Composite polymer material, manufacturing method thereof, and optical material

Abstract

Provided are: a novel composite polymer material having excellent mechanical properties; a method for producing the composite polymer material; and an optical material comprising the composite polymer material. This composite polymer material contains a cross-linked polymer obtained by cross-linking a silicone polymer S having a polysiloxane skeleton as the main chain and a polymer P having a skeleton other than the polysiloxane skeleton as the main chain, a host-guest interaction based on a host group and a guest group is formed between the silicone polymer S and the polymer P, and the host group is a monovalent group obtained by removing one hydrogen atom or one hydroxyl group from cyclodextrin or a cyclodextrin derivative.

Description

Technical Field

[0001] The present invention relates to a composite polymer material, a method for manufacturing the same, and an optical material. Background Art

[0002] It is known that organosilicon polymers (polysiloxanes) having a siloxane bond (Si-O bond) in the main skeleton have unique properties not present in organic polymers and are used in various fields. The siloxane bond has a stronger bonding force than carbon-carbon or carbon-oxygen bonds present in general organic polymers and has chemically stable properties. Therefore, polysiloxanes formed by repeating siloxane bonds, for example, have excellent heat resistance and weather resistance. In addition, polysiloxanes can form a helical structure in which inorganic siloxane bonds are arranged on the inside and organic side chain substituents are arranged on the outside, so they are soft, water-repellent, and have low biotoxicity. Therefore, polysiloxanes are highly valuable materials in various applications such as medical devices, rubbers, coatings, and protective films.

[0003] In recent years, functions have been further imparted to polysiloxane-based materials. For example, Non-Patent Document 1 proposes the following technique: introducing a functional group capable of forming a hydrogen bond into the polysiloxane skeleton and exhibiting self-healing properties through the hydrogen bond of this functional group.

[0004] Prior Art Documents

[0005] Non-Patent Documents

[0006] Non-Patent Document 1: Adv. Mater. 2018, 30, 1706846 Summary of the Invention

[0007] Technical Problem to be Solved by the Invention

[0008] Recently, in order to apply polysiloxanes to various uses, there has been a strong desire to impart more functions to polysiloxanes. In particular, organosilicon materials represented by polysiloxanes exhibit characteristics different from those of general-purpose resins, so they are expected to be applied to various fields. Therefore, the industry strongly demands the creation of new organosilicon materials. For example, the use value of a new composite polymer material containing an organosilicon polymer and having excellent mechanical properties is extremely high.

[0009] The present invention has been completed in view of the above circumstances, and an object thereof is to provide a new composite polymer material having excellent mechanical properties, a method for manufacturing the same, and an optical material containing the composite polymer material.

[0010] Technical Means for Solving the Problem

[0011] To achieve the above object, the present inventors repeatedly conducted in-depth studies and found that by using a crosslinked polymer of a silicone-based polymer and polymer P, wherein the silicone-based polymer has a specific polysiloxane backbone as the main chain and the polymer P has a backbone other than the specific polysiloxane backbone as the main chain, the above object can be achieved, and thus the present invention was completed.

[0012] That is, the present invention includes, for example, the subject matters described in the following items.

[0013] Item 1

[0014] A composite polymer material comprising a crosslinked polymer formed by crosslinking a silicone-based polymer S and a polymer P, wherein the silicone-based polymer S has a polysiloxane backbone as the main chain and the polymer P has a backbone other than the polysiloxane backbone as the main chain.

[0015] A host-guest interaction based on a host group and a guest group is formed between the silicone-based polymer S and the polymer P.

[0016] The host group is a monovalent group obtained by removing one hydrogen atom or a hydroxyl group from cyclodextrin or a cyclodextrin derivative.

[0017] Item 2

[0018] The composite polymer material according to Item 1, wherein the host-guest interaction is formed between the side chain of the silicone-based polymer S and the side chain of the polymer P.

[0019] Item 3

[0020] The composite polymer material according to Item 1, wherein the host-guest interaction is formed between the side chain of the silicone-based polymer S and the end of the polymer P.

[0021] Item 4

[0022] The composite polymer material according to Item 2, wherein the polymer P is a vinyl-based polymer.

[0023] Item 5

[0024] The composite polymer material according to Item 3, wherein the polymer P is one or more selected from the group consisting of addition polymers and condensation polymers.

[0025] Item 6

[0026] The composite polymer material according to Item 1, wherein the silicone-based polymer S has at least one of the host groups and the polymer P has at least one of the guest groups.

[0027] Item 7

[0028] The composite polymer material according to any one of Items 1 to 6, wherein a hydrogen bond is further formed between the silicone-based polymer S and the polymer P.

[0029] Item 8

[0030] An optical material containing the composite polymer material according to any one of Items 1 to 7.

[0031] Item 9

[0032] A method for manufacturing a composite polymer material, which is the method for manufacturing the composite polymer material according to any one of Items 1 to 7,

[0033] The above manufacturing method includes a step of forming the above crosslinked polymer by synthesizing the polymer P in the presence of the silicone-based polymer S.

[0034] Advantages of the Invention

[0035] The composite polymer material of the present invention has excellent mechanical properties. Description of the Drawings

[0036] Figure 1 It is a schematic diagram of a crosslinked polymer formed by forming a host-guest interaction between the side chain of the silicone-based polymer S and the side chain of the above polymer P.

[0037] Figure 2 It is a schematic diagram of a crosslinked polymer formed by forming a host-guest interaction between the side chain of the silicone-based polymer S and both ends of the above polymer P.

[0038] Figure 3 It is the reaction route of the silicone-based polymer Sh obtained in Example 1-1 and the reaction route of the crosslinked polymer of the silicone-based polymer Sh and the polymer Pg.

[0039] Figure 4 It is the result of the tensile test of the crosslinked polymer obtained in each example. (a) is the stress-strain curve, and (b) is a chart showing the correlation between Young's modulus and toughness.

[0040] Figure 5 It is the result of the tensile test of the crosslinked polymer obtained in each example. (a) is the stress-strain curve, and (b) is a chart showing the correlation between Young's modulus and toughness.

[0041] Figure 6These are the evaluation results of the self-healing properties of the crosslinked polymers obtained in each example. (a) is the stress-strain curve of the tensile test of the test piece after "standing at room temperature for 24 hours", (b) is the stress-strain curve of the tensile test of the test piece after "standing at 70 °C for 12 hours", and (c) is the result of the repair rate (%).

[0042] Figure 7 These are the results of the tensile tests of the crosslinked polymers obtained in each example. (a) is the stress-strain curve, and (b) is a graph showing the correlation between Young's modulus and toughness.

[0043] Figure 8 These are the evaluation results of the self-healing properties of the crosslinked polymers obtained in each example. (a) is the stress-strain curve of the tensile test of the test piece, and (b) is the result of the repair rate (%).

[0044] Figure 9 These are the results of the tensile tests of the crosslinked polymers obtained in each example. (a) is the stress-strain curve, and (b) is a graph showing the correlation between Young's modulus and toughness.

[0045] Figure 10 These are the evaluation results of the self-healing properties of the crosslinked polymers obtained in each example. (a) is the stress-strain curve of the tensile test of the test piece after "standing at room temperature for 24 hours", (b) is the stress-strain curve of the tensile test of the test piece after "standing at 70 °C for 12 hours", and (c) is the result of the repair rate (%).

[0046] Figure 11 This is the reaction route of the crosslinked polymer obtained in Example 6-1.

[0047] Figure 12 These are the results of the tensile tests of the crosslinked polymers obtained in each example. (a) is the stress-strain curve, and (b) is a graph showing the correlation between Young's modulus and toughness. Detailed Embodiments

[0048] The embodiments of the present invention will be described in detail below. It should be noted that in this specification, the expressions "containing" and "comprising" include concepts such as "containing", "comprising", "substantially consisting of...", and "consisting only of...".

[0049] 1. Composite polymer material

[0050] The composite polymer material of the present invention comprises a crosslinked polymer, which is formed by crosslinking a silicone-based polymer S having a polysiloxane backbone as the main chain and a polymer P having a backbone other than the polysiloxane backbone as the main chain, and a host-guest interaction based on a host group and a guest group is formed between the silicone-based polymer S and the polymer P. The above host group is a monovalent group formed by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative.

[0051] Herein, the "host-guest interaction based on a host group and a guest group" may, for example, mean that the host group and the guest group form an inclusion complex. The inclusion complex is a complex formed by including a guest group within the ring of one host group. Hereinafter, the host group and the guest group will be described in detail.

[0052] As described above, the host group is a group formed by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative. The host group is preferably a group formed by removing one hydrogen atom or hydroxyl group from a cyclodextrin derivative. The host group is not limited to a monovalent group, and for example, the host group may be a divalent group.

[0053] The above cyclodextrin derivative preferably has the following structure, in which at least one hydrogen atom of the hydroxyl group in cyclodextrin is replaced by a hydrophobic group. That is, the cyclodextrin derivative is a molecule having a structure in which a cyclodextrin molecule is replaced by other hydrophobic organic groups. Among them, the cyclodextrin derivative has at least one hydrogen atom or at least one hydroxyl group, and preferably has at least one hydroxyl group.

[0054] The above hydrophobic group preferably has a structure in which at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is methyl or ethyl) is substituted. Hereinafter, in this specification, for convenience, the foregoing "at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is methyl or ethyl)" is sometimes expressed as "hydrocarbon group, etc.".

[0055] Here, just for the sake of caution, the expression 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 derivative, β-cyclodextrin derivative, and γ-cyclodextrin derivative.

[0056] The host group is a group with a valence of one or more obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin derivative, but the hydrogen atom or hydroxyl group removed from the cyclodextrin derivative can be any part of the cyclodextrin or cyclodextrin derivative.

[0057] Here, when the total number of hydroxyl groups in one molecule of cyclodextrin is set to N, N = 18 for α-cyclodextrin, N = 21 for β-cyclodextrin, and N = 24 for γ-cyclodextrin.

