WO2024204165A1 - Polymer material and production thereof, and method for decomposing polymer material - Google Patents

Abstract

Provided are: a polymer material which is tough but can be easily decomposed; a method for producing the same; and a method for decomposing the polymer material.　This polymer material comprises: a polymer composition containing a polymer compound H; and a photoacid generator. The polymer compound H has at least one host group in the molecule. The host group is obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative, and is covalently bonded to the polymer compound H via a hemiaminal bond.

Description

Polymeric material, its production, and method for decomposing polymeric material

The present invention relates to a polymeric material and a method for producing the same, as well as a method for decomposing the polymeric material.

In recent years, the uses of polymeric materials have become increasingly diverse, and so there is a demand for the creation of polymeric materials with various functions that can keep up with this diversification. For example, polymeric materials that have improved physical properties that are in a trade-off relationship, such as being hard yet having excellent extensibility, are expected to be applied in a variety of fields.

From this perspective, for example, Patent Document 1 proposes polymer materials with a reversible cross-linked structure that utilizes host-guest interactions, and polymer materials with a mobile cross-linked structure. Such polymer materials have significantly improved mechanical properties such as toughness and strength, and are also capable of self-repairing, making them highly durable, which is why they are expected to be applied in a variety of fields.

JP 2021-181573 A

On the other hand, in the field of polymer materials, there is a strong demand these days for reducing the environmental burden, and there is a demand for polymer materials that can be "extended in use" and that can be "easily recovered as raw materials through decomposition." In other words, there is a demand for polymer materials that are stable and durable when in use, and that decompose easily after use or when being recovered. However, there is generally a trade-off between the mechanical properties (strength, etc.) of polymer materials and the decomposition efficiency of polymer materials, so it is considered difficult to impart both toughness and easy decomposition to polymer materials.

To explain more specifically, first, methods for improving the strength of polymer materials generally include strengthening the intermolecular interactions between polymer chains, forming crystals within the material, and introducing chemical crosslinks. However, no matter which of these methods is used, the polymer material obtained has extremely low polymer molecular mobility. For this reason, even if a component that decomposes the polymer material (decomposing agent) is added to the polymer material, the decomposing agent will not easily diffuse into the polymer material, resulting in a decrease in the decomposition efficiency of the polymer material. Although there are various decomposing agents for decomposing polymer materials, their decomposition effect is small when it comes to toughened polymer materials, making it difficult to decompose them efficiently.

The present invention has been made in consideration of the above, and aims to provide a polymeric material that is strong yet easily decomposable, a method for producing the same, and a method for decomposing the polymeric material.

As a result of extensive research into achieving the above objective, the inventors discovered that the above objective can be achieved by combining a polymer compound having a specific host group with a photoacid generator, and thus completed the present invention.

That is, the present invention includes, for example, the subject matter described in the following sections.
Item 1
A polymer composition containing a polymer compound H and a photoacid generator,
The polymer compound H has at least one host group in the molecule,
the host group is a group in which at least one hydrogen atom or hydroxyl group has been removed from a cyclodextrin or a cyclodextrin derivative,
The host group is covalently bonded to the polymeric compound H via a hemiaminal bond.
Item 2
Item 2. The polymer material according to item 1, wherein the hemiaminal bond is a bond represented by the formula -O-CH ₂ -NR ^b - (R ^b represents a hydrogen atom or an alkyl group).
Item 3
The polymer compound H is represented by the following general formula (1):

（式（１）中、Ｒ^ａは水素原子またはメチル基を表し、Ｒ^ｂは水素又はアルキル基を表し、Ｒ^Ｈは前記ホスト基を表す）
で表される単量体に基づく構成単位を有する、項１又は２に記載の高分子材料。
項４
前記高分子化合物Ｈが架橋構造体を形成している、項１～３のいずれか１項に記載の高分子材料。
項５
項１～４のいずれか１項に記載の高分子材料の製造方法であって、
前記ホスト基を有する重合性単量体を含有するモノマーと、前記光酸発生剤とを含有する原料の重合反応によって、前記高分子材料を得る工程を具備する、製造方法。
項６
項１～４のいずれか１項に記載の高分子材料の製造方法であって、
前記ポリマー組成物と、前記光酸発生剤とを混合することによって、前記高分子材料を得る工程を具備する、製造方法。
項７
項１～４のいずれか１項に記載の高分子材料の分解方法であって、
前記高分子材料に紫外線を照射する工程を具備する、高分子材料の分解方法。
項９
項８に記載の接着組成物を含有する接着剤層を備える積層体。

(In formula (1), R ^a represents a hydrogen atom or a methyl group, R ^b represents a hydrogen atom or an alkyl group, and R ^H represents the host group.)
Item 3. The polymer material according to item 1 or 2, having a structural unit based on a monomer represented by the following formula:
Item 4
Item 4. The polymer material according to any one of items 1 to 3, wherein the polymer compound H forms a crosslinked structure.
Item 5
A method for producing a polymeric material according to any one of items 1 to 4,
a step of obtaining the polymer material by a polymerization reaction of a raw material containing a monomer containing a polymerizable monomer having a host group and the photoacid generator.
Item 6
A method for producing a polymeric material according to any one of items 1 to 4,
The method includes a step of obtaining the polymer material by mixing the polymer composition with the photoacid generator.
Item 7
Item 5. A method for decomposing a polymer material according to any one of items 1 to 4, comprising:
A method for decomposing a polymer material, comprising the step of irradiating the polymer material with ultraviolet light.
Item 9
Item 9. A laminate comprising an adhesive layer containing the adhesive composition according to item 8.

The polymeric material of the present invention is a strong material, yet can be easily decomposed.

FIG. 2 is a schematic diagram of a crosslinked structure containing a polymer compound having a host group. 1 is a UV-Vis absorption spectrum of PAG. 1 shows the results of MALDI measurement in preliminary test 2. 1A is a MALDI-TOF-MS spectrum of PAcγCD obtained in Production Example 1, and FIG. 1B is a MALDI-TOF-MS spectrum of the dried product obtained in Test Example 1. FIG. 2 is a schematic diagram illustrating how a hemiaminal bond in a polymer compound is cleaved. 1 shows the results of USAXS-SAXS measurement of a polymeric material after ultraviolet irradiation in Test Example 1. 1 shows the results of stretching SAXS measurement of a polymeric material after ultraviolet irradiation in Test Example 1. 13 shows the results of mechanical properties obtained in Test Example 2. 4 shows the results of SEC measurement after irradiating a chloroform solution of the polymer material obtained in Example 3 with a mercury lamp. The results of the mechanical properties obtained in Test Examples 4-1 and 4-2 are shown below. 13 shows the results of mechanical properties obtained in Test Example 5. 1A is a schematic diagram showing the state of a tensile test performed in Application Example 1, and FIG. 1B is a diagram showing the results of mechanical properties performed in Application Example 1.

The following describes in detail the embodiments of the present invention. In this specification, the expressions "contain" and "include" include the concepts of "contain," "include," "consist essentially of," and "consist only of."

The polymer material of the present invention contains a polymer composition containing a polymer compound H and a photoacid generator. In the polymer material of the present invention, the polymer compound H has at least one host group in the molecule, and the host group is a group in which at least one hydrogen atom or hydroxyl group has been removed from cyclodextrin or a cyclodextrin derivative, and the host group is covalently bonded to the polymer compound H via a hemiaminal bond.

The polymer material of the present invention contains the polymer composition and a photoacid generator, making it a tough material that can be easily decomposed.

(Polymer Compound H)
The polymer material of the present invention contains, as an essential component, a polymer compound H having at least one host group. As described above, the host group is a group in which at least one hydrogen atom or hydroxyl group has been removed from cyclodextrin or a cyclodextrin derivative. The host group is not limited to a monovalent group, and may be, for example, a divalent group, and is preferably monovalent in terms of ease of production.

The cyclodextrin derivative preferably has a structure in which the hydrogen atom of at least one of the hydroxyl groups of cyclodextrin is replaced with a hydrophobic group. In other words, the cyclodextrin derivative refers to a molecule having a structure in which a cyclodextrin molecule is replaced with another organic group having hydrophobicity. However, the cyclodextrin derivative has at least one hydrogen atom or at least one hydroxyl group, and preferably has at least one hydroxyl group. The cyclodextrin derivative may be a cyclodextrin polymer, for example, a dimer. When the cyclodextrin derivative is a cyclodextrin polymer, the host group may be monovalent or may be divalent or higher.

The hydrophobic group is preferably a group 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). Hereinafter, in this 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)" may be referred to as "hydrocarbon group, etc." for convenience.

