JP7337377B2 - Polymer composite material, polymerizable monomer composition, and method for producing polymer composite material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polymer composite material, a polymerizable monomer composition, and a method for producing a polymer composite material.

Polymer materials are widely used, for example, in films, adhesives, coating agents, molding raw materials, paints, etc., and are indispensable functional materials in the fields of electronic parts, automobile parts, packaging materials, and the like. Especially in recent years, there is a demand in various fields to provide products with higher performance and higher precision. Research and development of molecular materials are actively carried out.

In recent years, the development of polymer materials with various functionalities has been actively developed by skillfully utilizing non-covalent interactions represented by host-guest interactions. For example, Patent Literatures 1 and 2 disclose polymer materials utilizing host-guest interaction. Polymeric materials utilizing such host-guest interactions are attracting attention from various fields as novel materials because they have excellent properties not conventionally available, such as excellent mechanical properties.

WO2016/163550 WO2018/159791

Recently, there is a demand for imparting various functions to polymer materials themselves, and there is a strong demand for development of polymer materials that further improve mechanical properties, for example. Techniques for improving the performance of polymeric materials include, for example, compositing and hybridizing with different components (eg, cellulose materials). However, conventional polymer materials that utilize host-guest interactions have the property of being difficult to mix with different materials due to their structural characteristics. It didn't work as intended.

In particular, the effective use of biomass resources for the construction of a low-carbon society and a recycling-oriented society has been strongly advocated in recent years. It can be said that its utility value is extremely high as a well-thought-out highly functional material.

The present invention has been made in view of the above, and a polymer composite material that can effectively utilize a cellulose material and has excellent flexibility, toughness and hardness, and a polymer composite material used for producing the same It is an object of the present invention to provide a polymerizable monomer composition and a method for producing a polymer composite material.

As a result of intensive studies aimed at achieving the above object, the present inventors achieved the above object by combining a host-guest polymer having a specific structure with a cellulose material using hydrogen bonding. I found that it can be done, and came to complete the present invention.

That is, the present invention includes, for example, the subject matter described in the following sections.
Item 1
comprising a cellulose material and a polymer having host and guest groups;
The host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative,
The guest group is a monovalent group capable of penetrating the host group in a skewered manner,
The polymer comprises a structural unit having the host group in a side chain, a structural unit having a guest group in the side chain, and a third structural unit that does not have both the host group and the guest group,
the cellulose material is at least one of cellulose and a cellulose derivative;
The polymer composite material, wherein the cellulose material forms hydrogen bonds with at least side chains of the polymer.
Item 2
Item 2. The polymer composite material according to Item 1, wherein the cellulose derivative is cellulose modified with a compound having at least one functional group F selected from the group consisting of carboxyl groups, hydroxyl groups, amino groups and amido groups.
Item 3
Item 3. The polymer composite material according to Item 2, wherein the side chain of the polymer forms a hydrogen bond with the functional group F.
Item 4
Item 4. The polymer composite material according to item 3, wherein the end of the guest group and the functional group F form a hydrogen bond.
Item 5
Item 5. The polymer composite material according to Item 3 or 4, wherein the side chain of the third structural unit and the functional group F form a hydrogen bond.
Item 6
Items 1 to 5, wherein at least one of the side chain terminal of the third structural unit and the terminal of the guest group has at least one functional group selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amide group. The polymer composite material according to any one of .
Item 7
A polymerizable monomer composition comprising an inclusion complex formed from a polymerizable monomer having a host group and a polymerizable monomer having a guest group,
The host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative,
The inclusion complex is a polymerizable monomer composition in which the guest group penetrates the host group in a skewed manner.
Item 8
Item 7. The polymerizable monomer composition according to Item 7, which is used for producing the polymer composite material according to any one of Items 1 to 6.
Item 9
A method for producing a polymer composite material, comprising:
an inclusion complex formed from a polymerizable monomer having a host group and a polymerizable monomer having a guest group; and a third polymerizable monomer not having both the host group and the guest group , a step of performing a polymerization reaction of a raw material containing a cellulose material,
The host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative,
In the inclusion complex, the guest group penetrates the host group in a skewered manner,
The production method, wherein the cellulose material is at least one of cellulose and a cellulose derivative.
Item 10
10. The manufacturing method according to claim 9, wherein the cellulose material is dissolved or dispersed in an ionic liquid.
Item 11
Item 11. The production method according to item 10, wherein the cellulose derivative is cellulose modified with a compound having at least one functional group F selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amido group.
Item 12
At least one of the side chain terminal of the third polymerizable monomer and the terminal of the guest group has at least one functional group selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amide group. The production method according to any one of 9 to 11.
Item 13
A self-healing material comprising the polymeric composite material according to any one of Items 1 to 6.

The polymer composite material of the present invention can effectively utilize cellulosic materials and has excellent flexibility, toughness and hardness.

The polymerizable monomer composition of the present invention is suitable as a raw material for producing the polymer composite material.

The method for producing a polymer composite material of the present invention can produce a polymer composite material of a cellulose material and a polymer having a host group and a guest group by a simple method.

1 is a reaction scheme for obtaining an inclusion complex in Production Example 1-1. It is a reaction scheme for obtaining a polymer composite material in Example 1-1. 1 is an FT-IR spectrum of the polymer composite material obtained in Example 1-1. FIG. 2 is a schematic diagram showing hydrogen bonding between the citric acid-modified cellulose and the host-guest polymer in the polymer composite material obtained in Example 1-1. (a) is an SEM image of the polymer material obtained in Comparative Example 1-1, and (b) is an SEM image of the polymer composite material obtained in Example 1-1. 1 shows the results of a tensile test of the polymer composite material obtained in Example 1-1 and the polymer composite material obtained in Comparative Example 1-1. 1 shows the results of a tensile test of the polymer composite material obtained in Example 1-1 and the polymer composite materials obtained in Comparative Examples 1-2, 1-3 and 1-4. 1 shows the results of a tensile test of the polymer composite material obtained in Example 1-1 and the polymer composite material obtained in Example 1-2.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. In this specification, the expressions "contain" and "include" include the concepts of "contain", "include", "substantially consist of" and "consist only of".

1. Polymeric Composite Material The polymeric composite material of the present invention comprises a cellulosic material and a polymer having host and guest groups. In the polymer composite material of the present invention, the host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative, and the guest group skewers the host group. is a monovalent group that can penetrate into Further, the polymer includes a structural unit having the host group in a side chain, a structural unit having a guest group in the side chain, and a third structural unit that does not have both the host group and the guest group. . Furthermore, the cellulose material is at least one of cellulose and a cellulose derivative, and the cellulose material forms hydrogen bonds with at least side chains of the polymer.

The polymer composite material of the present invention is a material that effectively utilizes a cellulose material by having the above structure, and has particularly excellent flexibility, toughness and hardness. In addition, below, the above-mentioned "polymer which has a host group and a guest group" is described as "polymer A."

(Polymer A)
Polymer A is formed having at least a host group and a guest group. More specifically, the polymer A has a structural unit having the host group in its side chain, a structural unit having a guest group in its side chain, and a third structure that does not have both the host group and the guest group. Including units. Host groups and guest groups can be present, for example, chemically bonded (particularly covalently bonded) to the side chains of polymer A.

<Host group>
In polymer A, the host group represents a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative.

In the cyclodextrin derivative, the hydrogen atom of at least one hydroxyl group of the cyclodextrin is substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group and --CONHR (R is a methyl group or an ethyl group). It is preferable to have a structure In other words, a cyclodextrin derivative refers to a molecule having a structure in which a cyclodextrin molecule is substituted with another organic group. However, the cyclodextrin derivative has at least one hydrogen atom or one hydroxyl group, preferably at least one hydroxyl group. In addition, in the present invention, the host group is not limited to a monovalent group, and for example, the host group may be a divalent group.

In the present specification, the aforementioned "at least one group selected from the group consisting of a hydrocarbon group, an acyl group and -CONHR (R is a methyl group or an ethyl group)" is referred to as a "hydrocarbon group or the like" for convenience. may be indicated.

Here, just to be sure, the notation cyclodextrin in this specification means at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin. . Accordingly, the cyclodextrin derivative is at least one selected from the group consisting of α-cyclodextrin derivatives, β-cyclodextrin derivatives and γ-cyclodextrin derivatives.

The host group may contain a monovalent group obtained by removing one hydrogen atom or hydroxyl group from the β-cyclodextrin derivative or γ-cyclodextrin derivative, in that penetration of the guest group described later is likely to be facilitated. preferable. When the host group contains a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a β-cyclodextrin derivative or a γ-cyclodextrin derivative, the content is 90 mol% of the total amount of the host group. It is preferably 99 mol % or more, more preferably 99 mol % or more, and may be 100 mol %.