[0058] Assume that in the case where the host group is a monovalent group obtained by removing one "hydroxyl group" from a cyclodextrin derivative, the cyclodextrin derivative is formed by substituting the hydrogen atoms of up to N - 1 hydroxyl groups in each molecule of cyclodextrin with a hydrocarbon group or the like. On the other hand, in the case where the host group is a monovalent group obtained by removing one "hydrogen atom" from a cyclodextrin derivative, the hydrogen atoms of up to N hydroxyl groups in each molecule of cyclodextrin of the cyclodextrin derivative can be substituted with a hydrocarbon group or the like.

[0059] The above-mentioned host group preferably has a structure in which the hydrogen atoms of 70% or more of all the hydroxyl groups present in one molecule of cyclodextrin are substituted with the above-mentioned hydrocarbon group or the like. The above-mentioned host group is more preferably one in which the hydrogen atoms of 80% or more of all the hydroxyl groups present in one molecule of cyclodextrin are substituted with the above-mentioned hydrocarbon group or the like, and particularly preferably one in which the hydrogen atoms of 90% or more of all the hydroxyl groups are substituted with the above-mentioned hydrocarbon group or the like.

[0060] The above-mentioned host group preferably has a structure in which the hydrogen atoms of 13 or more hydroxyl groups among all the hydroxyl groups present in one molecule of α-cyclodextrin are substituted with the above-mentioned hydrocarbon group or the like. The above-mentioned host group is more preferably one in which the hydrogen atoms of 15 or more hydroxyl groups among all the hydroxyl groups present in one molecule of α-cyclodextrin are substituted with the above-mentioned hydrocarbon group or the like, and particularly preferably one in which the hydrogen atoms of 17 hydroxyl groups are substituted with the above-mentioned hydrocarbon group or the like.

[0061] The above-mentioned host group preferably has a structure in which the hydrogen atoms of 15 or more hydroxyl groups among all the hydroxyl groups present in one molecule of β-cyclodextrin are substituted with the above-mentioned hydrocarbon group or the like. The above-mentioned host group is more preferably one in which the hydrogen atoms of 17 or more hydroxyl groups among all the hydroxyl groups present in one molecule of β-cyclodextrin are substituted with the above-mentioned hydrocarbon group or the like, and particularly preferably one in which the hydrogen atoms of 19 or more hydroxyl groups are substituted with the above-mentioned hydrocarbon group or the like.

[0062] The above-mentioned host group preferably has a structure in which the hydrogen atoms of 17 or more hydroxyl groups among all the hydroxyl groups present in one molecule of γ-cyclodextrin are substituted with the above-mentioned hydrocarbon group or the like. The above-mentioned host group is more preferably one in which the hydrogen atoms of 19 or more hydroxyl groups among all the hydroxyl groups present in one molecule of γ-cyclodextrin are substituted with the above-mentioned hydrocarbon group or the like, and particularly preferably one in which the hydrogen atoms of 21 or more hydroxyl groups are substituted with the above-mentioned hydrocarbon group or the like.

[0063] In the cyclodextrin derivative, the type of the above-mentioned hydrocarbon group is not particularly limited. Examples of the above-mentioned hydrocarbon group include: alkyl group, alkenyl group, and alkynyl group.

[0064] The number of carbon atoms of the above-mentioned hydrocarbon group is not particularly limited. For example, the number of carbon atoms of the hydrocarbon group is preferably 1 to 4.

[0065] Specific examples of the hydrocarbon group having 1 to 4 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, and butyl. When the hydrocarbon group is propyl or butyl, it can be either linear or branched.

[0066] In the cyclodextrin derivative, the acyl group can be exemplified by acetyl, propionyl, formyl, etc. Considering that host-guest interaction is easily formed, or other polymer chains are easily penetrated into the host group ring, or a composite polymer material with excellent toughness and strength is easily obtained, the acyl group is preferably acetyl.

[0067] In the cyclodextrin derivative, -CONHR (R is methyl or ethyl) is methylcarbamate group or ethylcarbamate group. Considering that host-guest interaction is easily formed, or other polymer chains are easily penetrated into the host group ring, and also considering that a composite polymer material with excellent toughness and strength is easily obtained, -CONHR is preferably ethylcarbamate group.

[0068] In the cyclodextrin derivative, the hydrocarbon group etc. are preferably an alkyl group or an acyl group having 1 to 4 carbon atoms, preferably methyl and acyl group, more preferably methyl, acetyl, propionyl, and particularly preferably methyl and acetyl.

[0069] The guest group refers to a group that can be included in cyclodextrin or a cyclodextrin derivative. That is, as long as the guest group is a group that can form an inclusion complex with the above-mentioned host group, its type is not limited. The guest group is not limited to a monovalent group, for example, the guest group can be a divalent group.

[0070] As the guest group, there can be mentioned a linear or branched hydrocarbon group having 3 to 30 carbon atoms, a cycloalkyl group, a heteroaryl group, an organometallic complex, etc., and they can have one or more substituents. As the substituent, similarly to the above-mentioned substituents, for example, there can be mentioned a halogen atom (such as fluorine, chlorine, bromine, etc.), a hydroxyl group, a carboxyl group, an ester group, an amide group, a hydroxyl group that can be protected, etc.

[0071] As more specific guest groups, there can be mentioned: a linear or cyclic alkyl group having 4 to 18 carbon atoms, a group derived from a polycyclic aromatic hydrocarbon. The linear alkyl group having 4 to 18 carbon atoms can be either linear or branched. The cyclic alkyl group can also be a cage structure. As the polycyclic aromatic hydrocarbon, for example, there can be mentioned a π-conjugated system compound formed by at least two or more aromatic rings, specifically, there can be mentioned: naphthalene, anthracene, tetracene, pentacene, benzopyrene, picene, pyrene, triphenylene, etc. The guest group is preferably a linear or cyclic alkyl group having 4 to 18 carbon atoms, more preferably a linear or cyclic alkyl group having 6 to 18 carbon atoms, and further preferably a cyclic alkyl group having 6 to 18 carbon atoms.

[0072] In addition, the guest group may also be a monovalent group formed by removing one atom (such as a hydrogen atom) from the guest molecules exemplified below, i.e., at least one selected from the group consisting of alcohol derivatives; aryl compounds; carboxylic acid derivatives; amino derivatives; azobenzene derivatives having a cyclic alkyl or 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 fullerenes; dansyl compounds.

[0073] More specific examples of the guest group include: tert-butyl, n-octyl, n-dodecyl, isobornyl, adamantyl, a group derived from pyrene, and a group formed by bonding a substituent thereto.

[0074] Hereinafter, the organosilicon polymer S and the polymer P will be described in detail.

[0075] (Organosilicon polymer S)

[0076] The organosilicon polymer S is a high molecular compound having a polysiloxane skeleton as the main chain. The organosilicon polymer S may have either the above-mentioned host group or the above-mentioned guest group in the molecule, and preferably has only one of them.

[0077] For example, the organosilicon polymer S may have at least one host group in the side chain, or may have at least one guest group in the side chain. Hereinafter, the organosilicon polymer S having the above-mentioned host group will be denoted as "organosilicon polymer Sh", and the organosilicon polymer S having the above-mentioned guest group will be denoted as "organosilicon polymer Sg".

[0078] <Organosilicon polymer Sh>

[0079] The organosilicon polymer Sh has a polysiloxane skeleton as the main chain and has at least one of the above-mentioned host groups. In the organosilicon polymer Sh, the host group is, for example, bonded to the side chain of the polysiloxane skeleton by a covalent bond. The organosilicon polymer Sh may contain a siloxane unit having a host group in its structural unit. Such a siloxane unit having a host group is a structural unit having the following structure: having a siloxane bond in the main chain and having a host group covalently bonded directly or indirectly to the side chain.

[0080] As long as the siloxane unit having a host group has a siloxane bond and a host group, its structure is not particularly limited. For example, as the siloxane unit having a host group, a structural unit represented by the following general formula (1.1) can be cited.

[0081] [Chemical formula 1]

[0082]

[0083] In formula (1.1), R H represents the above-mentioned main group. R 1 represents a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of a hydroxyl group, a thiol group, an 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. R 5 represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted by a substituent, or an aryl group having 6 to 20 carbon atoms which may be substituted by a substituent, and R 6 represents an alkylene group which may have a hetero atom interposed therein.

[0084] Alternatively, the siloxane unit having a main group may also be a structural unit represented by the following general formula (1.2).

[0085] [Chemical formula 2]

[0086]

[0087] In formula (1.2), R H , R 1 , R 5 and R 6 have the same meanings as R H , R 1 , R 5 and R 6 in the above formula (1.1).

[0088] In formula (1.1) and formula (1.2), R 5 is preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably an alkyl group having 1 or 2 carbon atoms. Specifically, examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc., and preferably methyl, ethyl, n-propyl, isopropyl, and particularly preferably methyl.

[0089] When R

[0090] has a substituent, examples of the substituent include: a hydroxyl group, an alkoxy group, an ester group, a cyano group, a nitro group, a sulfo group, a carboxyl group, an aryl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), etc. 5 In formula (1.1) and formula (1.2), R

[0091] 1 ​The substituents therein may include: alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, halogen atoms, hydroxyl groups, carboxyl groups, nitro groups, sulfo groups, carbonyl groups, aryl groups, cyano groups, etc.

[0092] In formulas (1.1) and (1.2), if R 1 is a divalent group formed by removing one hydrogen atom from an amino group that may have one substituent, the nitrogen atom of the amino group may bond to R 6 bond.

[0093] In formulas (1.1) and (1.2), if R 1 is a divalent group formed by removing one hydrogen atom from an amide group that may have one substituent, the carbon atom of the amide group may bond to R 6 bond.

[0094] In formulas (1.1) and (1.2), if R 1 is a divalent group formed by removing one hydrogen atom from an aldehyde group, the carbon atom of the aldehyde group may bond to R 6 bond.

[0095] In formulas (1.1) and (1.2), when R 1 is a divalent group formed by removing one hydrogen atom from a carboxyl group, the carbon atom of the carboxyl group may bond to R 6 bond.