As a precaution, the term cyclodextrin in this specification means at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Therefore, 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 is a monovalent or higher group in which at least one hydrogen atom or hydroxyl group has been removed from a cyclodextrin or cyclodextrin derivative, but the hydrogen atom or hydroxyl group removed in the cyclodextrin derivative may be from any part of the cyclodextrin or cyclodextrin derivative. It is particularly preferable that the host group is a monovalent group in which one hydrogen atom or hydroxyl group has been removed from a cyclodextrin or cyclodextrin derivative.

If the total number of hydroxyl groups in one cyclodextrin molecule is N, then for α-cyclodextrin, N is 18, for β-cyclodextrin, N is 21, and for γ-cyclodextrin, N is 24.

If the host group is a monovalent group obtained by removing one "hydroxyl group" from a cyclodextrin derivative, the cyclodextrin derivative is formed by replacing the hydrogen atoms of up to N-1 hydroxyl groups per cyclodextrin molecule with hydrocarbon groups, etc. On the other hand, if the host group is a monovalent group obtained by removing one "hydrogen atom" from a cyclodextrin derivative, the cyclodextrin derivative can have the hydrogen atoms of up to N hydroxyl groups per cyclodextrin molecule replaced with hydrocarbon groups, etc.

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 cyclodextrin molecule are substituted with the hydrocarbon group or the like. It is more preferable that the hydrogen atoms of 80% or more of the total number of hydroxyl groups present in one cyclodextrin molecule are substituted with the hydrocarbon group or the like, and it is particularly preferable that the hydrogen atoms of 90% or more of the total number of hydroxyl groups are substituted with the hydrocarbon group or the like.

The host group preferably has a structure in which the hydrogen atoms of 13 or more of the total hydroxyl groups present in one molecule of α-cyclodextrin are substituted with the hydrocarbon group or the like. It is more preferable that the hydrogen atoms of 15 or more of the total hydroxyl groups present in one molecule of α-cyclodextrin are substituted with the hydrocarbon group or the like, and it is particularly preferable that the hydrogen atoms of 17 of the total hydroxyl groups are substituted with the hydrocarbon group or the like.

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

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

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

The number of carbon atoms in the hydrocarbon group is not particularly limited, but for example, it is preferable that the number of carbon atoms in the hydrocarbon group is 1 to 4.

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 either linear or branched.

In the cyclodextrin derivative, examples of the acyl group include an acetyl group, a propionyl group, and a formyl group. The acyl group is preferably an acetyl group, since it is easy to form a host-guest interaction, or other polymer chains can easily penetrate the host group ring, and it is easy to obtain a polymer material with excellent toughness and strength.

In the cyclodextrin derivative, -CONHR (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 is easy to form a host-guest interaction, or other polymer chains can easily penetrate the host group ring, and it is easy to obtain a polymer material with excellent toughness and strength.

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

The structure of the polymer compound H is not particularly limited as long as it has at least one host group. For example, the host group can be covalently bonded to the side chain of the polymer compound H. Even in this case, the host group is covalently bonded to the side chain of the polymer compound H via a hemiaminal bond.

An example of a hemiaminal bond is a bond represented by -O-CH ₂ -NR ^b -. Here, R ^b represents hydrogen or an alkyl group. When R ^b is an alkyl group, it has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a butyl group. The hydrocarbon group may be either linear or branched. Preferred R ^b is hydrogen, a methyl group, or an ethyl group, more preferably R ^b is hydrogen or a methyl group, and even more preferably R ^b is hydrogen.

In the hemiaminal bond --O--CH ₂ --NR ^b --, the host group may be bonded directly or indirectly to the oxygen atom of the hemiaminal bond, and it is preferred that the host group is bonded directly to the oxygen atom of the hemiaminal bond.

The polymer compound H can have a host group-containing monomer unit. In other words, the polymer compound H can be a polymer of a monomer that contains a host group-containing polymerizable monomer. Therefore, a monomer unit means a repeating structural unit that is formed when a polymerizable monomer is polymerized.

The host group-containing polymerizable monomer is, for example, a compound having at least one (preferably one) host group and at least one (preferably one) polymerizable functional group, with the hemiaminal bond between the host group and the polymerizable functional group.

The polymerizable functional group preferably has radical polymerizability, and examples thereof include groups containing a carbon-carbon double bond. Specific polymerizable functional groups include an acryloyl group (CH ₂ ═CH(CO)—), a methacryloyl group (CH ₂ ═CCH ₃ (CO)—), and other groups such as a styryl group, a vinyl group, and an allyl group. These groups containing a carbon-carbon double bond may further have a substituent as long as the radical polymerizability is not inhibited.

An example of a host group-containing polymerizable monomer is a compound represented by the following general formula (1):

In other words, the polymer compound H can have a constituent unit based on the monomer represented by formula (1).

Here, in the formula (1), R ^a represents a hydrogen atom or a methyl group, R ^b represents hydrogen or an alkyl group, and R ^H represents the host group. R ^b has the same meaning as R ^b in the above-mentioned hemiaminal bond -O-CH ₂ -NR ^b -. Therefore, in the formula (1), when R ^b is an alkyl group, it has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms, and examples of such groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a butyl group. The hydrocarbon group may be either linear or branched. Preferred R ^b is hydrogen, a methyl group, or an ethyl group, more preferably hydrogen or a methyl group, and ^even more preferably ^hydrogen .

The host group R ^H in the host group-containing polymerizable monomer represented by formula (1) is an example of a monovalent group obtained by removing one hydroxyl group from cyclodextrin or a derivative thereof. The host group-containing polymerizable monomer represented by formula (1) is a (meth)acrylamide derivative.

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

As can be seen from the structural formula, the host group-containing polymerizable monomer represented by formula (1) has a structure in which a host group is directly bonded to the oxygen atom of the hemiaminal bond, and an acryloyl group or methacryloyl group is bonded to the nitrogen atom of the hemiaminal bond.

The method for producing the host group-containing polymerizable monomer is not particularly limited, and for example, any known production method can be widely adopted.

The polymer compound H can have a monomer unit other than the host group-containing monomer unit. For example, the polymer compound H can have a guest group-containing monomer unit. The guest group-containing monomer unit means a repeating structural unit formed when a guest group-containing polymerizable monomer is polymerized.

The guest group-containing polymerizable monomer is, for example, a compound having at least one (preferably one) guest group and at least one (preferably one) polymerizable functional group. It is preferable that the guest group-containing polymerizable monomer does not have the hemiaminal bond.

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 in particular as long as it is a group that is included in the host group. The guest group is not limited to a monovalent group, and may be, for example, a divalent group. Furthermore, the guest group-containing monomer unit may contain only one guest group, or may contain two or more guest groups.

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. The substituents are the same as those described above, and examples of the substituents include halogen atoms (e.g., fluorine, chlorine, bromine, etc.), hydroxyl groups, carboxyl groups, ester groups, amide groups, and hydroxyl groups that may be protected.

More specific guest groups include linear or cyclic alkyl groups having 4 to 18 carbon atoms, and groups derived from polycyclic aromatic hydrocarbons. The linear alkyl groups having 4 to 18 carbon atoms may be either linear or branched. The cyclic alkyl groups may have a cage structure. Examples of polycyclic aromatic hydrocarbons include π-conjugated compounds formed of at least two or more aromatic rings, and specific examples include naphthalene, anthracene, tetracene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, etc.

Other examples of the guest group 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 consisting of alcohol derivatives; aryl compounds; carboxylic acid derivatives; amino derivatives; azobenzene derivatives having a cyclic alkyl group or a phenyl group; cinnamic acid derivatives; aromatic compounds and their alcohol derivatives; amine derivatives; ferrocene derivatives; azobenzene; naphthalene derivatives; anthracene derivatives; pyrene derivatives; perylene derivatives; clusters composed of carbon atoms such as fullerene; and dansyl compounds.

Further specific examples of guest groups include t-butyl groups, n-octyl groups, n-dodecyl groups, isobornyl groups, adamantyl groups, groups derived from pyrene, and groups to which the above-mentioned substituents are bonded.

The guest group-containing polymerizable monomer is not particularly limited as long as it is a compound having the guest group and polymerizability, and for example, a wide variety of known guest group-containing polymerizable monomers can be exemplified. The guest group-containing polymerizable monomer preferably has a functional group having radical polymerizability. Examples of the functional group having radical polymerizability include groups containing a carbon-carbon double bond, and specific examples thereof include an acryloyl group (CH ₂ ═CH(CO)—), a methacryloyl group (CH ₂ ═CCH ₃ (CO)—), and other groups such as a styryl group, a vinyl group, and an allyl group. These groups containing a carbon-carbon double bond may further have a substituent as long as the radical polymerizability is not inhibited.