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

Here, where N is the total number of hydroxyl groups possessed by one cyclodextrin molecule, α-cyclodextrin has N=18, β-cyclodextrin has N=21, and γ-cyclodextrin has N=24.

If the host group is a monovalent group obtained by removing one "hydroxyl group" from the cyclodextrin derivative, the cyclodextrin derivative is such that up to N-1 hydrogen atoms of hydroxyl groups per cyclodextrin molecule are carbonized. It is formed by substitution with a hydrogen group or the like. On the other hand, when the host group is a monovalent group obtained by removing one "hydrogen atom" from the cyclodextrin derivative, the cyclodextrin derivative is such that up to N hydroxyl hydrogen atoms per cyclodextrin molecule are hydrocarbons. may be substituted with groups and the like.

The host group preferably has a structure in which the hydrogen atoms of 70% or more of the total number of hydroxyl groups present in one molecule of cyclodextrin are substituted with the hydrocarbon group or the like. In this case, penetration of the guest group described later tends to be facilitated. In the host group, hydrogen atoms of 80% or more of the total number of hydroxyl groups present in one molecule of cyclodextrin are more preferably substituted with the hydrocarbon group or the like, and 90 of the total number of hydroxyl groups % or more of the hydrogen atoms of the hydroxyl groups are particularly preferably substituted with the aforementioned hydrocarbon groups or the like.

The host group preferably has a structure in which the hydrogen atoms of 13 or more hydroxyl groups out of all the hydroxyl groups present in one molecule of α-cyclodextrin are substituted with the hydrocarbon group or the like. In the host group, hydrogen atoms of 15 or more hydroxyl groups out of all the hydroxyl groups present in one molecule of α-cyclodextrin are more preferably substituted with the hydrocarbon group or the like. It is particularly preferable that the hydrogen atoms of one hydroxyl group are substituted with the above-mentioned hydrocarbon group or the like.

The host group preferably has a structure in which the hydrogen atoms of 15 or more hydroxyl groups out of all the hydroxyl groups present in one molecule of β-cyclodextrin are substituted with the hydrocarbon group or the like. In the host group, hydrogen atoms of 17 or more hydroxyl groups out of all the hydroxyl groups present in one molecule of β-cyclodextrin are more preferably substituted with the hydrocarbon group or the like. It is particularly preferable that one or more hydrogen atoms of hydroxyl groups are substituted with the above hydrocarbon group or the like.

The host group preferably has a structure in which the hydrogen atoms of 17 or more hydroxyl groups out of all the hydroxyl groups present in one molecule of γ-cyclodextrin are substituted with the hydrocarbon group or the like. In the host group, it is more preferable that hydrogen atoms of 19 or more hydroxyl groups out of all the hydroxyl groups present in one molecule of γ-cyclodextrin are substituted with the hydrocarbon group or the like, and 21 out of all the hydroxyl groups It is particularly preferable that one or more hydrogen atoms of hydroxyl groups are substituted with the above hydrocarbon group or the like.

When the host group has two or more hydrocarbon groups, all of them may be the same or some may be different.

The host group is preferably a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a β-cyclodextrin derivative or a γ-cyclodextrin derivative. In this case, since the diameter of the opening of the host group is sufficiently large, the guest group described below easily penetrates the host group in a skewered manner, and the desired polymer composite material can be easily obtained. Among them, the host group is more preferably a monovalent group obtained by removing one hydrogen atom or hydroxyl group from the γ-cyclodextrin derivative. In this case, the obtained polymer composite material has particularly excellent flexibility. strength, toughness and hardness.

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

The number of carbon atoms in the hydrocarbon group is not particularly limited, and for example, the number of carbon atoms in the hydrocarbon group is preferably 1 to 4.

Specific examples of hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, propyl and butyl groups. When the hydrocarbon group is a propyl group or a butyl group, it may be linear or branched.

The hydrocarbon group may have a substituent as long as the effects of the present invention are not impaired.

In the cyclodextrin derivative, the acyl group can be exemplified by acetyl group, propionyl group, formyl group and the like. The acyl group can also have a substituent. The acyl group is preferably an acetyl group from the viewpoint of facilitating the formation of host-guest interaction and facilitating the production of a polymer composite material having excellent flexibility, toughness and hardness.

In cyclodextrin derivatives, —CONHR (R is methyl or ethyl) is a methyl carbamate or ethyl carbamate group. -CONHR is preferably an ethyl carbamate group from the viewpoint of easy formation of host-guest interaction.

In the cyclodextrin derivative, the hydrocarbon group or the like is preferably an acyl group, particularly preferably an acetyl group.

<Guest group>
In the polymer A, the guest group is a group capable of penetrating the host group in a skewed manner, and is usually a monovalent group. The type of the guest group is not limited as long as it can penetrate the host group in a skewed manner.

Examples of the guest group include an optionally substituted linear or branched hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted cycloalkyl group, and a substituted an aryl group which may be substituted, a heteroaryl group which may have a substituent, and the like. Any of these groups may have only one substituent, or may have two or more substituents. As a more specific guest group,

Among them, the guest group preferably contains at least a chain alkyl group having 8 to 18 carbon atoms which may have a substituent.

When the guest group has a substituent, the type of substituent is not particularly limited. As will be described later, the guest group preferably has a substituent, particularly a functional group capable of forming a hydrogen bond, in that the polymer A can easily form a hydrogen bond with the cellulose material. is preferred.

From this point of view, the substituent that the guest group has is preferably at least one functional group selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, a urea group, a urethane group, an imide group and an amide group. More preferably, it is at least one functional group (hereinafter referred to as "functional group G") selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amido group. The functional group G is more preferably a hydroxyl group or a carboxy group, and particularly preferably a carboxy group.

If the guest group has a substituent, such substituent may be attached to any position on the guest group. From the viewpoint that the substituent easily forms a hydrogen bond and the penetration of the host group is facilitated, the binding site of the substituent to the guest group is preferably closer to the terminal side of the guest group. Terminal binding is particularly preferred. The terminal of the guest group as used herein means one end of the guest group opposite to the main chain of the polymer A among both ends of the guest group.

Further specific examples of the guest group include an alkyl group having 8 to 18 carbon atoms which may have a functional group G, an alkyl group having 1 to 2 branches which may have a functional group G, a functional A fluoroalkyl group optionally having a group G, a dimethylsiloxane chain derivative optionally having a functional group G, an aromatic containing a heterocyclic ring optionally having a functional group G, and a group based on a derivative thereof , a polycyclic saturated/unsaturated hydrocarbon group optionally having a functional group G, and the like. For example, an alkyl group having 8 to 18 carbon atoms may be linear, cyclic or cage-like. Examples of the alkyl group having 8 to 18 carbon atoms which may have the functional group G include, for example, an n-octyl group which may have the functional group G; n-nonyl group, n-decyl group optionally having functional group G, n-dodecyl group optionally having functional group G, lauryl optionally having functional group G A stearyl group which may have the functional group G described above. The guest group is an alkyl group having 8 to 18 carbon atoms and having a carboxy group or a hydroxyl group at the end, from the viewpoint of easy production and easy production of a polymer composite material having excellent flexibility, toughness and hardness. is preferred.

The number of guest groups contained in the polymer A may be one or two or more, and the number of guest groups contained in the polymer A is one in that production is easy and stable hydrogen bonds are likely to be formed. is preferred.

<Constituent Unit of Polymer A>
As described above, the polymer A has a structural unit having the host group in its side chain, a structural unit having a guest group in its side chain, and a third structure that does not have both the host group and the guest group. Including units. Hereinafter, a structural unit having the host group in the side chain is referred to as "structural unit H", and a structural unit having the guest group in the side chain is referred to as "structural unit G".

<Structural unit H>
Structural unit H is not particularly limited as long as it has the host group in its side chain. ) can be widely applied.

The type of the host group-containing polymerizable monomer is not particularly limited as long as it has a host group and a functional group exhibiting polymerizability. Specific examples of functional groups exhibiting polymerizability include alkenyl groups, vinyl groups, and the like, as well as —OH, —SH, —NH ₂ , —COOH, —SO ₃ H, —PO ₄ H, isocyanate groups, epoxy groups ( glycidyl group) and the like.

A specific example of the host group-containing polymerizable monomer is a compound in which a host group is bonded to a vinyl compound having a radically polymerizable functional group. Examples of radically polymerizable functional groups include groups containing carbon-carbon double bonds, and specific examples include acryloyl groups (CH ₂ =CH(CO)-), methacryloyl groups (CH ₂ = _CCH (CO)-), styryl group, vinyl group, allyl group and the like. These carbon-carbon double bond-containing groups may further have substituents to the extent that radical polymerizability is not inhibited.

Specific examples of the host group-containing polymerizable monomer include vinyl-based polymerizable monomers having the host group. Examples of the host group-containing vinyl-based monomer include compounds represented by the following general formula (h1).