[0096] In formulas (1.1) and (1.2), R 6 is an alkylene group that may have a heteroatom. The number of carbon atoms of the alkylene group is not particularly limited, and may be, for example, 1 to 10 carbon atoms. In R 6 the number of carbon atoms of the alkylene group is preferably 1 to 8, more preferably 2 to 6.

[0097] R 6 may be an alkylene group interposed with a heteroatom. In this case, as R 6 an alkylene group having a thioether bond may be mentioned, for example, it may be exemplified by -(CH2) m1 -S-(CH2) m2 -bond. Here, m1 and m2 are the same or different and are numbers from 1 to 10, preferably 1 to 8, more preferably 1 to 5.

[0098] When R 6 is an alkylene group interposed with a sulfur atom, the organosilicon-based polymer compound has a thioether bond between Si in the polysiloxane backbone and the above-mentioned main group.

[0099] In the structural units of the silicone-based polymer Sh, in addition to the siloxane units having the main group, other siloxane units may also be present. As the other siloxane units, for example, the structural units represented by the following formula (3.1) may be contained.

[0100] [Chemical formula 3]

[0101]

[0102] In formula (3.1), R 3 and R 4 are the same or different and represent hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted by a substituent, or an aryl group having 6 to 20 carbon atoms which may be substituted by a substituent.

[0103] In formula (3.1), the number of carbon atoms of the linear or branched alkyl group having 1 to 10 carbon atoms is preferably 1 to 4, particularly preferably 1 or 2. Specifically, as the alkyl group, examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc.

[0104] In formula (3.1), when the linear or branched alkyl group having 1 to 10 carbon atoms is substituted by a substituent, the number of substituents can be 1 or more. As the substituent in this case, examples include: hydroxyl group, alkoxy group, ester group, cyano group, nitro group, sulfo group, carboxyl group, aryl group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), etc.

[0105] In formula (3.1), examples of the aryl group having 6 to 20 carbon atoms include: phenyl group, naphthyl group, tetrahydronaphthyl group, etc. When the aryl group is substituted by a substituent, the number of substituents can be 1 or more. As the substituent in this case, examples include: hydroxyl group, alkoxy group, ester group, cyano group, nitro group, sulfo group, carboxyl group, aryl group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), etc.

[0106] In formula (3.1), R 3 and R 4 can be the same or different. In formula (3.1), R 3 and R 4 are both preferably methyl, ethyl, n-propyl, or isopropyl, particularly preferably methyl. When R 3 and R 4 are both methyl, the polysiloxane backbone contains polydimethylsiloxane.

[0107] The silicone-based polymer Sh may contain, in its structural unit, together with the structural unit represented by the above formula (3.1) or in place of the structural unit represented by the above formula (3.1), a structural unit represented by the following formula (3.2).

[0108] [Chemical formula 4]

[0109]

[0110] In formula (3.2), R 7 represents hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted by a substituent, or an aryl group having 6 to 20 carbon atoms which may be substituted by a substituent. In formula (3.2), R 8 represents an alkylene group which may have a hetero atom interposed therein. A represents hydrogen, a mercapto group, a hydroxyl group or an amino group.

[0111] In formula (3.2), R 7 is preferably methyl, ethyl, n-propyl or isopropyl, and particularly preferably methyl.

[0112] In formula (3.2), R 8 is an alkylene group which may have a hetero atom interposed therein. The number of carbon atoms of the alkylene group is not particularly limited, and may be, for example, 1 to 10 carbon atoms. In R 8 the number of carbon atoms of the alkylene group is preferably 1 to 8, and more preferably 2 to 6.

[0113] R 8 may be an alkylene group having a hetero atom interposed therein. In this case, as R 8 , an alkylene group having a thioether bond can be cited, for example, -(CH2) m1 -S-(CH2) m2 -bond. Here, m1 and m2 are the same or different and are numbers from 1 to 10, preferably 1 to 8, and more preferably 1 to 5.

[0114] When the silicone-based polymer Sh contains the structural unit represented by the above formula (3.1) and the structural unit represented by the above formula (3.2), the mechanical properties of the composite polymer material, particularly both the Young's modulus and toughness, are liable to be improved, and the transparency is also liable to be improved. In this case, when R 8 in the structural unit represented by the formula (3.2) is an alkylene group having a hetero atom interposed therein, both the Young's modulus and toughness of the composite polymer material are further improved, and the transparency is particularly liable to be improved.

[0115] When the silicone-based polymer Sh contains the structural unit represented by the above formula (3.2), when A is a mercapto group, a part or all of the mercapto groups in the silicone-based polymer Sh can be protected by a hydrocarbon group (that is, the hydrogen of the mercapto group can be replaced by other groups). At this time, the mechanical properties of the composite polymer material are further improved. Examples of the hydrocarbon group include alkyl groups and alkenyl groups having 1 to 10 carbon atoms, and an alkyl group having 3 to 8 carbon atoms is preferred.

[0116] In one embodiment, the silicone-based polymer Sh contains the above-mentioned siloxane unit having a main group and the above-mentioned other siloxane units. Specific examples of the silicone-based polymer Sh include: a silicone-based polymer Sh having the structural unit represented by the above formula (1.1) and / or the structural unit represented by the above formula (1.2), and one or both of the structural unit represented by the above formula (3.1) and the structural unit represented by the above formula (3.2) as required. It should be noted that the silicone-based polymer Sh is a polymer that does not have a guest group, for example, it does not have the structural unit represented by the following formula (2.1) and the structural unit represented by the following formula (2.2) (that is, the siloxane unit having a guest group described later).

[0117] In all the structural units of the silicone-based polymer Sh, the content ratio of the above-mentioned siloxane unit having a main group is, for example, 0.1 mol% or more and 30 mol% or less. From the viewpoint of more easily improving the mechanical properties of the composite polymer material, in all the structural units of the silicone-based polymer Sh, the content ratio of the above-mentioned siloxane unit having a main group is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, further preferably 0.8 mol% or more, and particularly preferably 1 mol% or more. In addition, from the viewpoint of more easily improving the mechanical properties of the composite polymer material, in all the structural units of the silicone-based polymer Sh, the content ratio of the above-mentioned siloxane unit having a main group is preferably 20 mol% or less, more preferably 15 mol% or less, further preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0118] It should be noted that the content ratio of the above-mentioned siloxane unit having a main group in the silicone-based polymer Sh can be regarded as being consistent with the content ratio of the above-mentioned siloxane monomer having a main group in the monomers used in the production of the silicone-based polymer Sh.

[0119] Among all the structural units of the silicone-based polymer Sh, the content ratio of the above-mentioned other siloxane units is, for example, 70 mol% or more and 99.9 mol% or less. From the perspective of easily forming a composite polymer material with further improved mechanical properties, among all the structural units of the silicone-based polymer Sh, the content ratio of the above-mentioned other siloxane units is preferably 80 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, and particularly preferably 95 mol% or more. In addition, from the perspective of easily forming a composite polymer material with further improved mechanical properties, among all the structural units of the silicone-based polymer Sh, the content ratio of the above-mentioned other siloxane units is preferably 99.8 mol% or less, more preferably 99.5 mol% or less, further preferably 99.2 mol% or less, and particularly preferably 99 mol% or less.

[0120] When the silicone-based polymer Sh contains the structural unit represented by the above formula (3.1) as other siloxane units, among all the structural units of the silicone-based polymer Sh, its content ratio is preferably 80 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, and particularly preferably 95 mol% or more. In addition, when the silicone-based polymer Sh contains the structural unit represented by the above formula (3.1) as other siloxane units, among all the structural units of the silicone-based polymer Sh, its content ratio is preferably 99.8 mol% or less, more preferably 99.5 mol% or less, further preferably 99.2 mol% or less, and particularly preferably 99 mol% or less.

[0121] When the silicone-based polymer Sh contains the structural unit represented by the above formula (3.2) as other siloxane units, among all the structural units of the silicone-based polymer Sh, its content ratio is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, further preferably 0.8 mol% or more, and particularly preferably 1 mol% or more. In addition, when the silicone-based polymer Sh contains the structural unit represented by the above formula (3.1) as other siloxane units, among all the structural units of the silicone-based polymer Sh, its content ratio is preferably 20 mol% or less, more preferably 15 mol% or less, further preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0122] When the silicone-based polymer Sh contains the structural unit represented by the above formula (3.2), the mechanical properties (especially both Young's modulus and toughness) are improved, and the transparency is also easily improved. In particular, when R in the structural unit represented by the formula (3.2) 8 is an alkylene group with a heteroatom in between, the mechanical properties (especially both Young's modulus and toughness) of the composite polymer material are further improved, and the transparency is particularly easily improved.

[0123] The organosilicon polymer Sh may also have structural units other than the structural units represented by the above formulas (1.1), (1.2), (3.1), and (3.2) (hereinafter referred to as structural unit S). In all the structural units of the organosilicon high molecular compound (H), the content ratio of the structural unit S is 5 mol% or less, preferably 1 mol% or less, more preferably 0.1 mol% or less, and may also be 0 mol%.

[0124] <Organosilicon polymer Sg>

[0125] The organosilicon polymer Sg has a polysiloxane backbone as the main chain and has at least one of the above-mentioned guest groups. In the organosilicon polymer Sg, the guest group can be bonded to the side chain of the polysiloxane backbone by a covalent bond, for example. The organosilicon polymer Sg may contain a siloxane unit having a guest group in its structural unit. Such a siloxane unit having a guest group is a structural unit having the following structure: having a siloxane bond in the main chain and having a guest group covalently bonded directly or indirectly in the side chain.

[0126] The organosilicon polymer Sg may have the same constitution as the organosilicon polymer Sh except that the siloxane unit having a guest group is used instead of the siloxane unit having a host group in the above-mentioned organosilicon polymer Sh. Except that the siloxane unit having a host group in the organosilicon polymer Sh is replaced by a siloxane unit having a guest group, the preferred mode of the organosilicon polymer Sg is the same as the preferred mode of the above-mentioned organosilicon polymer Sh.