Specific examples of guest group-containing polymerizable monomers include vinyl polymerizable monomers having the above-mentioned guest group. For example, examples of guest group-containing polymerizable monomers include compounds represented by the following general formula (g1):

In formula (g1), Ra represents a hydrogen atom or a methyl group, R ^G represents the guest group, and ^R2 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 alkoxy group which may have one or more substituents, a thioalkoxy group which may have one or more substituents, an alkyl group which may have one or more substituents, an amino group which may have one substituent, an amide group which may have one substituent, an aldehyde group, and a carboxyl group.

Among the polymerizable monomers represented by formula (g1), (meth)acrylic acid ester or a derivative thereof (i.e., ^R2 is -COO-) or (meth)acrylamide or a derivative thereof (i.e., ^R2 is -CONH- or -CONR-, and R has the same meaning as ^Rb ) is preferable. In this case, the polymerization reaction is likely to proceed, and therefore the production of the polymer compound H becomes easy.

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)acrylamidoadamantane, 2-ethyl-2-adamantyl (meth)acrylate, N-dodecyl (meth)acrylamide, t-butyl (meth)acrylate, 1-acrylamidoadamantane, N-(1-adamantyl) (meth)acrylamide, N-benzyl (meth)acrylamide, N-1-naphthylmethyl (meth)acrylamide, ethoxylated o-phenylphenol acrylate, phenoxy polyethylene glycol acrylate, isostearyl acrylate, nonylphenol EO adduct acrylate, isobornyl (meth)acrylate, (meth)acrylates having a pyrene moiety, and (meth)acrylamides having a pyrene moiety.

The guest group-containing polymerizable monomer can be produced by a known method. In addition, commercially available guest group-containing polymerizable monomers can also be used.

The polymer compound H may also have a monomer unit other than the host group-containing monomer unit and the guest group-containing monomer unit. Hereinafter, the monomer unit other than the host group-containing monomer unit and the guest group-containing monomer unit is referred to as the "third monomer unit."

The third monomer unit refers to a repeating structural unit formed when a polymerizable monomer (third polymerizable monomer) copolymerizable with the host group-containing polymerizable monomer and the guest group-containing polymerizable monomer is polymerized. The third polymerizable monomer does not have the host group or the guest group. It is preferable that the third polymerizable monomer does not have the hemiaminal bond.

The third polymerizable monomer may be any of various known vinyl polymerizable monomers. Specific examples of the third polymerizable monomer include compounds represented by the following general formula (a1).

In formula (a1), Ra represents a hydrogen atom or a methyl group, and ^R3 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.

In formula (a1), when R ³ is a carboxyl group having one substituent, examples of the carboxyl group include a carboxyl group (i.e., an ester) in which the hydrogen atom of the carboxyl group is substituted with a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyalkyl group (e.g., a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group), a methoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5), an ethoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5), or the like. The hydrocarbon group having 1 to 20 carbon atoms preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 3 carbon atoms. The hydrocarbon group may be either linear or branched.

In formula (a1), when ^R3 is an amide group having one or more substituents, i.e., a secondary amide or a tertiary amide, examples of such a group include amide groups in which one hydrogen atom or two hydrogen atoms of the primary amide are independently substituted with a hydrocarbon group or a hydroxyalkyl group having 1 to 20 carbon atoms (e.g., a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group). The hydrocarbon group having 1 to 20 carbon atoms preferably has 1 to 15 carbon atoms, and more preferably has 2 to 10 carbon atoms. The hydrocarbon group may be either linear or branched.

Specific examples of monomers represented by formula (a1) include (meth)acrylic acid, allylamine, maleic anhydride, 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, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethylacrylamide, N-isopropyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, ethoxy-diethylene glycol (meth)acrylate, methoxy-triethylene glycol (meth)acrylate, methoxy-polyethylene glycol (meth)acrylate, and styrene. These can be used alone or in combination of two or more types.

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 polymer compound H.

As described above, in one embodiment, polymer compound H contains a host group-containing monomer unit, and may contain one or more types selected from the group consisting of guest group-containing monomer units and third monomer units, as necessary, and polymer compound H preferably contains at least both the host group-containing monomer unit and the third monomer unit.

The content of the host group-containing monomer units in all the structural units of polymer compound H 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. In addition, the content of the host units in all the structural units of polymer compound H 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 the present invention, the ratio (molar ratio) of each structural unit in polymer compound H can be considered to be the same as the molar ratio of each monomer used in the production of the polymer compound.

The mass average molecular weight (Mw) of the polymer compound H is not particularly limited, and can be, for example, 10,000 to 2,000,000, and preferably 20,000 to 1,000,000. The polymer compound H can be, for example, a random polymer, and can be linear, and can also have a branched structure and a crosslinked structure as long as the effects of the present invention are not inhibited.

The host group-containing monomer unit, guest group-containing monomer unit, and third monomer unit contained in the polymer compound H may each be one type alone or two or more types.

The method for producing the polymer compound H is not particularly limited, and any known production method can be widely adopted. For example, the polymer compound H can be produced by a polymerization reaction of a raw material containing the host group-containing polymerizable monomer and, if necessary, the guest group-containing monomer unit and/or the third polymerizable monomer. The polymerization reaction is also not particularly limited, and, for example, when the raw material contains a radical polymerizable monomer, any known radical polymerization reaction can be widely applied.

More specific embodiments of polymer compound H include polymer compound H1, polymer compound H2, and polymer compound H3 shown below.
Polymer compound H1: a polymer compound containing a host group-containing monomer unit, a guest group-containing monomer unit, and a third monomer unit.
Polymer compound H2: a polymer compound containing a host group-containing monomer unit and a third monomer unit, but not containing a guest group-containing monomer unit.
Polymer compound H3: a polymer compound comprising a host group-containing monomer unit and a third monomer unit large enough to penetrate the host group.

<High molecular compound H1>
Polymer compound H1, which is one embodiment of polymer compound H, contains a host group-containing monomer unit, a guest group-containing monomer unit, and a third monomer unit.

In the polymer compound H1, the content of the guest group-containing monomer unit 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, and 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, based on the total constituent units of the polymer compound 1.

In the polymer compound H1, the content of the third monomer unit is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more, preferably 99.8 mol% or less, and more preferably 99 mol% or less, of all the constituent units of the polymer compound H1.

In the polymer compound H1, the combination of the host group and the guest group is not particularly limited, and the host group and the guest group described above can be combined in any way. In particular, 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 and dodecyl groups, because it is easy to form the host-guest interaction described below and to improve the mechanical properties of the polymer material. For the same reason, 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 and isobornyl groups, and 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, dodecyl, cyclododecyl, adamantyl, and groups derived from polycyclic aromatic hydrocarbons. Examples of polycyclic aromatic hydrocarbons include pyrene.

The polymer compound H1 can also be formed from only the host group-containing monomer unit, the guest group-containing monomer unit, and the third monomer unit.

<High molecular compound H2>
Polymer compound H2, which is one embodiment of polymer compound H, contains a host group-containing monomer unit and a third monomer unit, but does not contain a guest group-containing monomer unit.

The polymer compound H2 having such a structure can form a host-guest interaction with the guest group-containing polymer compound G described below. In addition, in the polymer compound H2, it is preferable that the third monomer unit has a size that does not allow it to penetrate the host group.

The polymer compound H2 can also be formed from only the host group-containing monomer unit and the third monomer unit.

<High molecular compound H3>
Polymer compound H3, which is one embodiment of polymer compound H, contains a host group-containing monomer unit and a third monomer unit having a size capable of penetrating the host group.

In the polymer compound H3, the third monomer unit having a size capable of penetrating the host group is preferably based on (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide or a derivative thereof when the host group is derived from γ-cyclodextrin or a derivative thereof, more preferably methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, etc., and particularly preferably ethyl (meth)acrylate when the host group is γ-cyclodextrin or a derivative thereof.

It is preferable that the polymer compound H3 does not contain a guest group-containing monomer unit, and the polymer compound H3 may also be formed only from a host group-containing monomer unit and a third monomer unit.

(Polymer Composition)
The polymer composition contained in the polymer material of the present invention contains at least the polymer compound H. The polymer composition may contain other polymer compounds in addition to the polymer compound H. Examples of the other polymer compounds include a polymer compound containing a guest group and a chain polymer compound. Hereinafter, the polymer compound containing a guest group will be referred to as "polymer compound G" and the chain polymer compound will be referred to as "chain polymer compound P".

<Guest Group-Containing Polymer Compound G>
The polymer compound G has the guest group-containing monomer unit and the third monomer unit in its molecule, but does not contain the host monomer unit. The guest group is bonded to the main chain or side chain of the polymer compound G by a covalent bond.