In formula (h1), Ra represents a hydrogen atom or a methyl group, ^RH represents the host group, ^R1 represents a hydroxyl group, a thiol group, an alkoxy group optionally having one or more substituents, thioalkoxy group optionally having one or more substituents, alkyl group optionally having one or more substituents, amino group optionally having one substituent, one represents a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of an optionally substituted amide group, an aldehyde group and a carboxyl group.

Alternatively, the host group-containing polymerizable monomer can include compounds represented by the following general formula (h2).

In formula (h2), Ra, R ^H and R ¹ have the same meanings as Ra, R ^H and R ¹ in formula (h1).

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

In formula (h3), Ra, R ^H and R ¹ have the same definitions as Ra, R ^H and R ¹ in formula (h1). n is an integer of 1-20, preferably 1-10, more preferably 1-5. 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).

The host group ^RH in the host group-containing polymerizable monomers represented by formulas (h1), (h2) and (h3) is a monovalent This is an example in the case of being a group.

In addition, the host group-containing polymerizable monomer may be one of the compounds represented by formula (h1), formula (h2) and formula (h3), or may contain two or more of them. can be done. In this case, Ra in formula (h1), formula (h2) and formula (h3) may be the same or different. Similarly, R ^H in formula (h1), formula (h2) and formula (h3) and R ¹ in formula (h1), formula (h2) and formula (h3) may each be the same or different.

Substituents defined in formulas (h1) to (h3) are not particularly limited. For example, substituents include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, halogen atoms, carboxyl groups, carbonyl groups, sulfonyl groups, sulfone groups, cyano and the like.

In formulas (h1) to (h3), if R ¹ is a divalent group formed by removing one hydrogen atom from an optionally substituted amino group, amino A nitrogen atom of the group may be attached to the carbon atom of the C═C double bond.

In formulas (h1) to (h3), if R ¹ is a divalent group formed by removing one hydrogen atom from an amide group optionally having one substituent, then amide A carbon atom of the group may be attached to the carbon atom of the C═C double bond.

In formulas (h1) to (h3), if R ¹ is a divalent group formed by removing one hydrogen atom from an aldehyde group, the carbon atom of the aldehyde group is a C=C double bond. It can bond with a carbon atom.

In formulas (h1) to (h3), when R ¹ is a divalent group formed by removing one hydrogen atom from a carboxyl group, the carbon atom of the carboxyl group is a C=C double bond. It can bond with a carbon atom.

Host group-containing polymerizable monomers represented by formulas (h1) to (h3) are, for example, (meth)acrylic acid ester derivatives (that is, R ¹ is —COO—), (meth)acrylamide derivatives (that is, R ¹ is -CONH- or -CONR-, and R is the same as defined above for the substituent). R in -CONR- is, for example, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms.

In this specification, "(meth)acryl" means "acrylic" or "methacryl", "(meth)acrylate" means "acrylate" or "methacrylate", and "(meth)allyl" means " Means "allyl" or "methallyl".

In the present invention, specific examples of the host group-containing polymerizable monomer include compounds represented by the following formulas (h1-7), (h1-8) and (h1-9).

Compounds represented by formulas (h1-7), (h1-8) and ( ^h1-9 ) are α-cyclodextrin derivatives and β- It has a host group obtained by removing one hydroxyl group from a cyclodextrin derivative or a γ-cyclodextrin derivative. In both cases, hydrogen atoms of N−1 hydroxyl groups in the cyclodextrin derivatives are substituted with acetyl groups (denoted as “Ac” in each formula).

The method for producing the host group-containing polymerizable monomer is not particularly limited, and for example, a wide range of known production methods can be employed. For example, the method for producing a host group-containing polymerizable monomer described in Patent Document 2 (specifically, the method for producing a host group-containing vinyl monomer or the production of a host group-containing non-vinyl monomer method) can be adopted.

<Structural unit G>
Structural unit G is not particularly limited as long as it has the guest group in its side chain. ) can be widely applied.

The type of the guest group-containing polymerizable monomer is not particularly limited as long as it has a guest group and a functional group exhibiting polymerizability. Specific examples of functional groups exhibiting polymerizability include alkenyl groups, vinyl groups, and the like, as well as —OH, —SH, —NH ₂ , —COOH, —SO ₃ H, —PO ₄ H, isocyanate groups, epoxy groups ( glycidyl group) and the like.

A specific example of the guest group-containing polymerizable monomer is a compound in which the guest group is bonded to a vinyl compound having a radically polymerizable functional group. Examples of radically polymerizable functional groups include groups containing carbon-carbon double bonds, and specific examples include acryloyl groups (CH ₂ =CH( _CO )-), methacryloyl groups (CH ₂ =CCH (CO)-), styryl group, vinyl group, allyl group and the like. These carbon-carbon double bond-containing groups may further have substituents to the extent that radical polymerizability is not inhibited.

Specific examples of the guest group-containing polymerizable monomer include vinyl-based polymerizable monomers to which the guest group is bonded.

Examples of the guest group-containing vinyl-based monomer include compounds represented by the following general formula (g1).

In formula (g1), Ra represents a hydrogen atom or a methyl group, ^RG represents the guest group, and ^R2 has the same definition as _R1 in formula (h1).

Among the polymerizable monomers represented by formula (g1), (meth)acrylic acid esters or derivatives thereof (that is, R ² is —COO—), (meth)acrylamides or derivatives thereof (that is, R ¹ is — CONH- or -CONR-, where R is the same as defined above for the substituent). In this case, the polymerization reaction proceeds easily, and the toughness and strength of the resulting polymer composite material can be increased.

Specific examples of the guest group-containing vinyl monomer include 12-(meth)acrylamidodecanoic acid, (12-aminododecyl)acrylic acid, (12-hydroxydodecyl)acrylic acid (meth)acrylic acid, and the like. be able to.

A guest group-containing vinyl-based monomer can be produced by a known method. Moreover, a commercial item can also be used for a guest group containing polymerizable monomer.

<Third Structural Unit>
The third structural unit is not particularly limited as long as it does not have the host group and the guest group in the side chain. For example, the host group-containing polymerizable monomer and the guest group-containing polymerizable monomer Structural units derived from various copolymerizable polymerizable monomers (hereinafter referred to as "polymerizable monomer C") can be widely applied.

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

In formula (a1), Ra is a hydrogen atom or a methyl group, ^R3 is a halogen atom, a hydroxyl group, a thiol group, an amino group optionally having one substituent or a salt thereof, one substituent A carboxyl group optionally having one or more substituents or a salt thereof, an amide group optionally having one or more substituents or a salt thereof, and a phenyl group optionally having one or more substituents.

In formula (a1), when R ³ is a carboxyl group having one substituent, the hydrogen atom of the carboxyl group is a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyalkyl group (e.g., hydroxymethyl group, 1- hydroxyethyl group, 2-hydroxyethyl group), methoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5), ethoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5) substituted carboxyl groups (ie, esters). The hydrocarbon group having 1 to 20 carbon atoms preferably has 1 to 15 carbon atoms, more preferably 2 to 10 carbon atoms. The hydrocarbon group may be linear or branched.

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

As will be described later, the polymerizable monomer C has a functional group capable of forming a hydrogen bond on its side chain in that the polymer A easily forms a hydrogen bond with the cellulose material. is preferred. From this point of view, the side chain of the polymerizable monomer C contains at least one functional group selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amide group (hereinafter referred to as "functional group C"). Among them, the functional group C is more preferably a hydroxyl group or a carboxyl group, and particularly preferably a hydroxyl group.

When the polymerizable monomer C has a functional group capable of forming a hydrogen bond on its side chain, such functional group may be attached to any site of the side chain. From the viewpoint that the polymer A easily forms a hydrogen bond, the binding site of the functional group to the side chain of the polymerizable monomer C is preferably closer to the terminal side, and is particularly preferably bound to the terminal. The end of the polymerizable monomer C side chain as used herein means one end of the polymer A on the side opposite to the main chain.

Specific examples of the polymerizable monomer C include (meth)acrylic acid, allylamine, maleic anhydride, N-hydroxymethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylamide , hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, vinyl acetate, mixtures of the vinyl acetate and hydrolysates, N,N-dimethylacrylamide, acryloylmorpholine and the like. These can be used individually by 1 type, or can use 2 or more types together.

<Structure of polymer A>
The content ratio of the host group and the guest group in the polymer A is not particularly limited. The content of structural unit H (that is, host group) can be, for example, 0.01 to 10 mol % based on the total amount of structural unit H, structural unit G and third structural unit. In this case, the flexibility, toughness and hardness of the polymer composite material obtained are also better. The content of the structural unit H is, for example, preferably 0.05 mol% or more, and preferably 0.1 mol% or more based on the total amount of the structural unit H, the structural unit G and the third structural unit. It is more preferably 0.2 mol % or more, and particularly preferably 0.5 mol % or more. Further, the content of the structural unit H is preferably 8 mol% or less, more preferably 6 mol% or less, based on the total amount of the structural unit H, the structural unit G and the third structural unit, for example. , is more preferably 5 mol % or less, and particularly preferably 4 mol % or less.