[0127] Hereinafter, the siloxane unit having a guest group will be described. As long as the siloxane unit having a guest group has a siloxane bond and a guest group, its structure is not particularly limited. For example, as the siloxane unit having a guest group, the structural unit represented by the following general formula (2.1), the structural unit represented by the following general formula (2.2), and the structural unit represented by the following general formula (2.3) can be cited.

[0128] [Chemical formula 5]

[0129]

[0130] In formula (2.1), R G represents the above-mentioned guest group. R 1 , R5, and R 6 are the same as R 1 , R 5 , and R 6 in the above formula (1.1), respectively, and have the same meaning.

[0131] [Chemical formula 6]

[0132]

[0133] In formula (2.2), R G , R 1 , R5 and R 6 have the same meanings as R G , R 1 , R5 and R 6 in formula (2.1) above.

[0134] [Chemical Formula 7]

[0135]

[0136] In formula (2.3), R G and R 5 have the same meanings as R G and R 5 in formula (2.1) above.

[0137] In formulas (2.1), (2.2) and (2.3), R 5 is preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 or 2 carbon atoms. Specifically, examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. Preferably, it is methyl, ethyl, n-propyl or isopropyl, and particularly preferably methyl.

[0138] When R 5 has a substituent, examples of the substituent include hydroxyl, alkoxy, ester, cyano, nitro, sulfo, carboxyl, aryl, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), etc.

[0139] In formulas (2.1) and (2.2), if R 1 is a divalent group formed by removing one hydrogen atom from an amino group which may have one substituent, the nitrogen atom of the amino group may be bonded to R 6 .

[0140] In formulas (2.1) and (2.2), if R 1 is a divalent group formed by removing one hydrogen atom from an amide group which may have one substituent, the carbon atom of the amide group may be bonded to R 6 .

[0141] In formulas (2.1) and (2.2), if R 1 is a divalent group formed by removing one hydrogen atom from an aldehyde group, the carbon atom of the aldehyde group may be bonded to R 6 .

[0142] In Formula (2.1) and Formula (2.2), if R 1 is a divalent group formed by removing one hydrogen atom from a carboxyl group, the carbon atom of the carboxyl group can be bonded to R 6 .

[0143] In Formula (2.1) and Formula (2.2), the number of carbon atoms of the alkylene group of R 6 is preferably 1 to 8, more preferably 2 to 6. R 6 can be an alkylene group interposed with a heteroatom. At this time, as R 6 , an alkylene group having a thioether bond can be cited. For example, it can be exemplified by a -(CH2) m1 -S-(CH2) m2 - bond. Here, m1 and m2 are the same or different and are numbers from 1 to 10, preferably 1 to 8, more preferably 1 to 5.

[0144] In Formula (2.1) and Formula (2.2), when R 6 is an alkylene group interposed with a sulfur atom, the organosilicon-based polymer compound has a thioether bond between Si in the polysiloxane skeleton and the above-mentioned main group.

[0145] <Organosilicon-based polymer S>

[0146] As described above, in one embodiment, the organosilicon-based polymer S is the organosilicon-based polymer Sh, and in another embodiment, the organosilicon-based polymer S is the organosilicon-based polymer Sg.

[0147] The organosilicon-based polymer S can be linear or branched. From the aspect of easily forming a crosslinked polymer with the polymer P, the organosilicon-based polymer S is preferably linear.

[0148] The organosilicon-based polymer S can have any structure such as a random polymer or a block polymer. From the aspect of easy manufacture, it is preferably a random polymer.

[0149] The weight-average molecular weight of the organosilicon-based polymer S is not particularly limited and is 1,000 to 1,000,000, preferably 5,000 to 800,000, more preferably 10,000 to 600,000. The weight-average molecular weight mentioned here is the weight-average molecular weight measured by gel permeation chromatography (GPC) method and converted with an arbitrary standard substance (polystyrene).

[0150] (Polymer P)

[0151] The polymer P is a high-molecular compound having a backbone other than the polysiloxane backbone as the main chain. The polymer P can have either the above-mentioned main group or the above-mentioned guest group in the molecule, and preferably has only either one.

[0152] For example, the polymer P may have at least one host group on the side chain, or may have at least one guest group on the side chain. Additionally, as described later, the polymer P may have a host group at one end or both ends, or may have a guest group at one end or a guest group at each of the two ends. Hereinafter, the polymer P having the host group is referred to as "polymer Ph", and the polymer P having the guest group is referred to as "polymer Pg".

[0153] <polymer Pg>

[0154] The type of the polymer Pg is not particularly limited as long as it has a backbone other than the polysiloxane backbone as the main chain and has a guest group. For example, a known polymer containing a guest group can be used as the polymer Pg.

[0155] Examples of the polymer Pg include vinyl polymers having a guest group, addition polymers having a guest group, and condensation polymers having a guest group. Hereinafter, each polymer will be described in detail.

[0156] 《Polymer Pg; Vinyl Polymer》

[0157] When the polymer Pg is a vinyl polymer having a guest group, examples include polymers formed by radical polymerization of vinyl monomers, such as known vinyl polymers containing a guest group. In the vinyl polymer containing a guest group, the guest group can be bonded to the end or side chain by a covalent bond, and preferably, the guest group can be bonded to the side chain by a covalent bond.

[0158] The vinyl polymer containing a guest group may have a vinyl monomer unit containing a guest group in its structural unit. The vinyl monomer unit containing a guest group is a structural unit formed from a vinyl monomer containing a guest group. The vinyl monomer containing a guest group is not particularly limited as long as it is a vinyl compound having the above guest group, and for example, known vinyl monomers containing a guest group can be widely exemplified. The vinyl monomer containing a guest group is a compound having any one of acryloyl (CH2=CH(CO)-), methacryloyl (CH2=CCH3(CO)-), styryl, vinyl, allyl, etc.

[0159] As a specific example of the vinyl monomer containing a guest group, a compound represented by the following general formula (g1) can be cited.

[0160] [Chemical Formula 8]

[0161]

[0162] In the formula (g1), Ra represents a hydrogen atom or a methyl group, RG represents the above-mentioned object group, R 2 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. Examples of the substituents mentioned here include: an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a halogen atom, a carboxyl group, a carbonyl group, a sulfonyl group, a sulfone group, a cyano group, etc.

[0163] In the compound represented by formula (g1), a (meth)acrylate or its derivative (i.e., R 2 is -COO-), a (meth)acrylamide or its derivative (i.e., R 2 is -CONH- or -CONR-, and R has the same meaning as the above-mentioned substituents) is preferred. In this case, the polymerization reaction can be easily carried out, and thus the production of the polymer Pg becomes easy.

[0164] It should be noted that in this specification, "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid", "(meth)acrylate" means "acrylate" or "methacrylate", and "(meth)allyl" means "allyl" or "methallyl".

[0165] In formula (g1), as long as R 2 is a divalent group formed by removing one hydrogen atom from an amino group which may have one substituent, the nitrogen atom of the amino group can be bonded to the carbon atom of the C═C double bond. As long as R 2 is a divalent group formed by removing one hydrogen atom from an amide group which may have one substituent, the carbon atom of the amide group can be bonded to the carbon atom of the C═C double bond. If R 2 is a divalent group formed by removing one hydrogen atom from an aldehyde group, the carbon atom of the aldehyde group can be bonded to the carbon atom of the C═C double bond. If R 2 is a divalent group formed by removing one hydrogen atom from a carboxyl group, the carbon atom of the carboxyl group can be bonded to the carbon atom of the C═C double bond.

[0166] As further specific examples of the vinyl monomer containing a guest group, the following can be cited: 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, tert-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)acrylate having a pyrene moiety, (meth)acrylamide having a pyrene moiety, etc.

[0167] The vinyl monomer containing a guest group can be produced by a known method. In addition, commercially available products can also be used as the vinyl monomer containing a guest group.

[0168] In the case where the polymer Pg is a vinyl polymer containing a guest group, the vinyl polymer containing a guest group may have at least one other vinyl monomer unit in addition to the vinyl monomer unit containing a guest group. The other monomer unit is referred to as the "third monomer unit".

[0169] The above-mentioned third monomer unit is a structural unit formed from a third monomer. The third monomer unit can be broadly cited as a polymerizable monomer capable of copolymerizing with the vinyl monomer containing a guest group.

[0170] As the third polymerizable monomer, various known vinyl-based polymerizable monomers can be cited. As a specific example of the third polymerizable monomer, the compound represented by the following general formula (a1) can be cited.

[0171] [Chemical formula 9]

[0172]

[0173] In formula (a1), Ra represents a hydrogen atom or a methyl group, and R 3 represents a halogen atom, a hydroxyl group, a mercapto group, an amino group which may have one substituent or a salt thereof, a carboxyl group which may have one substituent or a salt thereof, an amide group which may have one or more substituents or a salt thereof, or a phenyl group which may have one or more substituents.

[0174] In formula (a1), in R 3In the case of a carboxyl group having one substituent, examples include: a carboxyl group (i.e., an ester) obtained by substituting the hydrogen atom of the carboxyl group with a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyalkyl group (e.g., hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl), methoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5), ethoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5), etc. 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 can be either straight-chain or branched-chain.

[0175] In formula (a1), when R 3 In the case of an amide group having more than one substituent, i.e., a secondary amide or a tertiary amide, examples include: an amide group obtained by independently substituting one hydrogen atom or two hydrogen atoms of a primary amide with a hydrocarbon group having 1 to 20 carbon atoms or a hydroxyalkyl group (e.g., hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl). The hydrocarbon group having 1 to 20 carbon atoms preferably has 1 to 15 carbon atoms, more preferably 2 to 10 carbon atoms. The hydrocarbon group can be either straight-chain or branched-chain.