In terms of the polymer material being more likely to have improved mechanical properties and excellent flexibility, the content of the guest group-containing monomer unit in all the constituent units of the polymer compound G 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, and 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 terms of the polymer material being more likely to have improved mechanical properties and excellent flexibility, the content of the third monomer unit in all of the constituent units of polymer compound G is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more, and is preferably 99.9 mol% or less, and more preferably 99 mol% or less.

The polymer compound G may contain other monomer units (excluding the host unit) as long as the effect of the present invention is not inhibited, or the polymer compound G may be formed only from the host unit and the third unit.

The mass average molecular weight (Mw) of the polymer compound G is not particularly limited, and can be, for example, 10,000 to 2,000,000, and preferably 20,000 to 1,000,000. The polymer compound G can be, for example, a random polymer, and can be linear, and can also have a branched structure and a crosslinked structure, so long as the effects of the present invention are not inhibited. The method for producing the polymer compound G is not particularly limited, and a wide variety of known production methods can be adopted.

When the polymer composition contains polymer compound G, the third units between polymer compound H and polymer compound G may be the same as each other, or may be partially or completely different.

When the polymer composition contains polymer compound G, the combination of the host group of polymer compound H and the guest group of polymer compound G is not particularly limited, and the host group and guest group described above can be combined arbitrarily. Among them, 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 and dodecyl groups, because at least one of the host groups of polymer compound H and at least one of the guest groups of polymer compound G are likely to improve the mechanical properties of the polymer material through host-guest interaction. For the same reason, 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 and isobornyl groups, and 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, dodecyl, cyclododecyl, adamantyl, and groups derived from the polycyclic aromatic hydrocarbons.

<Chained polymer compound P>
The chain polymer compound P is, for example, a polymer compound having the third monomer unit and having no host group. The polymers are preferably polymers of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth)acrylamide or derivatives thereof. More preferably, it is a polymer such as isopropyl acrylate.

The chain polymer compound P may contain other monomer units (excluding host units and guest units) as long as the effects of the present invention are not impaired, or the chain polymer compound P may be formed only from the third unit.

The mass average molecular weight (Mw) of the chain polymer compound P is not particularly limited, and can be, for example, 10,000 to 2,000,000, and preferably 20,000 to 1,000,000. The chain polymer compound P can have a structure such as a homopolymer or a random polymer, and can be linear, and can also have a branched structure and a crosslinked structure as long as the effects of the present invention are not inhibited.

The method for producing the chain polymer compound P is not particularly limited, and a wide variety of known production methods can be used. For example, the chain polymer compound P can be produced by a polymerization reaction of a raw material containing the third polymerizable monomer. The polymerization reaction is also not particularly limited, and for example, when the raw material contains a radically polymerizable monomer, a wide variety of known radical polymerization reactions can be applied.

When the polymer composition contains a chain polymer compound P, the third units in the polymer compound H and the chain polymer compound P may be the same as each other, or may be partially or completely different.

<Form of polymer composition>
In the polymer material of the present invention, it is preferable that the polymer compound H contained in the polymer composition forms a crosslinked structure. In this case, the mechanical properties of the polymer material of the present invention are improved, and a tough material is easily formed. The crosslinked structure may be formed, for example, between the polymer compounds H, or between the polymer compound H and another polymer compound (for example, the polymer compound G or the chain polymer compound P).

The form of the polymer composition is not particularly limited as long as it contains polymer compound H. For example, the polymer composition may have the following forms: Polymer composition A, Polymer composition B, Polymer composition C, Polymer composition D, Polymer composition E, Polymer composition F, Polymer composition G, etc.

<Polymer composition A>
Polymer composition A, which is one embodiment of the polymer composition, contains the above-mentioned polymer compound H1. Since polymer compound H1 has a host group and a guest group in its molecule, host-guest interaction can be formed between the molecules. That is, at least one guest group of another polymer compound H1 is included in at least one host group of the polymer compound H1, and thus, host-guest interaction between the molecules is formed, and a crosslinked structure of polymer compound H1 can be formed.

Furthermore, such intermolecular host-guest interactions can give the polymer material self-repairing properties. In this case, even if the polymer material is cut, the cut surfaces can be re-adhered, and the host-guest interaction will be formed again at the adhesive surface, resulting in re-joining and self-repair.

The polymer composition A may consist only of the crosslinked structure of the polymer compound H1. The polymer composition A may further contain other polymer compounds, as long as the effect of the present invention is not impaired.

The method for preparing polymer composition A is not particularly limited, and for example, a wide variety of known methods can be used. For example, a crosslinked structure of polymer compound H1 can be formed by using an inclusion compound of a host group-containing polymerizable monomer and a guest group-polymerizable monomer, and polymerizing the inclusion compound with a third polymerizable monomer, and this can be used as polymer composition A.

<Polymer composition B>
Polymer composition B, which is one embodiment of the polymer composition, contains the above-mentioned polymer compound H2 and polymer compound G. In this case, the two polymer compounds can form a host-guest interaction between their molecules. That is, at least one guest group of polymer compound G is included in at least one host group of polymer compound H2, thereby forming an intermolecular host-guest interaction, and a crosslinked structure of polymer compound H2, more specifically, a crosslinked structure between polymer compound H2 and polymer compound G, can be formed. In addition, like polymer composition A, it can also have self-repairing properties.

Polymer composition B may consist only of a crosslinked structure of polymer compound H2 and polymer compound G. Polymer composition B may further contain other polymer compounds as long as the effects of the present invention are not impaired.

The method for preparing polymer composition B is not particularly limited, and any known method can be widely adopted. For example, polymer compound H2 and polymer compound G can be mixed to form a crosslinked structure, which can be used as polymer composition B.

<Polymer composition C>
The polymer composition C, which is one embodiment of the polymer composition, contains the above-mentioned polymer compound H2, and further contains the chain polymer compound P as necessary. When the polymer composition C contains the chain polymer compound P, the chain polymer compound P can penetrate into the ring of the host group of the polymer compound H2. This allows the polymer compounds H2 to be crosslinked with each other by the chain polymer compound P to form a crosslinked structure, and in such a crosslinked structure, the chain polymer compound P can slide within the host group ring, so that it can become a so-called mobile crosslinked structure.

FIG. 1(a) shows a schematic diagram of a crosslinked structure (mobile crosslinked structure) in polymer composition C in which polymer compounds H2 having host groups h are crosslinked with each other by a chain polymer compound P. As shown in FIG. 1(a), the chain polymer compound P penetrates the host h group of polymer compound H2, so that the polymer compounds H2 are crosslinked with each other by the chain polymer compound P, forming a mobile crosslinked structure. As a result, the mechanical properties of polymer composition C are improved, and the polymer composition C can have excellent flexibility while being tough.

In the polymer composition C, the content ratio of the polymer compound H2 and the chain polymer compound P is not particularly limited. For example, the content ratio of the host unit in the polymer compound H2 relative to the total amount of the constituent units of both the polymer compound H2 and the chain polymer compound P is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, even more preferably 0.3 mol% or more, and particularly preferably 0.5 mol% or more, and 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 polymer composition C, the third monomer unit in polymer compound H2 is preferably of a size that does not allow it to penetrate into the ring of the host group of polymer compound H2. Examples of the third polymerizable monomer for constituting such a third monomer unit include styrene, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, methoxyethyl (meth)acrylate, hexyl (meth)acrylate, 2-ethoxy-hexyl (meth)acrylate, dodecyl (meth)acrylate, and polyethylene glycol (meth)acrylate.

In the polymer composition C, the chain polymer compound P is preferably a polymer of (meth)acrylic acid, a (meth)acrylic acid ester, (meth)acrylamide or a derivative thereof, and more preferably a polymer of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, or the like.

The third monomer unit in the polymer compound H2 and the chain polymer compound P is of a different type. In other words, the third monomer unit in the polymer compound H2 cannot penetrate the host group in the polymer compound H2, whereas the third monomer unit in the chain polymer compound P can penetrate the host group in the polymer compound H2.

The polymer composition C may consist only of a crosslinked structure of the polymer compound H2 and the chain polymer compound P. The polymer composition C may further contain other polymer compounds as long as the effects of the present invention are not impaired.

The polymer composition C can be prepared, for example, by the following method. First, a polymerization reaction of a raw material (third monomer unit) for obtaining a chain polymer compound P is carried out in the presence of the polymer compound H2 that has been produced in advance. This polymerization reaction causes the growth reaction of the chain polymer compound P to proceed, and at the same time, the growing polymer chain can penetrate the host group. As a result, a mobile crosslinked structure composed of the polymer compound H2 and the chain polymer compound P is produced.