In the polymer A, the content of the structural unit G (that is, the guest group) is, for example, 0.01 to 10 mol% based on the total amount of the structural unit H, the structural unit G and the third structural unit. can. In this case, the resulting polymer composite has excellent flexibility, toughness and hardness. The content of the structural unit G is, for example, preferably 0.05 mol% or more, preferably 0.1 mol% or more, based on the total amount of the structural unit H, the structural unit G and the third structural unit. It is more preferably 0.2 mol % or more, and particularly preferably 0.5 mol % or more. Further, the content of the structural unit G is preferably 8 mol% or less, more preferably 6 mol% or less, based on the total amount of the structural unit H, the structural unit G and the third structural unit, for example. , is more preferably 5 mol % or less, and particularly preferably 4 mol % or less.

Polymer A includes a structural unit H (a structural unit having the host group in its side chain), a structural unit G (a structural unit having a guest group in its side chain), and a third structural unit (the host group and the guest other monomeric units can be included to the extent that the effects of the present invention are not hindered. When the polymer A contains other monomer units, the content of the structural unit is 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass, based on the total mass of the polymer A. % by mass or less, particularly preferably 0.05 mass % or less.

The polymer A may be in any form such as random polymer, block polymer, alternating copolymer and the like. Generally, polymer A can be a random polymer. Moreover, the polymer A can have a crosslinked structure or a branched structure, but it preferably has a linear structure or a non-crosslinked structure.

The molecular weight (for example, weight-average molecular weight) of polymer A is not particularly limited, and can be, for example, in the same range as the molecular weight of a polymer compound obtained by general radical polymerization.

As described above, the polymer A has at least one functional group selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amide group at the end of the guest group from the viewpoint of facilitating the formation of hydrogen bonds with the cellulose material. It is preferred to have a group (that is, functional group G). Moreover, in the polymer A, the side chain of the third structural unit preferably has at least one functional group (functional group C) selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amide group. .

Therefore, from the viewpoint that the polymer A easily forms a hydrogen bond with the cellulose material, at least one of the terminal of the side chain of the third structural unit and the terminal of the guest group is a carboxy group, a hydroxyl group, an amino group, or an amide group. It is preferable that the polymer A has at least one functional group selected from the group consisting of: both the side chain terminal of the third structural unit and the terminal of the guest group are a carboxy group, a hydroxyl group, an amino group and at least one functional group selected from the group consisting of an amide group. For example, the polymer A may have a structure in which the terminal of the side chain of the third structural unit is a hydroxyl group and the terminal of the guest group is a carboxy group.

The polymer A has a host group and a guest group capable of penetrating the host group. , thereby forming a crosslinked structure between the polymers A. Of course, depending on the type of polymer A, the guest group may penetrate the ring of the host group in a skewed manner even within the same molecule. The ability of the polymer A to form such a crosslinked structure enables the polymer composite material to have excellent flexibility, toughness and hardness.

Generally, one guest group penetrates the host group of the polymer A, but two guest groups may penetrate the host group, depending on the sizes of the host group and the guest group, for example.

The method for producing polymer A is not particularly limited, and a wide range of known methods for producing polymer compounds can be employed. In addition, as will be described later in the section on the method for producing the polymer composite material, the polymer A can also be produced during the process of producing the polymer composite material of the present invention.

(cellulose material)
In the polymer composite material of the present invention, at least one of cellulose and cellulose derivatives can be employed as the cellulose material. Among them, the cellulose material is preferably a cellulose derivative from the viewpoint that hydrogen bonding with the polymer A is likely to occur.

The cellulose derivative is, for example, a compound obtained by modifying cellulose with other functional groups, and can also be referred to as so-called modified cellulose. Specifically, a cellulose derivative has a structure in which a hydroxyl group in a structural unit constituting cellulose or a hydrogen atom of the hydroxyl group is substituted with another functional group. Preferably, it has a structure in which hydroxyl groups in structural units constituting cellulose are substituted with other functional groups.

The cellulose derivative is preferably cellulose modified with a compound having at least one functional group F selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amido group. That is, in the cellulose derivative, the hydroxyl group in the structural unit (glucose unit) constituting cellulose is substituted with at least one functional group F selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amide group. Having a structure is preferred. In this case, since the cellulose material is likely to form hydrogen bonds with the polymer A, the polymer composite material can have excellent flexibility, toughness and hardness.

Among them, in the cellulose derivative, the functional group F is preferably one selected from the group consisting of a carboxy group and a hydroxyl group.

A cellulose derivative can be obtained, for example, by modifying cellulose with a compound having the functional group (eg, functional group F). Here, the compound having the functional group is referred to as "compound F".

Compound F includes, for example, a compound having a carboxy group, a compound having a hydroxyl group, a compound having an amino group, and a compound having an amide group. For these, for example, a wide range of known compounds can be employed.

Specific examples of compound F include citric acid, succinic acid, malic acid, phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, oxalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, and malonic acid. be able to. Among them, the compound F is preferably citric acid from the viewpoint that the production of the cellulose derivative is easy and hydrogen bonding with the polymer A is likely to occur.

Therefore, the cellulose derivative is preferably citric acid-modified cellulose.

In the cellulose derivative, the introduction amount of the functional group derived from compound F is, for example, 0.1 to 5 mmol/g, preferably 0.5 to 3 mmol/g, more preferably 1 to 2 mmol/g.

As a specific method for producing a cellulose derivative, for example, a method of reacting cellulose with the compound F can be mentioned. The method of reacting cellulose with compound F is not particularly limited, and for example, a wide range of known condensation reactions, addition reactions, and the like can be employed.

The reaction between cellulose and compound F can be carried out, for example, in the presence of a catalyst. The type of catalyst is not particularly limited, and examples thereof include acids, alkalis, and the like. The catalyst is preferably an alkali, and specific examples thereof include hydroxides of alkali metals such as sodium hydroxide, ammonia, organic amines, and the like.

The reaction temperature between cellulose and compound F is not particularly limited, either, and can be appropriately selected according to reactivity and the like. For example, the reaction between cellulose and compound F can be carried out at 20-200°C, preferably 50-150°C. The reaction time is also not particularly limited, and can be set appropriately according to the reaction temperature, for example, 30 minutes to 20 hours.

The reaction between cellulose and Compound F can be carried out in various solvents, or can be carried out without solvent.

The molecular weight of the cellulose or cellulose derivative contained in the cellulose material is also not particularly limited. For example, the weight average molecular weight of cellulose or cellulose derivative is 5,000 to 1,000,000, preferably 10,000 to 900,000, more preferably 100,000 to 800,000.

(polymer composite material)
In the polymer composite material of the present invention, the cellulose material forms hydrogen bonds with at least side chains of the polymer A.

More specifically, when the cellulose material is the cellulose derivative, the side chain of the polymer A forms a hydrogen bond with the functional group F of the cellulose derivative. The side chain of the polymer A as used herein is the guest group having the functional group G and/or the side chain of the third structural unit having the functional group C.

On the other hand, when the cellulose material is the cellulose, the side chains of the polymer A form hydrogen bonds with the hydroxyl groups of the cellulose. The side chain of the polymer A here is also the guest group having the functional group G and/or the side chain of the third structural unit having the functional group C.

In the polymer composite material of the present invention, it is preferable that the terminal of the guest group of the polymer A (that is, the functional group G) and the functional group F of the cellulose derivative form a hydrogen bond. Alternatively, in the polymer composite material of the present invention, the side chain of the third structural unit of the polymer A (that is, the functional group C) and the functional group F of the cellulose derivative form a hydrogen bond. preferable. In this case, hydrogen bonds are formed more easily and become strong, and the polymer composite material can have particularly excellent flexibility, toughness and hardness. Particularly preferably, in the polymer composite material of the present invention, the terminal of the guest group of the polymer A (that is, the functional group G) and the functional group F of the cellulose derivative form a hydrogen bond, and the polymer A hydrogen bond is formed between the side chain of the third structural unit of A (that is, the functional group C) and the functional group F of the cellulose derivative (see FIG. 4 below).

In the polymer composite material of the present invention, the content ratio of the cellulose material and the polymer A is not particularly limited as long as the effects of the present invention are not inhibited. For example, from the viewpoint that the flexibility, toughness and hardness of the polymer composite material are likely to be improved, the cellulose material is 0.1 to 20% by mass, preferably 0.2 to 15% by mass, more preferably 0.5 to 10% by mass.