[0176] As specific examples of the compound represented by formula (a1), in addition to (meth)acrylic acid, allylamine, maleic anhydride, styrene, etc., examples also include: (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, 2-methoxy(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-phenylethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ethoxy-diethylene glycol (meth)acrylate, methoxy-triethylene glycol (meth)acrylate, methoxy-polyethylene glycol (meth)acrylate, etc.; (meth)acrylamide compounds such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethylacrylamide, N-isopropyl(meth)acrylamide, 2-hydroxyethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, etc. They can be used alone or in combination of two or more.

[0177] As the compound represented by the formula (a1), it is particularly preferably at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

[0178] In the case where the polymer Pg is a vinyl polymer containing a guest group, the content ratio of the guest group in the vinyl polymer containing the guest group is not particularly limited. For example, in all the structural units of the vinyl polymer containing the guest group, the content ratio of the vinyl monomer unit containing the guest group is, for example, 0.1 mol% or more and 30 mol% or less. From the aspect that the mechanical properties of the composite polymer material are more easily improved, in all the structural units of the vinyl polymer containing the guest group, the content ratio of the vinyl monomer unit containing the guest group is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, further preferably 0.8 mol% or more, and particularly preferably 1 mol% or more. In addition, from the aspect that the mechanical properties of the composite polymer material are more easily improved, in all the structural units of the vinyl polymer containing the guest group, the content ratio of the vinyl monomer unit containing the guest group is preferably 20 mol% or less, more preferably 15 mol% or less, further preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0179] It should be noted that the content ratio of the vinyl monomer unit containing the guest group in the vinyl polymer containing the guest group can be regarded as being consistent with the content ratio of the vinyl monomer containing the guest group in the monomer used in the production of the vinyl polymer containing the guest group.

[0180] The method for producing the vinyl polymer containing the guest group is not particularly limited. For example, the vinyl polymer containing the guest group can be produced by a known radical polymerization method.

[0181] 《Polymer Pg; Addition Polymerization Polymer》

[0182] In the case where the polymer Pg is an addition polymerization polymer having a guest group, for example, known addition polymerization polymers containing a guest group can be widely cited. Specifically, polymers having a urethane bond, that is, polyurethanes, can be cited.

[0183] The addition polymerization polymer containing the guest group is preferably, for example, a chain polymer having guest groups at both ends. At this time, the addition polymerization polymer containing the guest group easily forms a host-guest interaction with the organosilicon polymer S, and thus it is easy to stably form a crosslinked polymer.

[0184] As the addition polymer-based polymer containing a guest group, for example, a polymer having guest groups at both ends and having the following structural unit can be cited. This structural unit is formed by bonding a unit derived from a compound having two or more isocyanate groups and a unit derived from a compound having two or more hydroxyl groups.

[0185] As the compound having two isocyanate groups, the compound represented by the following formula (3) can be cited.

[0186] O=C=N-R A -N=C=O (3)

[0187] (In the formula, R A represents a divalent organic group)

[0188] In formula (3), as specific examples of R A (divalent organic group), the following can be cited: (CH2) n (n is an integer from 1 to 20), methylenediphenylene, methylenedicyclohexyl, 3-methyl-3,5,5-trimethylcyclohexylidene, dimethylphenylene, metaphenylene, phenylene, benzylidene, cyclohexylidene, isophorone group, etc. When the divalent organic group is (CH2) n , n is preferably 2 to 10, more preferably 3 to 8.

[0189] As the compound having two hydroxyl groups, the following can be cited: ethylene glycol, propylene glycol, 1,2-propylene glycol, butylene glycol, pentylene glycol, 3-methyl-1,5-pentanediol, hexylene glycol, neopentyl glycol, diethylene glycol, 1,3-propylene glycol (triethylene glycol, POD), tetraethylene glycol, polyethylene glycol, polyether diol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, dibromobisphenol A, 1,4-cyclohexanedimethanol, dihydroxyethyl terephthalate, dihydroxyethyl hydroquinone ether, etc. As the polyether diol, the following can be cited: polytetramethylene ether glycol (PTHF), etc.

[0190] The method for producing the addition polymer-based polymer containing a guest group is not particularly limited. For example, it can be produced by the same method as a known addition polymer-based polymer. For example, the addition polymer-based polymer containing a guest group can be produced by the addition polymerization of a raw material containing a guest molecule, a compound having two or more isocyanate groups, and a compound having two or more hydroxyl groups. The conditions for the addition polymerization are also not particularly limited, and the same conditions as those for known addition polymerization can be adopted.

[0191] As the above-mentioned guest molecule, as long as it has the above-mentioned guest group, its type is not particularly limited. For example, it may include: a guest molecule having one or two amino groups, a guest molecule having one or two hydroxyl groups, a guest molecule having one or two carboxyl groups, a guest molecule having one or two epoxy groups, a guest molecule having one or two isocyanate groups, a guest molecule having one or two mercapto groups, and a guest molecule having one or two carboxylic acid chlorides.

[0192] As the guest molecule having one or two amino groups, for example, it may include: 1-adamantanamine, benzylamine, tert-butylamine, n-butylamine, 1-aminopyrene, aminodicyclopentadienyliron, 4-aminoazobenzene, 4-aminostilbene, cyclohexylamine, hexylamine, 4,4'-diaminodiphenylmethane, p-xylenediamine, diaminodicyclopentadienyliron, 4,4'-diaminoazobenzene, 4,4'-diaminostilbene, 1,4-diaminocyclohexane, 1,6-diaminocyclohexane, α,ω-diaminopolyethylene glycol, α,ω-diaminopolypropylene glycol, 2,2-bis(4-aminophenyl)propane, 1,1-bis(4-aminophenyl)-1-phenylethane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)butane, bis(4-aminophenyl)diphenylmethane, 2,2-bis(3-methyl-4-aminophenyl)propane, bis(4-aminophenyl)-2,2-dichloroethylene, 1,1-bis(4-aminophenyl)ethane, 2,2-bis(4-amino-3-isopropylphenyl)propane, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, bis(4-aminophenyl)sulfone, 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene, 1,1-bis(4-aminophenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-aminophenyl)cyclohexane, etc.

[0193] As a compound having one or two hydroxyl groups, examples thereof include: 1-hydroxyadamantane, benzyl alcohol, tert-butanol, n-butanol, 1-hydroxypyrene, 1-hydroxymethyldicyclopentadienyliron, 4-hydroxyazobenzene, 4-hydroxystilbene, cyclohexanol, hexanol, 4,4'-dihydroxydiphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 1,4-benzenedimethanol, 1,1'-dihydroxymethyldicyclopentadienyliron, 4,4'-dihydroxyazobenzene, 4,4'-dihydroxystilbene, 1,4-cyclohexanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)butane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)-2,2-dichloroethylene, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, bis(4-hydroxyphenyl)sulfone, 1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bisphenol A, etc.

[0194] As a compound having one or two carboxyl groups, examples thereof include: 1-carboxyadamantane, benzoic acid, pivalic acid, butyric acid, 1-carboxypyrene, 1-carboxydicyclopentadienyliron, 4-carboxyazobenzene, 4-carboxystilbene, cyclohexanecarboxylic acid, hexanoic acid, 4,4'-dicarboxydiphenylmethane, 1,4-benzenedicarboxylic acid, 1,4-phenylenediacetic acid, 1,1'-dicarboxydicyclopentadienyliron, 4,4'-dicarboxyazobenzene, 4,4'-dicarboxystilbene, 1,4-cyclohexanedicarboxylic acid, 1,6-hexanedicarboxylic acid, α,ω-dicarboxypolyethylene glycol, α,ω-dicarboxypolypropylene glycol, 2,2-bis(4-carboxyphenyl)propane, 1,1-bis(4-carboxyphenyl)-1-phenylethane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(4-carboxyphenyl)butane, bis(4-carboxyphenyl)diphenylmethane, 2,2-bis(3-methyl-4-carboxyphenyl)propane, bis(4-carboxyphenyl)-2,2-dichloroethylene, 1,1-bis(4-carboxyphenyl)ethane, 2,2-bis(4-carboxy-3-isopropylphenyl)propane, 1,3-bis(2-(4-carboxyphenyl)-2-propyl)benzene, bis(4-carboxyphenyl)sulfone, 1,4-bis(2-(4-carboxyphenyl)-2-propyl)benzene, 1,1-bis(4-carboxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-carboxyphenyl)cyclohexane, etc.

[0195] Examples of the compound having one or two carboxylic acid chlorides include: 1-adamantanecarbonyl chloride, terephthaloyl chloride, pivaloyl chloride, butyryl chloride, 1-pyrenecarbonyl chloride, 1-ferrocenecarbonyl chloride, 4-azobenzenecarbonyl chloride, 4-stilbenecarbonyl chloride, cyclohexanecarbonyl chloride, hexyl chloride, 4,4'-diphenylmethanedicarbonyl chloride, 1,4-benzenedicarbonyl chloride, 1,4-phenylenedicarbonyl chloride, 1,1'-ferrocenedicarbonyl chloride, 4,4'-azobenzenedicarbonyl chloride, 4,4'-stilbenedicarbonyl chloride, 1,4-cyclohexanedicarbonyl chloride, 1,6-hexanedicarbonyl chloride, α,ω-polyethyleneglycol dicarbonyl chloride, α,ω-polypropyleneglycol dicarbonyl chloride, 2,2-bis(4-phenylcarbonyl chloride)propane, 1,1-bis(4-phenylcarbonyl chloride)-1-phenylethane, 2,2-bis(4-phenylcarbonyl chloride)hexafluoropropane, 2,2-bis(4-phenylcarbonyl chloride)butane, bis(4-phenylcarbonyl chloride)diphenylmethane, 2,2-bis(3-methyl-4-phenylcarbonyl chloride)propane, bis(4-phenylcarbonyl chloride)-2,2-dichloroethylene, 1,1-bis(4-phenylcarbonyl chloride)ethane, 2,2-bis(3-isopropylphenyl-4-carbonyl chloride)propane, 1,3-bis(2-(4-phenylcarbonyl chloride)-2-propyl)benzene, bis(4-phenylcarbonyl chloride)sulfone, 1,4-bis(2-(4-phenylcarbonyl chloride)2-propyl)benzene, 1,1-bis(4-phenylcarbonyl chloride)-3,3,5-trimethylcyclohexane, 1,1-bis(4-phenylcarbonyl chloride)cyclohexane, etc.