<Polymer composition D>
The polymer composition D, which is one embodiment of the polymer composition, contains the above-mentioned polymer compound H3. In the polymer composition D, the main chain of the other polymer compound H3 penetrates at least one of the host groups possessed by the polymer compound H3. The third monomer unit in the polymer compound H3 has a size capable of penetrating the inside of the ring of the host group possessed by the polymer compound H3, so that the main chain of the other polymer compound H3 can penetrate the inside of the host group ring of the polymer compound H3, and more strictly speaking, a segment composed of the third unit in the other polymer compound H3 penetrates the inside of the host group ring. As a result, in the polymer composition D, a crosslinked structure (mobile crosslinked structure) between the polymer compounds H3 is formed.

FIG. 1(b) is a schematic diagram showing a state in which the host group h of the polymer compound H3 is penetrated by another polymer compound H3. By the other polymer compound H3 penetrating the host group of the polymer compound H3, a mobile cross-linked structure X is formed by the polymer compound H3, which improves the mechanical properties of the polymer material and allows it to have excellent flexibility while being tough. In addition, since the polymer compound Hc that has penetrated the host group also has a host group, the host group acts as a so-called stopper and can prevent falling off.

The polymer composition D may consist only of the polymer compound H3. The polymer composition D may further contain other polymer compounds as long as the effect of the present invention is not impaired.

The method for forming the mobile cross-linked structure of the polymer compound H3 is not particularly limited. For example, a polymerization reaction for producing the polymer compound H3 can be carried out to form a mobile cross-linked structure while the polymer compound H3 is being produced. Specifically, in the polymerization reaction of the polymer compound H3, as the growth reaction of the polymer compound H3 progresses, the growing polymer chain penetrates the host group of another polymer chain, and thus a mobile cross-linked structure as shown in FIG. 1(b) can be formed.

<Polymer composition E>
Polymer composition E, which is one embodiment of the polymer composition, contains the above-mentioned polymer compound H3 and the chain polymer compound P. In polymer composition E, a mobile crosslinked structure is formed by polymer compound H3 similar to polymer composition D, and chain polymer compound P can be present in the mobile crosslinked structure. This can further improve the mechanical properties of the polymer material.

FIG. 1(c) is a schematic diagram of the crosslinked structure of polymer composition E. As shown in FIG. 1(c), in polymer composition E, similar to polymer composition D, a mobile crosslinked structure X is formed by a polymer compound H3 having a host group h, and a chain polymer compound P may exist penetrating the mesh of the crosslinked structure.

In the polymer composition E, the content ratio of the polymer compound H3 and the chain polymer compound P is not particularly limited. For example, in terms of being likely to improve mechanical properties, the content ratio of the polymer compound H3 relative to the total mass of the polymer compound H3 and the chain polymer compound P can be, for example, 10 mass% or more, preferably 20 mass% or more, more preferably 40 mass% or more, and even more preferably 50 mass% or more, and can be 90 mass% or less, preferably 80 mass% or less, and more preferably 70 mass% or less.

The polymer composition E may consist only of the polymer compound H3 and the chain polymer compound P. The polymer composition E may further contain other polymer compounds as long as the effect of the present invention is not impaired.

The method for producing the polymer composition E is not particularly limited, and for example, a wide variety of known methods can be used. For example, the polymer composition E can be prepared by carrying out a polymerization reaction to synthesize a chain polymer compound P in the presence of the polymer compound H3 that has been produced in advance to form a mobile cross-linked structure.

<Polymer composition F>
Polymer composition F, which is one embodiment of the polymer composition, contains a first polymer compound H3 and a second polymer compound H3. That is, polymer composition F contains at least two different kinds of polymer compounds H3.

In the polymer composition F, the third monomer units in the first polymer compound H3 and the second polymer compound H3 can both be (meth)acrylic acid ester units, for example. In this case, the (meth)acrylic acid ester units in the first polymer compound H3 and the second polymer compound H3 can be configured such that the number of carbon atoms in the alkyl group of the alkyl ester portion is different from each other. Specifically, a combination in which the (meth)acrylic acid ester unit in the first polymer compound H3 is methyl (meth)acrylate and the (meth)acrylic acid ester unit in the second polymer compound H3 is ethyl (meth)acrylate can be mentioned.

The polymer composition F contains a mobile cross-linked structure formed by a first polymer compound H3 and a mobile cross-linked structure formed by a second polymer compound H3. When the former mobile cross-linked structure is the first mobile cross-linked structure and the latter mobile cross-linked structure is the second mobile cross-linked structure, the mobile cross-linked structures can exist independently of each other, or can exist in a state where they are entangled with each other.

FIG. 1(d) is a schematic diagram showing the crosslinked structure of polymer composition F. As shown in FIG. 1(d), in polymer composition F, a mobile crosslinked structure X1 is formed by a first polymer compound H3(1) having a host group h, and a mobile crosslinked structure X2 is formed by a second polymer compound H3(2) having a host group h. The crosslinked structure X1 and the crosslinked structure X2 exist in a mutually entangled state.

(Photoacid generator)
The photoacid generator is not particularly limited in type, so long as it is a compound that is decomposed by ultraviolet light to generate an acid. Examples of the acid generated by the photoacid generator include sulfonic acids such as hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octane sulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctane sulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, and dodecylbenzenesulfonic acid, or hydrates or salts thereof.

Specific examples of photoacid generators include those disclosed in International Publication No. 2018/56281. Among them, a preferred photoacid generator is bis(cyclohexylsulfonyl)diazomethane. In these cases, the decomposition of the polymer material is easily accelerated by irradiation with light, which makes it easier to recover the raw materials, for example.

The ultraviolet light used to decompose the photoacid generator preferably has a wavelength of 150 to 300 nm, and more preferably 200 to 250 nm.

(Polymer materials)
The polymer material of the present invention contains a polymer composition containing a polymer compound H and a photoacid generator. In the polymer material of the present invention, the content ratio of the polymer compound H and the photoacid generator is not particularly limited. For example, in terms of facilitating decomposition of the polymer material, the content of the photoacid generator relative to 100 parts by mass of the polymer compound H can be 0.1 parts by mass or more, preferably 1 part by mass or more, more preferably 25 parts by mass or more, even more preferably 50 parts by mass or more, and particularly preferably 100 parts by mass or more, and can be 500 parts by mass or less, preferably 450 parts by mass or less, more preferably 400 parts by mass or less, even more preferably 350 parts by mass or less, and particularly preferably 300 parts by mass or less.

The photoacid generator may be incorporated into the crosslinked structure containing the polymer compound H, or may exist independently of the crosslinked structure. The photoacid generator may be unevenly distributed in the polymer material, or may exist uniformly.

The polymer material may contain additives other than the polymer composition and the photoacid generator, so long as the effect of the present invention is not impaired. The polymer material may be formed only from the polymer composition and the photoacid generator. The polymer composition and the photoacid generator may be 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 950% by mass or more, based on the total amount of the polymer material.

The method for producing the polymer material is not particularly limited. For example, the polymer material of the present invention can be obtained by a production method including the following step A.
Step A: A step of obtaining the polymer material by a polymerization reaction of a raw material containing a monomer containing a polymerizable monomer having a host group and the photoacid generator.

The manufacturing method including step A is a method in which the polymerization reaction of polymer compound H is carried out in the presence of the photoacid generator. In step A, the monomer containing a polymerizable monomer having a host group is, for example, a mixed monomer containing the host group-containing polymerizable monomer (for example, a monomer represented by formula (1)) described above. Such a mixed monomer can contain, for example, a predetermined amount of the guest group-containing polymerizable monomer and/or a third polymerizable monomer depending on the type of polymer composition.

When a photopolymerization initiator is used in the polymerization reaction of step A, it is preferable that such a photopolymerization initiator has the property of initiating polymerization with ultraviolet light in a wavelength range in which the photoacid generator does not decompose. Specifically, the ultraviolet light that can be used in the polymerization reaction of step A preferably has a wavelength of 350 to 450 nm, and more preferably 370 to 450 nm. It is preferable to use a photopolymerization initiator that can be used in this wavelength range in step A.

As for the method for producing a polymer material, the polymer material of the present invention can be obtained by, for example, a production method including the following step B.
Step B: A step of obtaining the polymer material by mixing the polymer composition with the photoacid generator.

In step B, the method for mixing the polymer composition and the photoacid generator is not particularly limited, and for example, the mixing process can be performed using a known mixing means.

The polymer material of the present invention can be obtained by a manufacturing method including step A or step B as described above.

The polymeric material of the present invention contains a polymer composition that contains polymer compound H, and is therefore a strong material with excellent mechanical properties and excellent toughness. In particular, when the polymer composition is any of the above-mentioned polymer compositions A, B, C, D, E, and F, the toughness is particularly excellent.