The polymer composite material of the present invention can also contain various additives other than the cellulose material and the polymer A as long as the effects of the present invention are not impaired. Examples of additives include light stabilizers, antioxidants, preservatives, surfactants, fillers such as inorganic particles, flame retardants, pigments, colorants, antifungal agents, and lubricants. One or more of these additives may be contained in the polymeric material.

The polymer composite material of the present invention contains 50% by mass or more of the cellulose material and the polymer A, preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. is more preferable, and 95% by mass or more is particularly preferable.

The polymer composite material of the present invention can be in various forms such as powder, granule, pellet, plate, film, block, sheet, fiber, paste, clay, solution and dispersion. can take

In the polymer composite material of the present invention, a crosslinked structure is formed by having a structure (host-guest interaction) in which the guest group penetrates the host in the polymer A, and the polymer A and the cellulose material are formed. They form hydrogen bonds. Due to the host-guest interaction of the polymer A, the polymer composite material exhibits flexibility and toughness. Excellent hardness is imparted to the composite material.

Additionally, the polymeric composites of the present invention may also have self-healing capabilities. In detail, for example, even if the polymer composite material is cut, the host-guest interaction and/or hydrogen bonding of the polymer A occurs again between the cut surfaces by re-adhering the cut surfaces. recombine and repair the polymer composite.

Therefore, it can be said that the polymer composite material of the present invention is also suitable as a self-healing material. Such a self-repairing material can be said to be a hard material, which has been considered difficult in the past, and to which self-repairing properties are imparted by including the polymer composite material of the present invention.

The polymer composite material of the present invention can be widely applied, for example, to applications in which existing hard plastics or lightweight plastics are used. can be used for

2. Method for Producing Polymer Composite Material The method for producing a polymer composite material of the present invention comprises, for example, step 1 below.
Step 1: an inclusion complex formed from a polymerizable monomer having a host group and a polymerizable monomer having a guest group;
a third polymerizable monomer that does not have both the host group and the guest group;
a step of carrying out a polymerization reaction of the polymerizable monomer composition containing the cellulose material;
Here, the host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative, and the inclusion complex is such that the guest group skewers the host group. The cellulosic material is at least one of cellulose and a cellulose derivative.

For example, the polymer composite material of the present invention described above can be produced by the production method including step 1 above.

The polymerization reaction in step 1 forms a polymer and forms hydrogen bonds between the polymer and the cellulosic material, resulting in a polymeric composite. The polymer formed here is, for example, the polymer A described above.

A polymerizable monomer having a host group, a polymerizable monomer having a guest group, and a polymerizable monomer having both the host group and the guest group contained in the polymerizable monomer composition used in step 1 The polymerizable monomers of No. 3 are the same as the host group-containing polymerizable monomer, the guest group-containing polymerizable monomer and the polymerizable monomer C, respectively.

Therefore, the side chain end of the third polymerizable monomer contained in the raw material used in step 1 has at least one functional group C selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amide group. Among them, the functional group C is more preferably a hydroxyl group or a carboxyl group, and particularly preferably a hydroxyl group.

In addition, the polymerizable monomer having a guest group contained in the raw material used in step 1 has at least one functional group G selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amide group. Among them, the functional group G is more preferably a hydroxyl group or a carboxy group, and particularly preferably a carboxy group.

The polymerizable monomer composition used in step 1 contains various polymerizable monomers and a cellulose material that is at least one of cellulose and a cellulose derivative. The cellulose derivative here is the same as the cellulose derivative contained in the above-described polymer composite material of the present invention. Therefore, the cellulose material used in step 1 is preferably a cellulose derivative, modified with a compound (compound F) having at least one functional group F selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amide group. It is more preferred that the cellulose is For example, citrate-modified cellulose can be used as the cellulosic material.

The form of the cellulose or cellulose derivative used in step 1 is not particularly limited, and examples include various forms such as powder, fibrous, and granular. Also, the cellulose material may be cellulose nanofibers or the like.

The polymerizable monomer composition is, for example, a polymerizable monomer mixture containing a polymerizable monomer having a host group, a polymerizable monomer having a guest group and a third polymerizable monomer; It can be prepared by mixing with a cellulose material.

In the polymerizable monomer mixture, the host group-containing polymerizable monomer and the guest group-containing polymerizable monomer form an inclusion complex. This makes it easier for the polymer A formed by the polymerization reaction in step 1 to form the crosslinked structure, so that the obtained polymer composite material tends to have excellent flexibility, toughness and hardness. The inclusion complex is a compound having a structure in which the guest group of the guest group-containing polymerizable monomer penetrates the inside of the ring of the host group of the host group-containing polymerizable monomer in a skewered manner.

A method for forming the inclusion complex is not particularly limited, and a wide range of known methods can be employed. For example, a polymerizable monomer mixture containing the host group-containing polymerizable monomer, the guest group-containing polymerizable monomer, and the polymerizable monomer C is prepared in advance, and the mixture is sonicated. The inclusion complex can be formed by the step of treatment and/or heat treatment. The inclusion complex is formed through host-guest interactions between the host and guest groups. Formation of such an inclusion complex can make the polymerizable monomer mixture a more homogeneous solution.

The ultrasonic treatment is not particularly limited, and can be performed, for example, by a known method. The ultrasonic treatment time is 1 minute to 12 hours, preferably 15 minutes to 1 hour. The conditions for the heat treatment are also not particularly limited. For heat treatment, the temperature is, for example, 30 to 100.degree. Of course, the inclusion complex can be formed even at room temperature of 30° C. or lower (eg, 10 to 28° C.) without heating. The heating means is also not particularly limited, and examples thereof include a method using a hot stirrer, a method using a constant temperature bath, and the like. The ultrasonic treatment can be performed together with heating or instead of heating.

Whether or not an inclusion complex is formed can be determined, for example, by visually observing the state of the polymerizable monomer mixture. Specifically, when an inclusion complex is not formed, the polymerizable monomer mixture is in a suspended state or in a phase-separated state when allowed to stand. The mixture can be in a viscous state such as a gel or cream. Also, the polymerizable monomer mixture may become transparent when an inclusion complex is formed.

When the polymerizable monomer mixture and the cellulose material are mixed, the cellulose material is preferably dissolved or dispersed in a solvent before use from the viewpoint that the two are easily mixed uniformly. is more preferred. A solvent for dissolving or dispersing the cellulose material is referred to as "solvent S".

The type of solvent S is not particularly limited, and various solvents can be widely used. Among them, ionic liquids are preferred because they are excellent in dissolving cellulose materials, particularly cellulose derivatives.

Examples of ionic liquids include nitrogen-containing onium salts and the like, as well as sulfur-containing onium salts and phosphorus-containing onium salts. More specific examples include 1-butyl-3-methylimidazolium chloride, methylethylimidazolium salts, tetraalkylammonium salts, N-alkylpyridinium salts, tetraalkylphosphonium salts and the like. The counter anion of the ionic liquid is not particularly limited, and examples thereof include chloride ion, bromo ion, trifluoromethylsulfonate anion, tetrafluoroboron anion, and hexafluorophosphorus anion.

The ratio of the cellulose material and the solvent S used is not particularly limited, and can be adjusted within the range in which the cellulose material dissolves in the solvent S, for example. For example, the proportion of the cellulose material and solvent S used can be adjusted so that the concentration of the cellulose material is in the range of 1 to 20% by mass, preferably 3 to 15% by mass.

The cellulose material and the solvent S can be mixed by an appropriate method, for example, using a known mixer or the like. In mixing both, heat treatment may be performed as necessary. The conditions for the heat treatment are not particularly limited. For example, when preparing a solution of a cellulose material using an ionic liquid as a solvent, the heating temperature can be 50 to 150° C., and the heating time is 1 hour to 5 days. can be

The raw material used in step 1 can be obtained, for example, by mixing the polymerizable monomer composition with a solution or dispersion of a cellulose material. A method for mixing the two is not particularly limited, and an appropriate method can be adopted.

In the polymerizable monomer composition, the content ratio of the host group-containing polymerizable monomer is, for example, the host group-containing polymerizable monomer, the guest group-containing polymerizable monomer and the polymerizable monomer. It can be 0.01 to 10 mol % based on the total amount of the monomer C. In this case, the resulting polymer composite has excellent flexibility, toughness and hardness. The content of the host group-containing polymerizable monomer is 0.05 mol based on the total amount of the host group-containing polymerizable monomer, the guest group-containing polymerizable monomer and the polymerizable monomer C. % or more, more preferably 0.1 mol % or more, even more preferably 0.2 mol % or more, and particularly preferably 0.5 mol % or more. The content of the host group-containing polymerizable monomer is 8 mol based on the total amount of the host group-containing polymerizable monomer, the guest group-containing polymerizable monomer and the polymerizable monomer C. % or less, more preferably 6 mol % or less, even more preferably 5 mol % or less, and particularly preferably 4 mol % or less.