[0196] Examples of the compound having one or two epoxy groups include adamantane oxide, styrene oxide, 1,2-epoxybutane, 1-epoxy pyrene, epoxy ferrocene, 4-epoxy azobenzene, 4-epoxy stilbene, cyclohexene oxide, 1,2-epoxyhexane, 2,2'-bis(4-glycidyloxyphenyl) propane, p-diglycidyloxybenzene, diglycidyloxy ferrocene, 4,4'-diglycidyloxy azobenzene, 4,4'-diglycidyloxy ferrocene, 1,4-diglycidyloxy cyclohexane, 1,6-diglycidyloxy cyclohexane, α,ω-diglycidyloxy polyethylene glycol, α,ω-diglycidyloxy polypropylene glycol, 1,1-bis(4-glycidyloxyphenyl)-1-phenylethane, 2,2-bis(4-glycidyloxyphenyl) hexafluoropropane, 2,2-bis(4-glycidyloxyphenyl) butane, bis(4-glycidyloxyphenyl) diphenylmethane, 2,2-bis(3-methyl-4-glycidyloxyphenyl) propane, bis(4-glycidyloxyphenyl)-2,2-dichloroethylene, 1,1-bis(4-glycidyloxyphenyl) ethane, 2,2-bis(4-glycidyloxy-3-isopropylphenyl) propane, 1,3-bis(2-(4-glycidyloxyphenyl)-2-propyl) benzene, bis(4-glycidyloxyphenyl) sulfone, 1,4-bis(2-(4-glycidyloxyphenyl)-2-propyl) benzene, 1,1-bis(4-glycidyloxyphenyl)-3,3,5-trimethyl cyclohexane, 1,1-bis(4-glycidyloxyphenyl) cyclohexane, etc.

[0197] Examples of the compound having one or two isocyanate groups include: 1-adamantane isocyanate, benzyl isocyanate, phenyl isocyanate, tert-butyl isocyanate, butyl isocyanate, 1-pyrene isocyanate, ferrocene isocyanate, azobenzene-4-isocyanate, stilbene-4-isocyanate, cyclohexane isocyanate, hexane isocyanate, 4,4'-diisocyanatophenylmethane, p-phenylene diisocyanate, ferrocene-1,1'-diisocyanate, azobenzene-4,4'-diisocyanate, stilbene-4,4'-diisocyanate, cyclohexane 1,4-diisocyanate, cyclohexane-1,6-diisocyanate, polyethylene glycol diisocyanate, polypropylene glycol diisocyanate, 2,2-bis(4-phenylisocyanate)propane, 1,1-bis(4-phenylisocyanate)-1-phenylethane, 2,2-bis(4-phenylisocyanate)hexafluoropropane, 2,2-bis(4-phenylisocyanate)butane, bis(4-phenylisocyanate)diphenylmethane, 2,2-bis(3-methyl-4-phenylisocyanate)propane, bis(4-phenylisocyanate)-2,2-dichloroethylene, 1,1-bis(4-phenylisocyanate)ethane, 2,2-bis(3-isopropyl-4-phenylisocyanate)propane, 1,3-bis(2-(4-phenylisocyanato-)-2-propyl)benzene, bis(4-phenylisocyanate-)sulfone, 1,4-bis(2-(4-phenylisocyanato-)-2-propyl)benzene, 1,1-bis(4-phenylisocyanate-)-3,3,5-trimethylcyclohexane, 1,1-bis(4-phenylisocyanate-)cyclohexane, etc.

[0198] Examples of the compound having one or two thiol groups include: 1-adamantane thiol, benzyl mercaptan, tert-butyl mercaptan, butyl mercaptan, 1-pyrene thiol, ferrocene thiol, 4-thioazobenzene, 4-thiostilbene, cyclohexanethiol, hexanethiol, 4,4'-dithiobiphenylmethane, p-phenylenedithiol, 1,1'-dithiobiferrocene, 4,4'-dithiothioazobenzene, 4,4'-dithiothiostilbene, 1,4-dithiocyclohexane, 1,6-dithiocyclohexane, α,ω-dithiopolyethylene glycol, α,ω-dithiopolypropylene glycol, 1,1-bis(4-thiophenyl)-1-phenylethane, 2,2-bis(4-thiophenyl)hexafluoropropane, 2,2-bis(4-thiophenyl)butane, bis(4-thiophenyl)diphenylmethane, 2,2-bis(3-methyl-4-thiophenyl)propane, bis(4-thiophenyl)-2,2-dichloroethylene, 1,1-bis(4-thiophenyl)ethane, 2,2-bis(3-isopropyl-4-thiophenyl)propane, 1,3-bis(2-(4-thiophenyl)-2-propyl)benzene, bis(4-thiophenyl)sulfone, 1,4-bis(2-(4-thiophenyl)-2-propyl)benzene, 1,1-bis(4-thiophenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-thiophenyl)cyclohexane, etc.

[0199] The guest molecule is preferably at least one selected from compounds having one or two amino groups and compounds having one or two hydroxyl groups. Specifically, it is preferably at least one selected from 1-hydroxyadamantane (adamantanol), 1-adamantanamine, 4,4'-dihydroxydiphenylmethane, 4,4'-diaminodiphenylmethane, polyethylene glycol, polypropylene glycol, α,ω-diaminopolyethylene glycol, and α,ω-diaminopolypropylene glycol.

[0200] "Polymer Pg; Condensation Polymer"

[0201] In the case where the polymer Pg is a condensation polymer having a guest group, for example, well-known condensation polymers having a guest group can be widely cited. Specifically, polyamides having a guest group, polyesters having a guest group, polycarbonates having a guest group, etc. can be cited.

[0202] <Polymer Ph>

[0203] The type of the polymer Ph is not particularly limited as long as it has a backbone other than the polysiloxane backbone and has a host group. For example, well-known polymers containing a host group can be used as the polymer Ph.

[0204] The polymer Ph can be, for example, a vinyl-based polymer having a host group, an addition polymer having a host group, and a condensation polymer having a host group. Hereinafter, each polymer will be described in detail.

[0205] "Polymer Ph; Vinyl-Based Polymer"

[0206] In the case where the polymer Ph is a vinyl-based polymer having a host group, polymers formed by radical polymerization of vinyl-based monomers can be cited. For example, well-known vinyl polymers containing a host group can be cited. In the vinyl polymer containing a host group, the host group is, for example, bonded to the side chain by a covalent bond, and preferably the host group is bonded to the side chain by a covalent bond.

[0207] The vinyl polymer containing a host group may have a vinyl monomer unit containing a host group in its structural unit. The vinyl monomer unit containing a host group is a structural unit formed from a vinyl monomer containing a host group. The vinyl monomer containing a host group is not particularly limited as long as it is the above-mentioned vinyl compound having a host group. For example, well-known vinyl monomers containing a host group can be widely exemplified. The vinyl monomer containing a host group is a compound having any one of acryloyl (CH2=CH(CO)-), methacryloyl (CH2=CCH3(CO)-), and styryl, vinyl, allyl, etc.

[0208] As a specific example of the vinyl monomer containing the main group, a compound represented by the following general formula (h1) can be cited.

[0209] [Chemical formula 10]

[0210]

[0211] In formula (h1), Ra represents a hydrogen atom or a methyl group, and R H represents the above-mentioned main group, and R 1 has the same meaning as R in the above formula (g1) 2 .

[0212] Alternatively, the vinyl monomer containing the main group may include a compound represented by the following general formula (h2).

[0213] [Chemical formula 11]

[0214]

[0215] In formula (h2), Ra, R H and R 1 respectively have the same meanings as Ra, R H and R 1 in formula (h1).

[0216] Furthermore, the vinyl monomer containing the main group may include a compound represented by the following general formula (h3).

[0217] [Chemical formula 12]

[0218]

[0219] In formula (h3), Ra, R H and R 1 respectively have the same meanings as Ra, R H and R 1 in formula (h1). n is an integer of 1 to 20, preferably 1 to 10, more preferably 1 to 5. Rb represents hydrogen or an alkyl group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms).

[0220] It should be noted that the main group R H in the vinyl monomer containing the main group represented by formulas (h1), (h2) and (h3) is an example when it is a monovalent group obtained by removing one hydroxyl group from cyclodextrin or its derivative.

[0221] In the formulas (h1) to (h3), the substituents are not particularly limited. For example, as the substituents, the following can be mentioned: an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a halogen atom, a carboxyl group, a carbonyl group, a sulfonyl group, a sulfone group, a cyano group, etc.

[0222] In the formulas (h1) to (h3), as long as R 1 is a divalent group formed by removing one hydrogen atom from an amino group that may have one substituent, the nitrogen atom of the amino group can be bonded to the carbon atom of the C═C double bond. In the formulas (h1) to (h3), if R 1 is a divalent group formed by removing one hydrogen atom from an amide group that may have one substituent, the carbon atom of the amide group can be bonded to the carbon atom of the C═C double bond. In the formulas (h1) to (h3), if R 1 is a divalent group formed by removing one hydrogen atom from an aldehyde group, the carbon atom of the aldehyde group can be bonded to the carbon atom of the C═C double bond. In the formulas (h1) to (h3), when R 1 is a divalent group formed by removing one hydrogen atom from a carboxyl group, the carbon atom of the carboxyl group can be bonded to the carbon atom of the C═C double bond.

[0223] The compounds represented by the formulas (h1) to (h3) are preferably, for example, (meth)acrylate derivatives (i.e., R 1 is -COO-), (meth)acrylamide derivatives (i.e., R 1 is -CONH- or -CONR-, and R has the same meaning as the above-mentioned substituents). As R of the above -CONR-, for example, an alkyl group having 1 to 20 carbon atoms is preferably used, an alkyl group having 1 to 10 carbon atoms is more preferably used, and an alkyl group having 1 to 6 carbon atoms is particularly preferably used.