The form of the polymeric material is not particularly limited, and may be, for example, a molded product such as a film, sheet, plate, or block, or may be in the form of particles, fibers, granules, pellets, or may be in a dispersed or dissolved state in a solvent.

When producing a molded body made of a polymer material, the manufacturing method is not particularly limited, and any known molding method can be widely used, such as a casting method, a press molding method, an extrusion molding method, an injection molding method, etc.

(Method of decomposing polymeric materials)
Since the polymer material of the present invention contains a photoacid generator in addition to the polymer composition, the polymer material can be decomposed by irradiating the polymer material with ultraviolet light. Specifically, when the polymer material is irradiated with ultraviolet light, the hemiaminal bond site is cleaved. This causes the host group to separate from the polymer compound H, and as a result, the crosslinked structure formed by the polymer compound H is dissolved, causing the so-called decomposition of the polymer material. This allows the cyclodextrin or its derivative derived from the host group to be recovered from the polymer material, or the polymer component in the polymer material to be recovered.

For example, when the polymer compound H contained in the polymer material has a constitutional unit based on the monomer represented by formula (1) above, when the hemiaminal bond site is cleaved, R ^H -OH (R ^H is a host group) can be generated.

The method for recovering the host group-derived cyclodextrin or its derivative from the polymer material is not particularly limited. For example, a recovery method using a solvent can be preferably adopted, taking advantage of the phenomenon that dissolution or extraction into a solvent becomes easier when the crosslinked structure is eliminated. The type of solvent is not limited, and an appropriate organic solvent can be selected depending on the solubility of the polymer or cyclodextrin compound.

The method for decomposing the polymeric material is not particularly limited. For example, the polymeric material can be decomposed by a method including a step of irradiating the polymeric material with ultraviolet light. As mentioned above, the wavelength of the ultraviolet light is preferably 150 to 300 nm, and more preferably 200 to 250 nm. The duration of the ultraviolet light exposure can be, for example, 30 to 90 minutes.

When decomposing the polymeric material, it is also possible to make the polymeric material contain moisture. In this case, it is easier to promote the decomposition of the polymeric material, and the recovery efficiency can be further increased. For example, when decomposing the polymeric material, the amount of moisture in the polymeric material is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, relative to the total mass of the polymeric material.

When a polymeric material contains moisture, the mechanical properties of the polymer (e.g., the breaking stress of the polymeric material) tend to decrease after the polymeric material is decomposed by UV irradiation. This tends to increase the efficiency of recovering cyclodextrin compounds and polymer components from the polymeric material.

Therefore, one aspect of the method for decomposing a polymeric material includes a step of irradiating a polymeric material containing moisture with ultraviolet light. There are no particular limitations on the method for adding moisture to the polymeric material, and for example, a method of adding a predetermined amount of moisture to the polymeric material can be used.

Whether the polymer composition contained in the polymer material is any of the above-mentioned polymer compositions, it can be decomposed and has excellent recovery efficiency, but among them, polymer composition F is particularly excellent in terms of recovery efficiency after decomposition of the polymer material.

Polymer materials have excellent mechanical properties and also excellent decomposition performance, so they can exhibit sufficient mechanical strength when in use, and when no longer needed, they can be easily decomposed and various components can be recovered as needed. Therefore, the polymer material of the present invention can be used for various purposes, and for example, the polymer material can be suitably used for various components such as automobiles, electronic parts, building materials, food containers, and transport containers.

The excellent mechanical properties and degradability of polymeric materials make them suitable for use in adhesives, for example. Adhesives containing the polymeric material of the present invention can firmly bond adherends together. To remove adhesion, i.e. to peel off the adherends, simply irradiate with ultraviolet light. This causes the polymeric material to decompose, reducing the adhesive strength between the polymeric material and the adherend, making it easier to peel them off.

Accordingly, an adhesive composition can be prepared using the polymer material of the present invention, and such an adhesive composition, by containing the polymer material of the present invention, can provide an adhesive layer that is excellent in adhesion and can be easily peeled off. This allows peeling without causing damage to the adherend, making it easy to reuse the adherend.

Various types of laminates can be formed using an adhesive layer formed from the adhesive composition. For example, a laminate can be formed by preparing a pair of adherends, forming an adhesive layer of the adhesive composition on one of the adherends, and attaching the other adherend to the adhesive layer.

In identifying the inventions encompassed by this disclosure, the configurations (properties, structures, functions, etc.) described in each embodiment of this disclosure may be combined in any way. In other words, this disclosure encompasses all subject matter consisting of all combinations of the combinable configurations described in this specification.

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

(Production Example 1)
5 g (3.9 mmol) of gamma cyclodextrin, 700 mg (6.9 mmol) of N-hydroxymethylacrylamide, and 95 mg (0.6 mmol) of p-toluenesulfonic acid monohydrate were weighed into a 200 mL round-bottom glass flask, and these were added to 25 mL of N,N-dimethylformamide to prepare a reaction solution. The solution was heated to 90°C in an oil bath and heated and stirred for 1 hour to obtain a reaction solution. The reaction solution was then allowed to cool and poured into 45 mL of vigorously stirred acetone. The resulting precipitate was filtered off, washed three times with 10 mL of acetone, and dried under reduced pressure at room temperature for 1 hour to obtain a reaction product. The reaction product was dissolved in 100 mL of distilled water, passed through a column (apparent density 600 g/L) packed with porous polystyrene resin (Mitsubishi Chemical Diaion HP-20), and adsorbed for 30 minutes. After that, the solution components were removed, and 50 mL of 10% methanol (or acetonitrile) aqueous solution was passed through the column three times to wash the polystyrene resin and remove unreacted γ-cyclodextrin. Next, 500 mL of 25% methanol aqueous solution was passed through the column twice to elute the target acrylamidomethyl γ-cyclodextrin (referred to as γCDAAmMe). The solvent was removed under reduced pressure to obtain γCDAAmMe as a white powder.

20 g of this γCDAAmMe was dissolved in 300 mL of pyridine, and 170.133 g of acetic anhydride was added and stirred at 55°C for at least 12 hours. Then, 50 mL of methanol was added to quench the mixture, and the mixture was concentrated in an evaporator until the content volume reached 200 mL. The resulting concentrated liquid was dropped into 2000 mL of water, and the precipitate was collected. The precipitate was dissolved in 200 mL of acetone, and dropped into 2000 mL of water. The resulting precipitate was collected and dried under reduced pressure to isolate the desired host group-containing polymerizable monomer. The resulting host group-containing polymerizable monomer was a compound represented by the following formula (h1) (hereinafter referred to as "PAcγCD").

Example 1
A solution was prepared by adding 0.03 mmol of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator to a raw material containing 0.06 mmol of PAcγCD obtained in Production Example 1 and 5.72 mmol of ethyl acrylate, and irradiating the mixture with ultrasonic waves for 1 minute. Photopolymerization was performed by irradiating the solution with ultraviolet light (wavelength 365 nm) for 2 hours. The polymer obtained by such polymerization was dried under reduced pressure at 60°C overnight, immersed in 10 mL of chloroform, and then washed for 24 hours while replacing the chloroform several times. Next, the polymer was dried under reduced pressure at 40°C for 1 hour, and then dried under reduced pressure at 40°C overnight. This resulted in a polymer compound H having a host group. The polymer compound H formed a crosslinked structure (mobile crosslinked structure) shown in FIG. 1(b).

The obtained polymer compound H was added to a chloroform solution in which 0.02 mmol of bis(cyclohexylsulfonyl)diazomethane (hereinafter referred to as PAG) was dissolved in 10 mL of chloroform as a photoacid generator, to obtain a polymer composition containing polymer compound H and a polymer material containing the photoacid generator.

Example 2
A solution was prepared by adding 0.06 mmol of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator and 0.05 mmol of PAG as a photoacid generator to a raw material containing 0.12 mmol of PAcγCD obtained in Production Example 1 and 12.83 mmol of ethyl acrylate, and irradiating the mixture with ultrasonic waves for 1 minute. Photopolymerization was carried out by irradiating the solution with ultraviolet light (wavelength 365 nm) for 3.5 hours. As a result, a polymer composition containing polymer compound H and a polymer material containing a photoacid generator were obtained. Polymer compound H formed a crosslinked structure (mobile crosslinked structure) as shown in FIG. 1(b).

