymerization reaction.

[0161] (Example 2-2) A polymer composite was obtained in the same manner as in Example 2-1, except that the slurry 1 was used as the first polymer and methyl methacrylate was used as the polymerizable monomer, mixed in a mass ratio (where the slurry 1 ratio is calculated on a solid content basis) of 50:50.

[0162] (Examples 2-3) A polymer composite was obtained in the same manner as in Example 2-1, except that the slurry 1 was used as the first polymer and methyl methacrylate was used as the polymerizable monomer, mixed in a mass ratio (where the slurry 1 is calculated on a solid content basis) of 40:60.

[0163] (Examples 2-4) A polymeric composite was obtained in the same manner as in Example 2-1, except that the polymerizable monomer was changed to acrylic acid.

[0164] (Examples 2-5) A polymeric composite was obtained in the same manner as in Example 2-2, except that the polymerizable monomer was changed to acrylic acid.

[0165] (Examples 2-6) A polymeric composite was obtained using the same method as in Examples 2-3, except that the polymerizable monomer was changed to acrylic acid.

[0166] (Examples 2-7) A polymeric composite was obtained in the same manner as in Example 2-1, except that the polymerizable monomer was changed to methacrylic acid.

[0167] (Examples 2-8) A polymeric composite was obtained in the same manner as in Example 2-2, except that the polymerizable monomer was changed to methacrylic acid.

[0168] (Examples 2-9) A polymeric composite was obtained in the same manner as in Example 2-3, except that the polymerizable monomer was changed to methacrylic acid.

[0169] (Example 3-1) Slurry preparation As a crosslinked structure, crosslinked structure A3 obtained in Production Example 3 was mixed with N,N-dimethylformamide or N-methylpyrrolidone as a solvent, and slurry 2 with a solid content of 10% by mass was prepared by grinding the mixture in a ball mill. Synthesis of polymer composite materials A mixture was prepared by mixing slurry 2 as the first polymer and methyl methacrylate as the polymerizable monomer in a mass ratio (however, slurry 2 is calculated on a solid content basis) of 60:40. To this mixture, 0.2% by mass of Omnirad184 (registered trademark) was added relative to the polymerizable monomer as a polymerization initiator. Next, the mixture was cast onto an aluminum foil substrate to form a cast film, and this cast film was subjected to ultraviolet irradiation using an ultraviolet irradiation device (AS ONE "SLUV-8") at an ultraviolet wavelength of 366 nm and an irradiation intensity of 1.6~1.7 mW / cm². 2 The polymerization reaction was carried out by irradiation for 5 minutes at (measured values). A polymer composite was obtained by this polymerization reaction.

[0170] (Example 3-2) A polymer composite was obtained in the same manner as in Example 3-1, except that the slurry 2 was used as the first polymer and methyl methacrylate was used as the polymerizable monomer, mixed in a mass ratio (however, the slurry 2 ratio was calculated on a solid content basis) of 50:50.

[0171] (Example 3-3) A polymer composite was obtained in the same manner as in Example 3-1, except that the slurry 2 was mixed as the first polymer and methyl methacrylate as the polymerizable monomer in a mass ratio (where the slurry 2 is calculated on a solid content basis) of 40:60.

[0172] (Examples 3-4) A polymeric composite was obtained in the same manner as in Example 3-1, except that the polymerizable monomer was changed to acrylic acid.

[0173] (Examples 3-5) A polymeric composite was obtained in the same manner as in Example 3-2, except that the polymerizable monomer was changed to acrylic acid.

[0174] (Examples 3-6) A polymeric composite was obtained in the same manner as in Example 3-3, except that the polymerizable monomer was changed to acrylic acid.

[0175] (Examples 3-7) A polymeric composite was obtained in the same manner as in Example 3-1, except that the polymerizable monomer was changed to methacrylic acid.

[0176] (Examples 3-8) A polymeric composite was obtained in the same manner as in Example 3-2, except that the polymerizable monomer was changed to methacrylic acid.

[0177] (Examples 3-9) A polymeric composite was obtained in the same manner as in Example 3-3, except that the polymerizable monomer was changed to methacrylic acid.