In the polymerizable monomer composition, the content of the guest group-containing polymerizable monomer is, for example, the host group-containing polymerizable monomer, the guest group-containing polymerizable monomer and the polymerizable monomer. It can be 0.01 to 10 mol % based on the total amount of the monomer C. In this case, the resulting polymer composite has excellent flexibility, toughness and hardness. The content of the guest group-containing polymerizable monomer is 0.05 mol based on the total amount of the host group-containing polymerizable monomer, the guest group-containing polymerizable monomer and the polymerizable monomer C. % or more, more preferably 0.1 mol % or more, even more preferably 0.2 mol % or more, and particularly preferably 0.5 mol % or more. The content of the guest group-containing polymerizable monomer is 8 mol based on the total amount of the host group-containing polymerizable monomer, the guest group-containing polymerizable monomer and the polymerizable monomer C. % or less, more preferably 6 mol % or less, even more preferably 5 mol % or less, and particularly preferably 4 mol % or less.

In the polymerizable monomer composition, the content ratio of the polymerizable monomer mixture and the cellulose material is not particularly limited as long as the effects of the present invention are not impaired. For example, from the viewpoint that the flexibility, toughness and hardness of the obtained polymer composite material are likely to be improved, the cellulose material is 0.1 to 20 masses relative to the total mass of the cellulose material and the polymerizable monomer mixture. %, preferably 0.2 to 15 mass %, more preferably 0.5 to 10 mass %.

The polymerizable monomer composition used in step 1 can contain a polymerization initiator. The type of polymerization initiator is not particularly limited, and known polymerization initiators can be used. Examples of polymerization initiators include ammonium persulfate (hereinafter sometimes referred to as APS), azobisisobutyronitrile (hereinafter sometimes referred to as AIBN), 2,2′-azobis[2-(2- imidazolin-2-yl)propane]dihydrochloride (hereinafter sometimes referred to as VA-044), 1,1′-azobis(cyclohexanecarbonitrile), di-tert-butyl peroxide, tert-butyl hydroperoxide, peroxide Examples include benzoyl and photopolymerization initiators (Irgacure (registered trademark) series, etc.). The concentration of the radically polymerizable polymerization initiator can be, for example, 0.1 to 5 mol % with respect to the total amount of polymerizable monomers.

In the step 1, other additives may be added to the polymerizable monomer composition, if necessary, in carrying out the polymerization reaction. Other additives are exemplified by polymerization accelerators, cross-linking agents and the like. Examples of the polymerization accelerator include N,N,N',N'-tetramethylethylenediamine. The concentration of the polymerization accelerator can be, for example, 0.5 to 5 mol % with respect to the total amount of polymerizable monomers.

The polymerization reaction may use a solvent for polymerization. When a polymerization solvent is used, the type of solvent is not particularly limited, and the amount used is also not particularly limited. The polymerization reaction can also be carried out in the absence of solvent.

The conditions for the polymerization reaction can be appropriately selected depending on the polymerization reactivity of the monomer, the type of the polymerization initiator, the half-life temperature, etc. For example, a known radical polymerization method or the like can be widely adopted. can. Moreover, the polymerization mode includes bulk polymerization, solution polymerization, dispersion polymerization, suspension polymerization, precipitation polymerization, etc., and is not particularly limited. When photopolymerization is employed, the polymerization reaction can be carried out, for example, by irradiating UV light with a wavelength of 200 to 400 nm.

After the polymerization reaction, the obtained polymer can be washed by an appropriate method. It is preferable to include a step for removing the solvent (particularly the ionic liquid) from the obtained polymer because the mechanical properties of the resulting polymer composite material are likely to be improved.

A method for removing the solvent is not particularly limited, and a wide range of known methods can be adopted. When an ionic liquid is used as the solvent S, the polymer can be washed with water and then dried.

A polymer composite material can be obtained by the above step 1. The content of the ionic liquid in the polymer composite material is, for example, 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, particularly preferably 0.1% by mass or less, relative to the polymer composite material. is 0.05% by mass or less.

3. Polymerizable Monomer Composition The polymerizable monomer composition of the present invention contains an inclusion complex formed from the polymerizable monomer having the host group and the polymerizable monomer having the guest group. The host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative, and the inclusion complex is formed by the guest group penetrating the host group in a skewered manner. Become.

In the polymerizable monomer composition of the present invention, the inclusion complex means the inclusion complex used in producing the above-described polymer composite material of the present invention, and its configuration, formation method and preferred embodiments are all The inclusion complex contained in the polymerizable monomer composition of the present invention can be used.

The polymerizable monomer composition can contain the third polymerizable monomer, cellulose material, solvent S (eg, ionic liquid), etc., in addition to the inclusion complex. That is, the polymerizable monomer of the present invention may have the same composition as the polymerizable monomer composition used in step 1 in the method for producing the polymer composite material of the present invention.

Therefore, the polymerizable monomer composition of the present invention can be used as a raw material for producing the above-mentioned polymer composite material of the present invention, since the polymer A can be obtained by a simple method. can.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the embodiments of these examples.

(Production Example 1-1)
As a host group-containing polymerizable monomer, a compound represented by the following formula (H1) was produced by a known method (for example, the same procedure as in Production Example 6 of Patent Document 2). This was designated as "PAcγCDAAmMe". It was confirmed that the host group of the resulting PAcγCDAAmMe was a monovalent group obtained by removing one hydroxyl group from γ-cyclodextrin, and that 100% of all hydroxyl groups were substituted with acetyl groups.

According to the reaction scheme shown in FIG. 1, PAcγCDAAmMe as a host group-containing polymerizable monomer and 12-(acrylamide) dodecanoic acid as a guest group-containing polymerizable monomer (also referred to as 12-acrylamido dodecanoic acid). A polymerizable monomer mixture containing an inclusion complex was prepared. Specifically, PAcγCDAAmMe (denoted as “PAcCD” in FIG. 1), 12-(acrylamido)dodecanoic acid (denoted as “Dod” in FIG. 1), and hydroxy A mixture was prepared by mixing ethyl acrylate (HEA) in a molar ratio of 1:1:98, respectively. Next, this mixture was subjected to ultrasonic treatment at 25° C. for 90 minutes, thereby preparing a polymerizable monomer mixture in which an inclusion complex of PAcγCDAAmMe and 12-(acrylamido)dodecanoic acid was present in HEA. .

(Production Example 1-2)
PAcγCDAAmMe and N-dodecylacrylamide were added to HEA in the same manner as in Production Example 1-1, except that 12-(acrylamido)dodecanoic acid was replaced with N-dodecylacrylamide (containing no carboxyl group). A mixture of polymerizable monomers containing an inclusion complex was prepared.

(Production Example 1-3)
An inclusion complex of PAcγCDAAmMe and 12-(acrylamido)dodecanoic acid in EA was prepared in the same manner as in Production Example 1-1, except that ethyl acrylate (EA) having no hydroxyl group was used instead of HEA. A mixture of existing polymerizable monomers was prepared.

(Production Example 1-4)
PAcγCDAAmMe in EA in the same manner as in Production Example 1-1, except that 12-(acrylamido)dodecanoic acid was replaced with N-dodecylacrylamide and HEA was replaced with ethyl acrylate (EA). and an inclusion complex of N-dodecyl acrylamide was prepared.

(Production Example 2-1)
As a host group-containing polymerizable monomer, a compound represented by the following formula (H2) was produced by a known method (for example, the same procedure as in Production Example 7 of Patent Document 2). This was denoted as "PAcβCDAAmMe". It was confirmed that the host group of the resulting PAcβCDAAmMe was a monovalent group obtained by removing one hydroxyl group from β-cyclodextrin, and that 100% of all hydroxyl groups were substituted with acetyl groups.

Next, a polymerizable monomer mixture in which an inclusion complex of PAcβCDAAmMe and 12-(acrylamido)dodecanoic acid is present in HEA was prepared in the same manner as in Production Example 1-1 except that PAcγCDAAmMe was changed to PAcβCDAAmMe.

(Example 1-1)
A polymer composite material was prepared according to the scheme shown in FIG. First, as a cellulose material, citric acid-modified cellulose represented by the following formula (C1) (hereinafter abbreviated as “CNF”) and 1-butyl-3-methylimidazolium chloride (BMImCl) were mixed and heated at 100°C. A CNF solution with a concentration of 7.5% by mass was prepared by holding for 3 days. The citric acid-modified cellulose nanofiber was synthesized by the following procedure.