Example 3
A solution was prepared by adding 0.03 mmol of 1-hydroxycyclohexylphenylketone as a photopolymerization initiator to a raw material containing 0.06 mmol of PAcγCD obtained in Production Example 1 and 5.61 mmol of ethyl acrylate, and irradiating the raw material with ultrasonic waves for 5 minutes. Photopolymerization was performed by irradiating the solution with ultraviolet light (wavelength 365 nm) for 2 hours. The polymer obtained by such polymerization was cut into 1/8 size, and the sample was immersed in 5 mL of chloroform, and then washed for 40 hours while replacing the chloroform several times. Next, air drying at 40°C was performed for 6 hours, and then reduced pressure drying at 40°C was performed overnight. The mass of the sample after washing was measured, and the substance amount of PAcγCD was estimated from the charge ratio. PAG was weighed so as to be equal to the substance amount, and this was dissolved in 3 mL of chloroform to prepare a chloroform solution, and the sample after washing was added to the chloroform solution. As a result, a polymer composition containing polymer compound H and a polymer material containing a photoacid generator were obtained. Polymer compound H formed the crosslinked structure (mobile crosslinked structure) shown in FIG. 1(b).

Example 4
A mixed monomer of PAcγCD obtained in Production Example 1, methyl methacrylate (MMA), and ethyl acrylate (EA) was prepared. The molar ratio of the mixed monomers, PAcγCD:MMA:EA, was set to 1:24.6:74.4. 1-Hydroxycyclohexylphenylketone as a photopolymerization initiator and PAG as a photoacid generator were added to this mixed monomer, and ultrasonic irradiation was performed for 1 minute to prepare a solution. The photopolymerization initiator added to the solution was 0.5 mol% relative to the mixed monomer, and the photoacid generator was 1 mol% relative to the mixed monomer. After photopolymerization was performed by irradiating the solution with ultraviolet light (wavelength 365 nm) for 2 hours, the solution was dried under reduced pressure at 60°C overnight. As a result, a polymer composition containing polymer compound H and a polymer material containing a photoacid generator were obtained. Polymer compound H formed a crosslinked structure (mobile crosslinked structure) shown in FIG. 1(b).

Example 5
A mixed monomer 1 of PAcγCD obtained in Production Example 1 and ethyl acrylate (EA) was prepared. The molar ratio of the mixed monomer 1, PAcγCD:EA, was set to 1.01:98.99. 1-Hydroxycyclohexylphenylketone was added as a photopolymerization initiator to the mixed monomer 1, and ultrasonic irradiation was performed for 1 minute to prepare a solution. The amount of the photopolymerization initiator added to the solution was 0.5 mol% relative to the mixed monomer 1. The solution was photopolymerized by irradiating it with ultraviolet light (wavelength 365 nm) for 2 hours, and then dried under reduced pressure at 60°C overnight. As a result, a crosslinked structure (mobile crosslinked structure) shown in FIG. 1(b) was obtained. Such a crosslinked structure was designated as a mobile crosslinked structure X1.

On the other hand, mixed monomer 2 of PAcγCD obtained in Production Example 1 and methyl methacrylate (MMA) was prepared. The molar ratio of mixed monomer 2, PAcγCD:MMA, was set to 1:99. 1-hydroxycyclohexylphenylketone as a photopolymerization initiator, PAG as a photoacid generator, and chloroform as a solvent were added to this mixed monomer 2, and ultrasonic irradiation was performed for 1 minute to prepare a chloroform solution. The photopolymerization initiator added to the chloroform solution was 0.5 mol % relative to mixed monomer 2, the photoacid generator was 2.5 mol % relative to mixed monomer 2, and chloroform was added in an amount of about 1.5 times the mass of mixed monomer 2. The mobile crosslinked structure X1 was immersed in this chloroform solution overnight, and then dried in a windy oven at 40°C for 1 hour, and the chloroform was dried to obtain a dried product. This dried product was irradiated with ultraviolet light (wavelength 365 nm) for 2 hours to perform photopolymerization, producing the crosslinked structure (mobile crosslinked structure) shown in Figure 1(b), thereby obtaining a polymer material containing a polymer composition having the structure shown in Figure 1(d) and a photoacid generator.

(Preliminary Test 1)
As a preliminary test, the ultraviolet-visible absorption spectrum of PAG (Bis(cyclohexylsulfonyl)diazomethane), a photoacid generator, was measured to examine the PAG absorption wavelength.

Figure 2 shows the UV-visible absorption spectrum of PAG.

(Preliminary Test 2)
The action of PAG on only the PAcγCD obtained in Production Example 1 was previously examined. Specifically, 0.05 mmol of PAcγCD obtained in Production Example 1 and 0.05 mmol of PAG were dissolved in 2 mL of chloroform to prepare a solution. This solution was irradiated with ultraviolet light (wavelength: white light (mercury lamp) having peaks of λ=253 and 365 nm) for 1 hour. Thereafter, the mixture was air-dried in a fume hood to remove the chloroform, and the molecular weight was measured by MALDI-TOF-MS spectroscopy.

Figure 3 shows the results of MALDI measurements in Preliminary Test 2. The upper spectrum in Figure 3 is the MALDI-TOF-MS spectrum of the solution before UV irradiation, and the lower spectrum is the MALDI-TOF-MS spectrum of the solution after UV irradiation. After UV irradiation, it was confirmed that the spectrum specific to PAcγCD that was seen before UV irradiation disappeared, and instead, a spectrum due to partial decomposition products of hemiaminal clearly appeared. In other words, it was found that the hemiaminal bond of PAcγCD was cleaved. From this result, it was found that PAG has the effect of cleaving the hemiaminal bond in PAcγCD. It is presumed that the cleavage of the hemiaminal bond in PAcγCD converts the hemiaminal oxygen to a hydroxyl group. Therefore, for example, it is presumed that PAcγCD changes to a structure shown in the following formula (h1-1).

(Test Example 1)
The chloroform solution of the polymer material obtained in Example 1 was irradiated with ultraviolet light (white light (mercury lamp) having peaks at wavelengths λ=253 and 365 nm) for 1.5 hours, and then the chloroform solution was air-dried in a draft to obtain a dried product. The molecular weight of the obtained dried product was measured by MALDI-TOF-MS spectrum.

Figure 4(b) is the MALDI-TOF-MS spectrum of the dried product obtained in Test Example 1. For comparison, Figure 4(a) shows the MALDI-TOF-MS spectrum of PAcγCD obtained in Production Example 1. Referring to the spectrum results in Figures 4(a) and 4(b) and the MALDI measurement results of Preliminary Test 2 (Figure 3), it is presumed that the hemiaminal bond in polymer compound H was broken by the ultraviolet irradiation performed in Test Example 1, and the hemiaminal oxygen was converted to a hydroxyl group (i.e., it is presumed that the compound represented by (h1-1) described above was generated). Therefore, it was shown that the presence of a photoacid generator in a polymer material can cause acid decomposition of the hemiaminal bond.

Figure 5 shows a schematic diagram of how the hemiaminal bond in polymer compound H is broken. In Figure 5, h represents a host group, and X1 represents a crosslinked structure.

(Test Example 1a: Raw Material Recovery)
In Test Example 1, the polymeric material after ultraviolet irradiation was washed with chloroform, and the residue after the washing liquid was dried and solidified was subjected to GPC measurement. It was found that the residue contained a compound in which the oxygen in the hemiaminal bond in PAcγCD had been converted to a hydroxyl group (i.e., the compound represented by (h1-1) above). The recovery rate was 13%. This shows that compounds derived from the raw materials of the polymeric material can be recovered by irradiating the polymeric material with ultraviolet light.

(Test Example 1b: Physical properties after acid decomposition)
Figure 6 shows the results of USAXS-SAXS measurement of the polymer material after ultraviolet irradiation in Test Example 1. In this measurement, the profiles obtained by connecting the USAXS and SAXS profiles at q = 0.06 nm ^-1 were compared. The results in Figure 6 suggest the possibility of the formation of a structure of a certain size after photodecomposition.

Figure 7 shows the results of stretching SAXS measurements of the polymeric material after UV irradiation in Test Example 1. Figure 7 (a) is before UV irradiation, and (b) is after UV irradiation. In both (a) and (b), the graphs on the left are SAXS measurements in the stretching direction, and the graphs on the right are SAXS measurements in the perpendicular direction. The results in Figure 7 suggest that there may be a tendency for stretching orientation to be easier after UV irradiation. This is presumably due to the breakage of crosslinking points.

(Test Example 2)
The polymer material obtained in Example 2 was cut in half, and one half was irradiated with ultraviolet light (white light (mercury lamp) having peaks of wavelengths λ=253 and 365 nm) for 1.5 hours, after which its mechanical properties were evaluated. The other half of the polymer material was not irradiated with ultraviolet light, and its mechanical properties were evaluated for comparison.

Figure 8 shows the results of the mechanical properties obtained in Test Example 2. Figure 8(a) is a graph showing the relationship between Young's modulus and fracture energy, and Figure 8(b) is a graph showing the relationship between strain and stress. Note that in Figure 8, "Before" is before UV irradiation, and "After" is after UV irradiation.