[0178] (Example 4-1) Powder preparation from slurry As a crosslinked structure, crosslinked structure A1 obtained in Production Example 1 was mixed with N,N-dimethylformamide or N-methylpyrrolidone as a solvent, and a slurry with a solid content of 10% by mass was prepared by grinding in a ball mill. By heating this slurry to 150°C, the solvent was removed to obtain powder 2 of crosslinked structure A1. Synthesis of polymer composite materials A mixture was prepared by mixing the aforementioned powder 2 as the first polymer and acrylamide as the polymerizable monomer in a mass ratio of 0.5:99.5. Ammonium persulfate and N,N,N,N',N'-tetramethylethylenediamine were added to this mixture at a mass percentage of 0.2% relative to the polymerizable monomer. The mixture was then placed in a mold measuring 70 × 10 × 3 mm made from a silicone sheet, and treated with an ultraviolet irradiation device (AS ONE "SLUV-8") at an ultraviolet wavelength of 366 nm and an irradiation intensity of 1.6~1.7 mW / cm². 2 The polymerization reaction was carried out by irradiation for 5 minutes at (measured values). A polymer composite was obtained by this polymerization reaction.

[0179] (Example 4-2) A polymer composite was obtained in the same manner as in Example 4-1, except that the powder 2 was used as the first polymer and acrylamide was used as the polymerizable monomer, mixed in a mass ratio of 1:99.

[0180] (Example 4-3) A polymer composite was obtained in the same manner as in Example 4-1, except that the powder 2 was used as the first polymer and acrylamide was used as the polymerizable monomer, mixed in a mass ratio of 2:98.

[0181] (Example 4-4) A polymer composite was obtained in the same manner as in Example 4-1, except that the powder 2 was used as the first polymer and acrylamide was used as the polymerizable monomer, mixed in a mass ratio of 4:96.

[0182] (Examples 4-5) A polymer composite was obtained in the same manner as in Example 4-1, except that the powder 2 was mixed as the first polymer and acrylamide as the polymerizable monomer in a mass ratio of 10:90.

[0183] (Examples 4-6) A polymeric composite was obtained in the same manner as in Example 4-1, except that the polymerizable monomer was changed to N,N-dimethylacrylamide.

[0184] (Examples 4-7) A polymeric composite was obtained in the same manner as in Example 4-2, except that the polymerizable monomer was changed to N,N-dimethylacrylamide.

[0185] (Examples 4-8) A polymeric composite was obtained in the same manner as in Example 4-3, except that the polymerizable monomer was changed to N,N-dimethylacrylamide.

[0186] (Examples 4-9) A polymeric composite was obtained in the same manner as in Example 4-4, except that the polymerizable monomer was changed to N,N-dimethylacrylamide.

[0187] (Examples 4-10) A polymeric composite was obtained in the same manner as in Examples 4-5, except that the polymerizable monomer was changed to N,N-dimethylacrylamide.

[0188] (Example 5-1) Create a sheet A polymerizable monomer mixture containing 1 mol% of the Ac-CDAA obtained in Production Example 2 and 99 mol% of ethyl acrylate was polymerized in ethyl acetate in the presence of AIBN to obtain a movable crosslinked structure A in the form of a 1 mm thick sheet. Synthesis of polymer composite materials A sheet-like mixture is prepared by mixing the sheet-like crosslinked structure A as the first polymer and N,N-dimethylacrylamide (containing 0.2% by mass of Omnirad184®) as a polymerizable monomer in a mass ratio of 40:60. This sheet-like mixture is then subjected to ultraviolet irradiation using an ultraviolet irradiation device (AS ONE "SLUV-8") at an ultraviolet wavelength of 366 nm and an irradiation intensity of 1.6-1.7 mW / cm². 2 The polymerization reaction was carried out by irradiation for 5 minutes at (measured values). A sheet-like polymer composite was obtained from this polymerization reaction.

[0189] (Example 5-2) A sheet-like polymer composite was obtained in the same manner as in Example 5-1, except that the mass ratio of the sheet-like crosslinked structure A as the first polymer and N,N-dimethylacrylamide (containing 0.2% by mass of Omnirad184®) as the polymerizable monomer was changed to 50:50.

[0190] (Example 5-3) A sheet-like polymer composite was obtained in the same manner as in Example 5-1, except that the mass ratio of the sheet-like crosslinked structure A as the first polymer and N,N-dimethylacrylamide (containing 0.2% by mass of Omnirad184®) as the polymerizable monomer was changed to 60:40.