30 g of cellulose (manufactured by nacalai tesque) was dispersed in 200 mL of deionized water, 1.4 mL of 1 M NaOH aqueous solution was added, and the mixture was stirred for 5 minutes. Therefore, 90 g of citric acid was added and dissolved completely, then heated to 130° C. and reacted for 12 hours. The reaction was carried out in an open system and proceeded in the solid phase after evaporation of water. After the reaction, the supernatant was washed with water until the pH reached 7 to remove unreacted citric acid. Subsequently, it was washed with 300 mL of methanol and acetone, and dried under reduced pressure to obtain citric acid-modified cellulose. The introduction of citric acid into cellulose was confirmed by FT-IR measurement, and the amount of carboxylic acid introduced was 1.8 mmol/g determined from electrical conductivity measurement.

Next, the CNF solution and the polymerizable monomer mixture prepared in Production Example 1-1 are mixed so that the content of CNF in the CNF solution is 5% by mass with respect to the polymerizable monomer mixture. and continued stirring to obtain a uniform solution. A polymerizable monomer composition was prepared by adding 0.2 mol % of IRGACURE 184 (registered trademark) as a photopolymerization initiator to the solution with respect to the total amount of the polymerizable monomer mixture. This polymerizable monomer composition was added to the mold and irradiated with a mercury lamp (wavelength: 365 nm) for 1 hour to carry out a polymerization reaction. The obtained polymer was washed with water and then heated at 70° C. for 24 hours to remove the ionic liquid (BMImCl) in the polymer. Thereby, a polymer composite material having a thickness of 1 mm was obtained. The obtained polymer composite material was denoted as "PAcγCD-Dod-HEA-CNF (x, y, z)".

Here, x is the content ratio of the host group to the total amount of the host group-containing polymerizable monomer, the guest group-containing polymerizable monomer and the third polymerizable monomer used in producing the polymer composite material ( mol %), y is the content ratio (mol %) of the guest group with respect to the total amount of the host group-containing polymerizable monomer, the guest group-containing polymerizable monomer and the third polymerizable monomer, z is the polymerizable It is the content ratio (% by mass) of CNF with respect to the monomer mixture. Therefore, the polymer composite material obtained in Example 1-1 was denoted as PAcγCD-Dod-HEA-CNF (1, 1, 5).

(Example 1-2)
A polymer composite material was prepared in the same manner as in Example 1-1, except that the polymerizable monomer mixture prepared in Production Example 1-1 was changed to the polymerizable monomer mixture prepared in Production Example 1-2. got The obtained polymer composite material was denoted as "PAcγCD-DodAA-HEA-CNF (1, 1, 5)".

(Example 1-3)
A polymer composite material was prepared in the same manner as in Example 1-1, except that the polymerizable monomer mixture prepared in Production Example 1-1 was changed to the polymerizable monomer mixture prepared in Production Example 1-3. got The resulting polymer composite material was denoted as "PAcγCD-Dod-EA-CNF (1, 1, 5)". This polymer composite material was not in a solid state but in a homogeneous liquid state.

(Example 2-1)
A polymer composite material was prepared in the same manner as in Example 1-1, except that the polymerizable monomer mixture prepared in Production Example 1-1 was changed to the polymerizable monomer mixture prepared in Production Example 2-1. got The obtained polymer composite material was denoted as "PAcβCD-Dod-HEA-CNF (x, y, z)". Here, x, y and z are synonymous with "PAcγCD-Dod-HEA-CNF (x, y, z)" except that the host group is derived from a β-cyclodextrin derivative. Therefore, the polymer composite material obtained in Example 2-1 was denoted as PAcβCD-Dod-HEA-CNF (1, 1, 5).

(Comparative Example 1-1)
A raw material was prepared by adding 0.2 mol % of IRGACURE 184 (registered trademark) as a photopolymerization initiator to the total amount of the polymerizable monomer mixture prepared in Production Example 1-1. 365 nm) was irradiated for 1 hour to carry out a polymerization reaction. A polymer material was thus obtained. The obtained polymer material was described as "PAcγCD-Dod-HEA (1, 1, 0)".

(Comparative Example 1-2)
The CNF solution with a concentration of 7.5% by mass used in Example 1-1 and HEA are mixed so that the CNF in the CNF solution is 5% by mass with respect to HEA, and the mixture is uniformly mixed by continuing stirring. A clear solution was obtained. A raw material was prepared by adding 0.2 mol % of IRGACURE 184 (registered trademark) as a photopolymerization initiator to the total amount of HEA to the solution, and the raw material was irradiated with a mercury lamp (wavelength: 365 nm) for 1 hour to initiate a polymerization reaction. did The obtained polymer was washed with water and then heated at 70° C. for 24 hours to remove the ionic liquid (BMImCl) in the polymer. A polymer composite material was thus obtained. The obtained polymer composite material was described as "HEA-CNF (0, 0, 5)".

(Comparative Example 1-3)
A mixture was prepared by mixing PAcγCDAAmMe used in Production Example 1-1 and HEA at a molar ratio of 1:99. Next, this mixture and the 7.5% by mass CNF solution used in Example 1-1 are mixed so that the CNF in the CNF solution is 5% by mass with respect to the mixture, and stirring is continued. A homogeneous solution was thus obtained. A raw material was prepared by adding 0.2 mol % of IRGACURE 184 (registered trademark) as a photopolymerization initiator to the total amount of the mixture, and the raw material was irradiated with a mercury lamp (wavelength: 365 nm) for 1 hour to polymerize. reacted. The obtained polymer was washed with water and then heated at 70° C. for 24 hours to remove the ionic liquid (BMImCl) in the polymer. A polymer composite material was thus obtained. The obtained polymer composite material was described as "PAcγCD-HEA-CNF (1, 0, 5)".

(Comparative Example 1-4)
A mixture was prepared by mixing 12-(acrylamido)dodecanoic acid and HEA as a third polymerizable monomer at a molar ratio of 1:99. Next, this mixture and the 7.5% by mass CNF solution used in Example 1-1 are mixed so that the CNF in the CNF solution is 5% by mass with respect to the mixture, and stirring is continued. A homogeneous solution was thus obtained. A raw material was prepared by adding 0.2 mol % of IRGACURE 184 (registered trademark) as a photopolymerization initiator to the total amount of the mixture, and the raw material was irradiated with a mercury lamp (wavelength: 365 nm) for 1 hour to polymerize. reacted. The obtained polymer was washed with water and then heated at 70° C. for 24 hours to remove the ionic liquid (BMImCl) in the polymer. A polymer composite material was thus obtained. The obtained polymer composite material was denoted as "Dod-HEA-CNF (0, 1, 5)".

(Comparative Example 1-5)
Polymer was prepared in the same manner as in Example 1-1 except that the polymerizable monomer composition prepared in Production Example 1-1 was changed to the polymerizable monomer composition prepared in Production Example 1-4. A composite material was obtained. The obtained polymer composite material was denoted as "PAcγCD-DodAA-EA-CNF (1, 1, 5)". However, this polymer composite material was fragile due to the apparent phase separation of CNF, and various physical properties could not be measured.

(Comparative Example 2-1)
A raw material was prepared by adding 0.2 mol % of IRGACURE 184 (registered trademark) as a photopolymerization initiator to the total amount of the polymerizable monomer composition prepared in Production Example 2-1, and a mercury lamp ( A polymerization reaction was carried out by irradiating for 1 hour at a wavelength of 365 nm. A polymer material was thus obtained. The obtained polymer material was described as "PAcβCD-Dod-HEA (1, 1, 0)".

<Confirmation of hydrogen bonding>
The state of hydrogen bonding was confirmed by FT-IR measurement of the polymer composite material PAcγCD-Dod-HEA-CNF (1, 1, 5) obtained in Example 1-1. For FT-IR measurement, ATR-FTIR "JASCO FT/IR-6100 spectrometer" was used.

FIG. 3 shows FT-IR spectra of the polymer composite material PAcγCD-Dod-HEA-CNF (1, 1, 5) obtained in Example 1-1. As a comparison, FIG. 3 shows citric acid-modified cellulose nanofibers (CNF) together with the polymer material PAcγCD-Dod-HEA (1, 1, 0) obtained in Comparative Example 1-1 (CNF not used), Also shown is the spectrum of the ionic liquid BMImCl.

In FIG. 3, in the polymer composite material obtained in Example 1-1, the C=O stretching vibration is on the lower wave number side than the C=O stretching vibration in the polymer composite material obtained in Comparative Example 1-1. (1735→1723 cm ⁻¹ ), and it was confirmed that the absorption spectrum based on the OH stretching vibration in CNF in the 3200 to 3600 cm ⁻¹ region was broadened. From this result, it was found that in the polymer composite material obtained in Example 1-1, a polymer having a host group and a guest group and CNF formed hydrogen bonds.