[0224] When the polymer Ph is a vinyl polymer containing a host group, the vinyl polymer containing a host group may have other vinyl monomer units in addition to the vinyl monomer units containing a host group. As the other monomer units, the above-mentioned third monomer units can be mentioned.

[0225] When the polymer Ph is a vinyl polymer containing a host group, the content ratio of the host group in the vinyl polymer containing the host group is not particularly limited. For example, in all the structural units of the vinyl polymer containing the host group, the content ratio of the vinyl monomer unit containing the host group is, for example, 0.1 mol% or more and 30 mol% or less. From the viewpoint of more easily improving the mechanical properties of the composite polymer material, in all the structural units of the vinyl polymer containing the host group, the content ratio of the vinyl monomer unit containing the host group is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, further preferably 0.8 mol% or more, and particularly preferably 1 mol% or more. In addition, from the viewpoint of more easily improving the mechanical properties of the composite polymer material, in all the structural units of the vinyl polymer containing the host group, the content ratio of the vinyl monomer unit containing the host group is preferably 20 mol% or less, more preferably 15 mol% or less, further preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0226] It should be noted that the content ratio of the vinyl monomer unit containing the host group in the vinyl polymer containing the host group can be regarded as being consistent with the content ratio of the vinyl monomer containing the host group in the monomer used in the production of the vinyl polymer containing the host group.

[0227] The production method of the vinyl polymer containing the host group is not particularly limited. For example, the vinyl polymer containing the host group can be produced by a known radical polymerization method.

[0228] "Polymer Ph: Addition Polymerization Polymer"

[0229] In the case where the polymer Ph is an addition polymerization polymer having a host group, for example, well-known addition polymerization polymers containing a host group can be widely cited. Specifically, polymers having a urethane bond, that is, polyurethanes, can be cited.

[0230] The addition polymerization polymer containing the host group is preferably, for example, a chain polymer having host groups at both ends. In this case, the addition polymerization polymer containing the host group easily forms a host-guest interaction with the organosilicon polymer S, and thus it is easy to stably form a crosslinked polymer.

[0231] As such an addition polymerization polymer containing a host group, for example, a polymer having host groups at both ends and having the following structural unit can be cited. This structural unit is formed by bonding a unit derived from a compound having two isocyanate groups and a unit derived from a compound having two hydroxyl groups.

[0232] The method for manufacturing a polyaddition polymer containing a main group is not particularly limited. For example, it can be manufactured by the same method as a known polyaddition polymer. For example, a polyaddition polymer containing a main group can be manufactured by a polyaddition reaction of a raw material containing a main molecule, a compound having two isocyanate groups, and a compound having two hydroxyl groups. The conditions for the polyaddition reaction are also not particularly limited, and the same conditions as those for known polyaddition reactions can be adopted. The compound having two isocyanate groups and the compound having two hydroxyl groups are the same as those used in the manufacture of a polyaddition polymer containing a guest group.

[0233] As the above-mentioned main molecule, as long as it has the above-mentioned main group, its type is not particularly limited. For example, examples include: a main molecule having one or two amino groups, a main molecule having one or two hydroxyl groups, a main molecule having one or two carboxyl groups, a main molecule having one or two epoxy groups, a main molecule having one or two isocyanate groups, a main molecule having one or two thiol groups, and a main molecule having one or two carboxylic acid chlorides.

[0234] 《Polymer Ph; Condensation Polymer》

[0235] In the case where the polymer Ph is a condensation polymer containing a guest group, for example, various known condensation polymers containing a guest group can be widely cited. Specifically, examples include polyamides having a main group, polyesters having a main group, and polycarbonates having a main group.

[0236] <Polymer P>

[0237] As described above, in one embodiment, the polymer P is a silicone-based polymer Ph. Additionally, in another embodiment, the polymer P is a polymer Pg. When the silicone-based polymer S is a silicone-based polymer Sh, the polymer P is a polymer Pg. When the silicone-based polymer S is a silicone-based polymer Sg, the polymer P is a polymer Ph.

[0238] The polymer P can be linear or branched. Considering the aspect of easily forming a crosslinked polymer with the silicone-based polymer S, the polymer P is preferably linear.

[0239] The polymer P can have any structure such as a random polymer or a block polymer. Considering the aspect of easy manufacture, it is preferably a random polymer.

[0240] The weight-average molecular weight of the polymer P is not particularly limited, and is from 1,000 to 1,000,000, preferably from 5,000 to 800,000, and more preferably from 10,000 to 600,000. The weight-average molecular weight referred to herein is the weight-average molecular weight determined by gel permeation chromatography (GPC) method and converted with an arbitrary standard substance (polystyrene).

[0241] (Composite polymer material)

[0242] The composite polymer material of the present invention contains a crosslinked polymer formed by crosslinking an organosilicon polymer S and a polymer P, and in this crosslinked polymer, a host-guest interaction based on a host group and a guest group is formed between the organosilicon polymer S and the polymer P. Such a host-guest interaction is formed by forming an inclusion complex of the host group and the guest group as described above, and can be said to form a crosslinked polymer with the inclusion complex as a crosslinking point.

[0243] In one embodiment of the composite polymer material of the present invention, the host-guest interaction in the crosslinked polymer can be formed between the side chain of the organosilicon polymer S and the side chain of the polymer P. In this embodiment, for example, the organosilicon polymer S can be set as the organosilicon polymer Sh, and the polymer P can be set as the polymer Pg, especially the above-mentioned vinyl polymer containing a guest group.

[0244] Figure 1 Schematically shows a crosslinked polymer formed by a host-guest interaction between the side chain of the organosilicon polymer S and the side chain of the above polymer P. Specifically, schematically shows a crosslinked polymer X1 formed by the host-guest interaction of the organosilicon polymer Sh ( Figure 1 in which is labeled Sh) and the vinyl polymer containing a guest group ( Figure 1 in which is labeled Pg) ( Figure 1 in which is labeled X1).

[0245] In Figure 1 the crosslinked polymer X1 shown, the guest group G of the side chain of the vinyl polymer (Pg) containing a guest group is included in the host group H of the side chain of the organosilicon polymer Sh to form an inclusion complex. This inclusion complex becomes a crosslinking point to form a crosslinked polymer X1.

[0246] When a crosslinked polymer is formed by a host-guest interaction between the side chain of the organosilicon polymer S and the side chain of the above polymer P, the polymer P is preferably a vinyl-based polymer. For example, as Figure 1 shown, a crosslinked polymer in which the organosilicon polymer S is the organosilicon polymer Sh and the polymer P is a vinyl polymer (Pg) containing a guest group can be cited.

[0247] In another embodiment of the composite polymer material of the present invention, host-guest interactions in the crosslinked polymer can be formed between the side chain of the silicone-based polymer S and the end of the polymer P. In this embodiment, for example, the silicone-based polymer S can be the silicone-based polymer Sh, and the polymer P can be the polymer Pg, particularly an addition polymer such as polyurethane.

[0248] Figure 2 Schematically shows a crosslinked polymer formed by host-guest interactions between the side chain of the silicone-based polymer S and the two ends of the above polymer P. Specifically, schematically shows a crosslinked polymer X2 formed by host-guest interactions between the silicone-based polymer Sh ( Figure 2 in which, labeled as Sh) and the addition polymer ( Figure 2 in which, labeled as Pg′). Figure 2 in which, labeled as X2).

[0249] In Figure 2 the crosslinked polymer X2 shown, a guest group at the end of the addition polymer (Pg′) is included in the host group H of the side chain of the silicone-based polymer Sh to form an inclusion complex. Specifically, the guest group at one end of the addition polymer (Pg′) is included in the host group H of the side chain of the silicone-based polymer Sh to form an inclusion complex, and the guest group at the other end is included in the host group H of the side chain of another silicone-based polymer Sh to form an inclusion complex. Each inclusion complex becomes a crosslinking point to form the crosslinked polymer X2.

[0250] When a crosslinked polymer is formed by host-guest interactions between the side chain of the silicone-based polymer S and the end of the polymer P, the polymer P is preferably at least one selected from the group consisting of addition polymers and condensation polymers, more preferably an addition polymer, and further preferably a polyurethane having guest groups at both ends.

[0251] The composite polymer material of the present invention can be composed only of a crosslinked polymer formed by crosslinking the silicone-based polymer S and the polymer P, or can be substantially composed only of the crosslinked polymer. In addition, as long as the effects of the present invention are not hindered, the composite polymer material can also contain other polymer components other than the crosslinked polymer. As other polymer components, non-crosslinking silicone-based polymers S and polymers P can be cited. In addition, polymers other than the silicone-based polymer S and the polymer P can be cited. The composite polymer material can also contain various additives other than polymer components.

[0252] In the crosslinked polymer contained in the composite polymer material of the present invention, the content ratio of the silicone-based polymer S to the polymer P is not particularly limited. For example, from the aspect that the mechanical properties of the composite polymer material are easily improved, the content ratio of the silicone-based polymer S to the total mass of the silicone-based polymer S and the polymer P is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and further preferably 40% by mass to 60% by mass.

[0253] In addition, in the crosslinked polymer contained in the composite polymer material of the present invention, the content ratio of the guest group to the polymer having the host group is preferably 0.1 mol% or more and 30 mol% or less, for example. In this case, the mechanical properties of the composite polymer material are more easily improved, and in addition, the self-healing property described later is also easily improved. The polymer having the host group referred to here means a silicone-based polymer Sh or a polymer Ph, etc. The content ratio of the guest group to the polymer having the host group is preferably 0.5 mol% or more, more preferably 1 mol% or more, further preferably 1.5 mol% or more, particularly preferably 2 mol% or more, and most preferably 3 mol% or more. In addition, it is preferably 20 mol% or less, more preferably 15 mol% or less, further preferably 10 mol% or less, particularly preferably 5 mol% or less. In particular, regarding the lower limit of the content ratio of the guest group, when the polymer Pg in the crosslinked polymer is an addition polymer, the content ratio of the guest group to the polymer having the host group is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, further preferably 0.2 mol% or more, particularly preferably 0.3 mol% or more, and most preferably 0.5 mol% or more.