[0191] (Example 6-1) Create a sheet A polymerizable monomer mixture containing 1 mol% of the Ac-CDAA obtained in Production Example 2 and 99 mol% of ethyl acrylate was polymerized in ethyl acetate in the presence of AIBN to obtain a movable crosslinked structure A in the form of a 1 mm thick sheet. Synthesis of polymer composite materials As the first polymer, the sheet-like movable crosslinked crosslinked structure A and a mixed monomer of N,N-dimethylacrylamide and PAcγCDAAmMe in a molar ratio of 99:1 as polymerizable monomers are mixed in a mass ratio of 40:60 to prepare a sheet-like mixture. This sheet-like mixture is then subjected to ultraviolet irradiation using an ultraviolet irradiation device (AS ONE "SLUV-8") at an ultraviolet wavelength of 366 nm and an irradiation intensity of 1.6~1.7 mW / cm². 2 The polymerization reaction was carried out by irradiation for 5 minutes at (measured values). A sheet-like polymer composite was obtained from this polymerization reaction.

[0192] PAcγCDAAmM was prepared as follows: 5 g (3.9 mmol) of γ-cyclodextrin, 700 mg (6.9 mmol) of N-hydroxymethylacrylamide, and 95 mg (0.6 mmol) of p-toluenesulfonic acid monohydrate were weighed and added to 25 mL of N,N-dimethylformamide to prepare the reaction solution. The solution was heated to 90°C in an oil bath and stirred for 1 hour to obtain the reaction solution. The reaction solution was then allowed to cool and poured into 45 mL of vigorously stirred acetone. After filtering off the resulting precipitate, it was washed three times with 10 mL of acetone and dried under reduced pressure at room temperature for 1 hour to obtain the reaction product. The reaction product was dissolved in 100 mL of distilled water and passed through a column packed with porous polystyrene resin (Mitsubishi Chemical Diaion HP-20) (apparent density 600 g / L) for 30 minutes to allow adsorption. Subsequently, the solution components were removed, and the polystyrene resin was washed by passing 50 mL of a fresh 10% methanol (or acetonitrile) aqueous solution through the column three times to remove unreacted γ-cyclodextrin. Next, 500 mL of a 25% methanol aqueous solution was passed through the column twice to elute the target product, acrylamidemethyl γ-cyclodextrin (denoted as γCDAAmMe). By removing the solvent under reduced pressure, γCDAAmMe was obtained as a white powder. 20 g of this γCDAAmMe was dissolved in 300 mL of pyridine, 170.133 g of acetic anhydride was added, and the mixture was stirred at 55°C for more than 12 hours. Then, 50 mL of methanol was added to quench the mixture, and it was concentrated in an evaporator until the volume was 200 mL. The obtained concentrate was added dropwise to 2000 mL of water, and the precipitate was collected. The precipitate was dissolved in 200 mL of acetone, added dropwise to 2000 mL of water, and the resulting precipitate was collected and dried under reduced pressure to obtain the target product, PAcγCDAAmM.

[0193] (Example 6-2) A sheet-like polymer composite was obtained in the same manner as in Example 5-1, except that the first polymer was the sheet-like movable crosslinked crosslinked structure A, and the polymerizable monomers were a mixed monomer of N,N-dimethylacrylamide and PAcγCDAAmMe in a molar ratio of 99:1, which was changed to a mass ratio of 50:50.

[0194] (Example 6-3) A sheet-like polymer composite was obtained in the same manner as in Example 5-1, except that the first polymer was the sheet-like movable crosslinked crosslinked structure A, and the polymerizable monomers were a mixed monomer of N,N-dimethylacrylamide and PAcγCDAAmMe in a molar ratio of 99:1, which was changed to a mass ratio of 60:40.

[0195] (Comparative Examples 1-6) Crosslinked structures A1, A2, A3, A4, A5, and A6 obtained in manufacturing examples 1 to 6 were prepared and designated as comparative examples 1 to 6 in order.