FIG. 4 is a schematic diagram showing that CNF and host-guest polymer in the polymer composite material obtained in Example 1-1 form hydrogen bonds. As shown in FIG. 4, the carboxyl group derived from citric acid of CNF forms a hydrogen bond with the carboxyl group derived from the guest group in the host-guest polymer and the hydroxyl group derived from the third structural unit in the host-guest polymer. It can be said that

<SEM Observation>
FIG. 5(a) is the polymer material PAcγCD-Dod-HEA (1, 1, 0) obtained in Comparative Example 1-1, and (b) is the polymer composite material PAcγCD obtained in Example 1-1. - SEM images of Dod-HEA-CNF (1,1,5). From this result, it was found that the polymer composite material obtained in Example 1-1 and the polymer material obtained in Comparative Example 1-1 differ greatly in surface state. Since the polymer composite material obtained in Example 1-1 contains CNF, it can be said to have a fiber structure.

<Evaluation of mechanical properties>
In order to evaluate the mechanical properties of the polymer composite material obtained in each example and comparative example, a tensile test was performed on the polymer composite material. Specifically, a stress-strain curve is obtained by a "stroke-test force curve" test (manufactured by Shimadzu Corporation "AUTOGRAPH" (model number: AGX-plus), and from this stress-strain curve the breaking point of the polymer composite material In addition, the breaking point is the end point, and the maximum stress to the end point is the breaking stress of the polymer material.This tensile test is performed by fixing the lower end of the polymer composite material and pulling the upper end at a speed of 0.1 to 1 mm. / min.In addition, the stroke at that time, that is, the value obtained by dividing the maximum length when the polymer composite material is pulled by the length of the polymer composite material before stretching, is drawn. In addition, the fracture energy of the polymer composite material was calculated from the area of the stress-strain curve.

FIG. 6 shows the polymer composite material PAcγCD-Dod-HEA-CNF (1, 1, 5) obtained in Example 1-1 and the polymer composite material PAcγCD-Dod obtained in Comparative Example 1-1. - Shows the results of tensile tests for HEA (1,1,0). From this result, the polymer composite material (Example 1-1) composited by CNF and hydrogen bonding has a large elongation and breaking stress compared to the polymer material of Comparative Example 1-1 that does not contain CNF, and is excellent. It was found to have both flexibility and toughness.

Table 1 shows the polymer composite material PAcγCD-Dod-HEA-CNF (1, 1, 5) obtained in Example 1-1 and the polymer composite material PAcγCD-Dod obtained in Comparative Example 1-1. - Shows the result of calculating the fracture energy and Young's modulus from the tensile test of HEA (1, 1). From this result, the polymer composite material (Example 1-1) composited with CNF and hydrogen bonds has a larger fracture energy than the polymer material of Comparative Example 1-1 that does not contain CNF. Ta.

From the above results, the polymer composite material PAcγCD-Dod-HEA-CNF (1, 1, 5) obtained in Example 1-1 is composed of cellulose materials bonded by hydrogen bonding, and has excellent flexibility. , has been demonstrated to be a material with toughness and hardness.

<Importance of host-guest interaction>
FIG. 7 shows the results of the tensile test of the polymer composite material obtained in Example 1-1 and the polymer composite materials obtained in Comparative Examples 1-2, 1-3 and 1-4. .

As a result, the polymer composite material obtained in Example 1-1 had greater elongation and breaking stress than the polymer composite materials obtained in Comparative Examples 1-2, 1-3 and 1-4, and was excellent. It was found to have both flexibility and toughness. If the polymer composites obtained in Comparative Examples 1-2, 1-3 and 1-4 do not have either or both of the host group and the guest group, for example, composite with CNF Even if it is possible, it can be said that it cannot have the desired flexibility and toughness. On the other hand, when a polymer having a host group and a guest group is included as in the polymer composite material of Example 1-1, the guest group penetrates the host group, thereby forming a crosslinked structure of the polymer. is formed, so it is thought that excellent mechanical properties are exhibited.

<Importance of hydrogen bonding>
FIG. 8 shows the results of a tensile test of the polymer composite material obtained in Example 1-1 and the polymer composite material obtained in Example 1-2. Although both had excellent mechanical properties, the polymer composite material obtained in Example 1-1 was superior in flexibility and toughness. In Example 1-2, only the carboxy group of the guest group forms a hydrogen bond with the carboxy group of CNF, whereas the polymer composite material of Example 1-1 has a carboxy group in the guest group and a third structure The units have hydroxyl groups, both of which form hydrogen bonds with the carboxyl groups of CNF. Therefore, the polymer composite material of Example 1-1 has a stronger interaction between the CNF and the host-guest polymer than the polymer composite material of Example 1-2, and as a result, the polymer composite material of Example 1-1 has better flexibility and toughness than Example 1-2.

<Self-healing properties>
After cutting the central portion of each of the polymer composite materials obtained in Examples 1-1 and 2-1 into two, both were heated at room temperature (25° C.) or at 70° C. for 24 hours. The self-healing property was evaluated by contact. As a result, it was found that the cut pieces re-adhered to each other at both 25°C and 70°C for all polymer materials.

The self-healing rate of the polymer composite material of Example 1-1 was about 35% at 25°C and about 85% at 70°C, while the polymer composite material of Comparative Example 1-1 had a self-healing rate of 25%. 8% at °C and about 25% at 70°C. Further, in the polymer composite material of Example 2-1, it was about 10% at 25°C and about 25% at 70°C, whereas in the polymer composite material of Comparative Example 2-1, it was about 3% at 25°C. %, about 8% at 70°C. Therefore, it was also found that the polymer composite materials obtained in Examples 1-1 and 2-1 had self-healing properties.

The self-healing rate means the ratio of the area of the stress-strain curve of the polymer composite material after rebonding to the area of the stress-strain curve of the polymer composite material before cutting.

The results of Examples and Comparative Examples above demonstrate that the polymer composite materials obtained in Examples have excellent flexibility, toughness and hardness. Moreover, it was also shown that the polymer composite materials obtained in the examples had self-repairing properties in spite of being hard materials. It is surprising that the hard material has self-healing properties, and it is presumed that this is based on the effective action of host-guest interaction and hydrogen bonding.

Claims (7)

comprising a cellulose material and a polymer having host and guest groups;
The host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative,
The guest group is a monovalent group capable of penetrating the host group in a skewered manner,
The polymer comprises a structural unit having the host group in a side chain, a structural unit having a guest group in the side chain, and a third structural unit that does not have both the host group and the guest group,
The cellulose material is cellulose modified with a compound having at least one functional group F selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amide group,
A terminal of the guest group and the functional group F form a hydrogen bond,
The third structural unit is
The following general formula (a1)

(In formula (a1), Ra is a hydrogen atom or a methyl group, and R3 ^is a halogen atom, a hydroxyl group, a thiol group, an amino group or a salt thereof, a carboxyl group or a salt thereof, or an amide group or a salt thereof.)
Maleic anhydride, N-hydroxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylamide, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) ) A polymer composite material, which is a structural unit derived from one or more third polymerizable monomers selected from the group consisting of acrylate, N,N-dimethylacrylamide, acryloylmorpholine and ethyl (meth)acrylate. comprising a cellulose material and a polymer having host and guest groups;
The host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative,
The guest group is a monovalent group capable of penetrating the host group in a skewered manner,
The polymer comprises a structural unit having the host group in a side chain, a structural unit having a guest group in the side chain, and a third structural unit that does not have both the host group and the guest group,
The cellulose material is cellulose modified with a compound having at least one functional group F selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amide group,
the side chain of the third structural unit and the functional group F form a hydrogen bond,
The third structural unit is
The following general formula (a1)

(In formula (a1), Ra is a hydrogen atom or a methyl group, and R3 ^is a hydroxyl group, a thiol group, an amino group or a salt thereof, a carboxyl group or a salt thereof, or an amide group or a salt thereof.)
Maleic anhydride, N-hydroxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylamide, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) ) A polymeric composite material, which is a structural unit derived from at least one third polymerizable monomer selected from the group consisting of acrylate, N,N-dimethylacrylamide and acryloylmorpholine. at least one of the side chain terminal of the third structural unit and the terminal of the guest group has at least one functional group selected from the group consisting of a carboxy group, a hydroxyl group, an amino group and an amide group, or 2. The polymer composite material according to 2 . A polymerizable monomer composition used for producing the polymer composite material according to any one of claims 1 to 3,
An inclusion complex formed from a polymerizable monomer having a host group and a polymerizable monomer having a guest group ,
The inclusion complex is a polymerizable monomer composition in which the guest group penetrates the host group in a skewed manner. A method for producing a polymer composite material according to any one of claims 1 to 3 ,
an inclusion complex formed from a polymerizable monomer having a host group and a polymerizable monomer having a guest group; and a third polymerizable monomer not having both the host group and the guest group , a step of performing a polymerization reaction of a polymerizable monomer composition containing a cellulose material ,
The method for producing the inclusion complex, wherein the guest group penetrates the host group in a skewered manner. The production method according to claim 5 , wherein the polymerizable monomer composition contains an ionic liquid. A self-healing material comprising a polymeric composite material according to any one of claims 1-3 .