From Figure 8, it can be seen that both Young's modulus and toughness (fracture energy) decrease with UV irradiation. This result supports the idea that UV irradiation of a polymeric material containing PAG causes an acid decomposition reaction in the elastomer, severing the hemiaminal bonds and reducing the number of crosslinking points.

(Test Example 3)
The chloroform solution of the polymer material obtained in Example 3 was irradiated with a mercury lamp (white light having a wavelength of λ=253 and 365 nm peaks) for 90 minutes. After irradiation, the solution was dried for 6 hours with air at 40° C., and then 1.5 mL of DMSO was added to the dried product and shaken for 30 minutes to prepare a DMSO solution. Then, SEC measurement was performed using the DMSO solution.

Figure 9 shows the results of SEC measurement. From this SEC, a peak identical to the peak due to the compound represented by (h1-1) (represented as "1" in Figure 9) was observed in the chloroform solution irradiated with the mercury lamp (represented as "AcγCD" in Figure 9). On the other hand, no peak due to the compound represented by (h1-1) was observed in the chloroform solution not irradiated with the mercury lamp (represented as "2" in Figure 9). Therefore, it was found that the compound represented by (h1-1) is generated by irradiating a polymeric material containing PAG with ultraviolet light.

(Test Example 4-1)
The polymer material obtained in Example 4 was cut in half to prepare a pair of polymer materials. Each polymer material was wrapped in a water-soaked Kimwipe and left in a sealed container for about two days to absorb water. After absorbing water, the polymer material turned cloudy. Then, one of the polymer materials was irradiated with ultraviolet light (white light (mercury lamp) having peaks of wavelength λ=253 and 365 nm) for 1.5 hours. After irradiation, the mechanical properties of the polymer material were evaluated. The other polymer material was not irradiated with ultraviolet light, and its mechanical properties were evaluated for comparison.

(Test Example 4-2)
The polymer material obtained in Example 4 was cut in half to prepare a pair of polymer materials. One of the polymer materials was irradiated with ultraviolet light (white light (mercury lamp) having peaks of wavelength λ=253 and 365 nm) for 1.5 hours. After irradiation, the mechanical properties of the polymer material were evaluated. The other polymer material was not irradiated with ultraviolet light, and its mechanical properties were evaluated for comparison.

Figure 10 shows the results of the mechanical properties measured in Test Examples 4-1 and 4-2. Specifically, (a) and (b) in Figure 10 show the results of Test Example 4-2, and (c) and (d) in Figure 10 show the results of Test Example 4-1.

From Figure 10, it can be seen that in the case of a polymeric material containing water (Test Example 4-1, Figures 10(c) and (d)), Young's modulus decreases due to ultraviolet light irradiation (UV irradiation), and mechanical strength decreases. This result shows that adding water to a polymeric material and irradiating it with ultraviolet light makes the polymeric material more easily decomposed. Therefore, it can be said that the water present in the polymeric material has the effect of promoting the decomposition of the polymeric material, and it is presumed that this makes the recovery and decomposition work easier.

(Test Example 5)
The polymer material obtained in Example 5 was irradiated with a mercury lamp for 90 minutes, and then a sample and a non-irradiated sample were evaluated by a tensile test.

Figure 11 shows the results of the mechanical properties obtained in Test Example 5. Specifically, Figure 11 shows that the Young's modulus of the polymer material obtained in Example 5 decreases when exposed to ultraviolet light (UV irradiation), and that the mechanical strength decreases. Unlike Figure 10, this result shows that the polymer material is easily decomposed by ultraviolet light irradiation even without adding water to the polymer material. Therefore, it is presumed that the recovery and decomposition process will be easier in the polymer material obtained in Example 5 when exposed to ultraviolet light.

(Application Example 1)
An adhesion test was performed using the method shown in Figure 12 (a). First, a mixed monomer of PAcγCD obtained in Production Example 1 and ethyl acrylate (EA) was prepared. The molar ratio of the mixed monomers, PAcγCD:EA, was set to 1:99. 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator and PAG as a photoacid generator were added to this mixed monomer, and ultrasonic irradiation was performed for 1 minute to prepare a solution. The photopolymerization initiator added to the solution was 0.5 mol% relative to the mixed monomer, and the photoacid generator was 1 mol% relative to the mixed monomer.

On the other hand, a pair of rectangular 6,10-nylon substrates were prepared, and their surfaces were plasma-treated, and then vinyl groups were modified with a silane coupling agent to prepare a pair of adherends S1 and S2. On the silane coupling agent-treated surface of one adherend S1, an area from one end to a distance of 1.5 cm was designated as the adhesive portion A1, and 25 μL of the solution was applied to the entire surface of the adhesive portion 50 to form a coating film M. The adhesive portion A2 of the other adherend S2 was placed on top of this coating film M, and the adherend S2 was bonded to the adherend S1 so that the surface other than the adhesive portion A2 did not overlap with the adherend S1, forming a laminate. The coating film M in this laminate was photopolymerized by irradiating it with ultraviolet light (wavelength 365 nm) for 2 hours, and the coating film M was hardened to bond the adherends together. Next, the hardened coating film M (adhesive layer M) was irradiated with a mercury lamp for 90 minutes, and then a tensile test of the laminate was performed. All of the above operations were performed a total of three times.

As shown in Figure 12 (a), in the tensile test of the laminate, the adherends S1 and S2 were pulled in a 180° direction until the coating broke, and the pulling distance x (mm) at the time of break was measured. The value obtained by dividing this x by the thickness y (mm) of the coating was determined as the shear strain (x/y).

Figure 12(b) shows the results of the tensile test carried out in Application Example 1, specifically, a graph showing the stress at break (average of three times) after irradiation with a mercury lamp. For comparison, Figure 12(b) also shows the results of a tensile test without irradiation with a mercury lamp. From the results of Figure 12(b), it can be seen that the stress at break can be reduced by irradiating with a mercury lamp. This result shows that the adhesive force between bonded adherends can be weakened by irradiating an adhesive (adhesive layer) formed from the polymer material of the present invention with a mercury lamp. Therefore, when the polymer material of the present invention is used as an adhesive, the bonded adherends can be easily peeled from each other.

(Method of evaluating mechanical properties)
The mechanical properties of the polymeric material were evaluated by observing the breaking point of the polymeric material through a tensile test (stroke-test force curve) (Shimadzu Corporation's "AUTOGRAPH" (model number: AGX-plus)). The breaking point was set as the end point, and the maximum stress up to the end point was taken as the breaking stress of the polymeric material. This tensile test was performed using the up method, in which the polymeric material was punched into a dumbbell test piece with a thickness of 0.76 mm, the lower end was fixed, and the upper end was operated at a tensile speed of 1 mm/min or 5 mm/min. The test was performed. The stroke at that time, i.e., the maximum length when the polymeric material was pulled, was divided by the length of the polymeric material before pulling to calculate the strain rate. In the "stroke-test force curve" (stress-strain curve) test, a material that shows high values for either or both of the breaking stress and breaking strain (also simply called strain) can be judged to have excellent toughness and strength. In particular, a material that shows high values for both the breaking stress and strain can be judged to have excellent fracture energy.

Claims (9)

A polymer composition containing a polymer compound H and a photoacid generator,
The polymer compound H has at least one host group in the molecule,
the host group is a group in which at least one hydrogen atom or hydroxyl group has been removed from a cyclodextrin or a cyclodextrin derivative,
The host group is covalently bonded to the polymeric compound H via a hemiaminal bond. 2. The polymer material according to claim 1, wherein the hemiaminal bond is a bond represented by -O-CH ₂ -NR ^b - (R ^b represents a hydrogen atom or an alkyl group). The polymer compound H is represented by the following general formula (1):

(In formula (1), R ^a represents a hydrogen atom or a methyl group, R ^b represents a hydrogen atom or an alkyl group, and R ^H represents the host group.)
The polymer material according to claim 1 , having a constitutional unit based on a monomer represented by the following formula: The polymer material according to claim 1, wherein the polymer compound H forms a cross-linked structure. A method for producing a polymeric material according to any one of claims 1 to 4, comprising the steps of:
a step of obtaining the polymer material by a polymerization reaction of a raw material containing a monomer containing a polymerizable monomer having a host group and the photoacid generator. A method for producing a polymeric material according to any one of claims 1 to 4, comprising the steps of:
The method includes a step of obtaining the polymer material by mixing the polymer composition with the photoacid generator. A method for decomposing a polymeric material according to any one of claims 1 to 4, comprising the steps of:
A method for decomposing a polymer material, comprising the step of irradiating the polymer material with ultraviolet light. An adhesive composition containing the polymer material according to any one of claims 1 to 4. A laminate comprising an adhesive layer containing the adhesive composition according to claim 8.

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