[0196] <Young's modulus and fracture energy of polymer composite materials> The mechanical properties of polymer composite materials were evaluated by observing the fracture point of the polymer material using a tensile test (stroke-force curve) (Shimadzu Corporation "AUTOGRAPH" (model: AGX-plus)). This fracture point was defined as the endpoint, and the maximum stress up to this endpoint was defined as the fracture stress of the polymer material. This tensile test was performed using an upward method, where the lower end of the sheet-like polymer composite material was fixed and the upper end was moved at a tensile speed of 1 mm / second. From this measurement, the Young's modulus and fracture energy of the polymer material were calculated.

[0197] <Self-healing properties of polymer materials> A polymer composite material (3 mm thick) was cut in the center to divide it into two pieces. The two pieces were then brought into contact at 80°C for 24 hours and rejoined to obtain a test specimen. Using this test specimen, the same evaluation as described in <Evaluation of Breaking Force and Elongation of Polymer Materials> was performed, measuring the breaking force and elongation. The percentage change in breaking force and elongation before and after cutting was calculated, and this was used as the recovery rate (an indicator of self-healing ability).

[0198] Table 1 shows the measurement results of Young's modulus and fracture energy, as well as the self-healing properties, for the polymer composite materials obtained in each example. The polymer composite materials obtained in the examples were found to have high Young's modulus and high fracture energy, indicating that they are materials with excellent mechanical strength.

[0199] Table 1

Claims

1. A first polymer comprising a crosslinked polymer having a host group, and a second polymer other than the first polymer, The host group is a group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative. The first polymer is The following general formula (h1) 【Chemistry 1】 (In formula (h1), Ra represents a hydrogen atom or a methyl group, R H represents the host group, and R 1 represents a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of a hydroxyl group, a thiol group, an optionally substituted alkoxy group, an optionally substituted thioalkoxy group, an optionally substituted alkyl group, an optionally substituted amino group, an optionally substituted amide group, an aldehyde group, and a carboxyl group.) A host group-containing polymerizable monomer represented by, The following general formula (h2) 【Chemistry 2】 (In equation (h2), Ra, R H, and R 1 are equivalent to Ra, R H, and R 1 in equation (h1), respectively.) A host group-containing polymerizable monomer represented by, The following general formula (h3) 【Transformation 3】 (In formula (h3), Ra, R H, and R 1 are equivalent to Ra, R H, and R 1 in formula (h1), respectively, n is 1 to 20, and Rb represents hydrogen or an alkyl group having 1 to 20 carbon atoms.) Host group-containing polymerizable monomer represented by A monomer unit based on one or more selected from the group consisting of, The following general formula (a1) 【Chemistry 4】 (In formula (a1), Ra represents a hydrogen atom or a methyl group, R3 represents a halogen atom, a hydroxyl group, a thiol group, an optionally substituted amino group or a salt thereof, an optionally substituted carboxyl group or a salt thereof, an optionally substituted amide group or a salt thereof, or an optionally substituted phenyl group.) It includes monomer units based on a third polymerizable monomer represented by The second polymer is A polymer of monomers containing one or more compounds represented by the above formula (a1), The content ratio of the crosslinked polymer is 20% by mass or more and 80% by mass or less, relative to the total mass of the crosslinked polymer and the second polymer. The crosslinked polymer further has guest groups, and the host group and the guest group form an inclusion complex, or The crosslinked polymer is a polymer composite material having a structure in which a linear polymer penetrates the host group.

2. The polymer composite material according to claim 1, wherein the crosslinked polymer is dispersed in the material.

3. The polymer composite material according to claim 1, wherein the second polymer penetrates the network of the crosslinked polymer.

4. A method for producing a polymer composite material according to any one of claims 1 to 3, Step 1 below Step 1: A step to obtain a polymer composite material comprising a first polymer containing a crosslinked polymer having a host group and a second polymer other than the first polymer by a polymerization reaction of a mixture containing a first polymer containing a crosslinked polymer having a host group and a polymerizable monomer. Equipped with, A method for producing a polymer composite material, wherein the host group is a group obtained by removing one hydrogen atom or a hydroxyl group from a cyclodextrin or a cyclodextrin derivative.

5. The manufacturing method according to claim 4, wherein the raw material containing the first polymer used in the above step is in the form of a powder, gel, slurry, or molded article.

6. The manufacturing method according to claim 4, wherein the polymerizable monomer is a radical polymerizable monomer.

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