[0254] As a preferred combination of the host group and the guest group for forming the crosslinked polymer, when the host group is derived from an α-cyclodextrin derivative, the guest group is preferably at least one selected from the group consisting of octyl and dodecyl. When the host group is derived from a β-cyclodextrin derivative, the guest group is preferably at least one selected from the group consisting of adamantyl and isobornyl. When the host group is derived from a γ-cyclodextrin derivative, the guest group is preferably at least one selected from the group consisting of octyl, dodecyl, cyclododecyl, and adamantyl.

[0255] The silicone-based polymer S contained in the crosslinked polymer may be one or more, and the polymer P contained in the crosslinked polymer may be one or more.

[0256] In the composite polymer material of the present invention, it is preferable that the above-mentioned silicone-based polymer S has at least one of the above-mentioned host groups, and the above-mentioned polymer P has at least one of the above-mentioned guest groups. That is, the crosslinked polymer is preferably formed from a silicone-based polymer Sh and a polymer Pg. In this case, the mechanical properties of the composite polymer material are easily improved, and in addition, when forming a molded article such as a film, the transparency is also easily improved.

[0257] As a specific form in the case where the crosslinked polymer is formed from a silicone-based polymer Sh and a polymer Pg, examples include Figure 1 the crosslinked polymer X1 shown in Figure 2 the crosslinked polymer X2 shown in

[0258] The host-guest interaction between the silicone-based polymer S and the polymer P is reversible. Therefore, the composite polymer material of the present invention can also have self-healing properties. For example, after cutting a molded article of the composite polymer material formed into a film shape or the like, the cut portions are re-bonded to each other, and thus the molded article can self-heal. This is because the host-guest interaction eliminated by cutting regenerates a new host-guest interaction due to its reversibility (that is, an inclusion complex can be re-formed).

[0259] In the crosslinked polymer, in addition to the host-guest interaction based on the inclusion complex, the silicone-based polymer S and the polymer P preferably further have an interaction based on hydrogen bonds. That is, it is preferable to further form hydrogen bonds between the above-mentioned silicone-based polymer S and the above-mentioned polymer P. At this time, the mechanical properties of the composite polymer material of the present invention are particularly easily improved. When both the silicone-based polymer S and the polymer P contain hydrogen-bonding functional groups, an interaction based on hydrogen bonds may occur between the silicone-based polymer S and the polymer P. Examples of the hydrogen-bonding functional group include a hydroxyl group, a carboxyl group, an amino group, and the like.

[0260] As an embodiment of the crosslinked polymer having hydrogen bonds, examples include a combination of a silicone-based polymer S containing the structural unit shown in the above formula (3.2) and a polymer P having a hydrogen-bonding functional group. In particular, examples include a combination of a silicone-based polymer Sh containing the structural unit shown in the above formula (3.2) and a polymer Pg having a hydrogen-bonding functional group.

[0261] The silicone-based polymer Sh for forming a crosslinked polymer having a hydrogen bond preferably contains a structural unit represented by the above formula (3.2) in which A is a hydroxyl group. That is, the silicone-based polymer Sh preferably contains the structural unit represented by the above formula (3.2) in which A is a hydroxyl group. In addition, as the polymer Pg for forming a crosslinked polymer having a hydrogen bond, a third monomer unit having a hydrogen-bonding functional group is preferably contained. As the third polymerizable monomer for forming the third monomer unit, examples include: (meth)acrylate containing a hydroxyl group, (meth)acrylate containing a carboxyl group, (meth)acrylate containing an amino group, and among them, (meth)acrylate containing a hydroxyl group is preferred. Examples of the (meth)acrylate containing a hydroxyl group include: 4-hydroxybutyl (meth)acrylate, 2-methoxy (meth)acrylate, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and the like.

[0262] The polymer Pg for forming a crosslinked polymer having a hydrogen bond is preferably a copolymer having a vinyl monomer unit containing a guest group, a (meth)acrylate unit containing a hydroxyl group, and a (meth)acrylate alkyl ester unit. In the (meth)acrylate alkyl ester unit, the number of carbon atoms of the alkyl group is preferably 1 to 8, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 1 to 2.

[0263] In the polymer Pg for forming a crosslinked polymer having a hydrogen bond, the content ratio of the above-mentioned (meth)acrylate containing a hydroxyl group is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and further preferably 10% by mass to 30% by mass, relative to the total amount of the structural units in the polymer Pg other than the vinyl monomer unit containing a guest group.

[0264] The shape of the composite polymer material of the present invention is not particularly limited. For example, it can be a molded body such as a film, sheet, plate, block, etc., or can be in the form of fine particles, fibers, granules, grains, etc. In addition, it can also be in a liquid form such as a solution, paste, dispersion, etc.

[0265] In the case of manufacturing a molded body of the composite polymer material, its manufacturing method is not particularly limited. For example, well-known molding methods can be widely used. Specifically, casting methods, compression molding methods, extrusion molding methods, injection molding methods, etc. can be cited.

[0266] The mechanical properties of the composite polymer material of the present invention are also excellent, especially one or both of the Young's modulus and toughness are improved. Therefore, the composite polymer material of the present invention is a soft and tough material. Moreover, the composite polymer material of the present invention can also have high transparency, and in addition, as described above, it also has excellent self-healing properties.

[0267] Therefore, the composite polymer material of the present invention can be used for various purposes, and considering the aspect of high transparency, it is also suitable for use as an optical material.

[0268] 2. Manufacturing method of composite polymer material

[0269] The manufacturing method of the composite polymer of the present invention is not particularly limited. For example, it may include a step of forming a crosslinked polymer by synthesizing polymer P in the presence of organosilicon polymer S. By using the manufacturing method including this step, the composite polymer of the present invention can be manufactured. In the manufacturing method including this step, host-guest interaction is easily formed (that is, inclusion complex is easily formed), and a crosslinked polymer can be synthesized efficiently.

[0270] Specifically, the composite polymer of the present invention can be manufactured by a manufacturing method including a step of synthesizing polymer Pg in the presence of organosilicon polymer Sh.

[0271] (Manufacturing method of organosilicon polymer Sh)

[0272] The manufacturing method of organosilicon polymer Sh is not particularly limited. For example, by reacting a compound containing a host group with a polysiloxane, a host group can be introduced into the side chain of the polysiloxane skeleton, and thus, organosilicon polymer Sh can be obtained. The type of this reaction is not particularly limited, and for example, an addition reaction can be cited.

[0273] Organosilicon polymer Sh can be obtained, for example, by a manufacturing method including the following step A.

[0274] Step A: A step of reacting a polysiloxane compound with at least one alkenyl compound.

[0275] In step A, as the polysiloxane compound, a polysiloxane compound having a -SH group and / or a -Si-H group in the side chain can be used. This polysiloxane compound can undergo an addition reaction with the above alkenyl compound. Thus, for example, when the alkenyl compound has a host group, the host group can be introduced into the side chain of the polysiloxane skeleton by covalent bonding.

[0276] As long as the type of the polysiloxane compound used in step A has a -SH group and / or a -Si-H group, its type is not particularly limited. For example, the polysiloxane compound used in step A may include: a compound having a structural unit represented by the above formula (3.1) and a structural unit represented by the above formula (3.2). Hereinafter, the polysiloxane compound having a structural unit represented by the above formula (3.1) and a structural unit represented by the above formula (3.2) is referred to as "polysiloxane compound a".

[0277] In the case where the polysiloxane compound a does not have an -SH group, for example, R in the above formula (3.1) 3 and R 4 at least one of them becomes hydrogen. When both R 3 and R 4 in the above formula (3.1) are not hydrogen, R 3 and R 4 are the same or different, preferably methyl, ethyl, n-propyl, isopropyl, and particularly preferably methyl.

[0278] In the polysiloxane compound a, in the above formula (3.2), R 7 is preferably methyl, ethyl, n-propyl, isopropyl, and particularly preferably methyl. In addition, when R 8 is an alkylene group having a heteroatom interposed therebetween, as R 8 , examples include: alkylene group, or an alkylene group having a thioether bond, for example, it can be exemplified as -(CH2) m1 -, -(CH2) m1 -S-(CH2) m2 -. Among these, m1 and m2 are numbers from 1 to 10, preferably from 1 to 8, more preferably from 1 to 5. m1 and m2 can be the same or different.

[0279] In the case where the polysiloxane compound a does not have an -SH group, in the above formula (3.2), A is a group other than a mercapto group. When the polysiloxane compound a has an -SH group, and when both R 3 and R 4 in the above formula (3.1) are not hydrogen, A is a mercapto group.

[0280] In all the structural units of the polysiloxane compound a, the content ratio of the structural unit represented by the above formula (3.1) can be, for example, 70 mol% or more, preferably 75 mol% or more, more preferably 80 mol% or more, further preferably 85 mol% or more, and particularly preferably 90 mol% or more. In addition, in all the structural units of the polysiloxane compound a, the content ratio of the structural unit represented by the above formula (3.1) can be, for example, 99.9 mol% or less, preferably 99 mol% or less, more preferably 98 mol% or less, further preferably 96 mol% or less, and particularly preferably 95 mol% or less.

[0281] In all the structural units of the polysiloxane compound a, the content ratio of the structural unit represented by the above formula (3.2) can be, for example, 0.1 mol% or more, preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 4 mol% or more, and particularly preferably 5 mol% or more. Further, in all the structural units of the polysiloxane compound a, the content ratio of the structural unit represented by the above formula (3.2) can be set to, for example, 30 mol% or less, preferably 25 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less, and particularly preferably 10 mol% or less.

[0282] The alkenyl group-containing compound used in Step A may be an alkenyl group-containing compound having a main group. Examples of the alkenyl group include vinyl group, allyl group, etc. The type of the alkenyl group-containing compound having a main group is not particularly limited, and for example, known compounds can be widely used. Specific examples of the alkenyl group-containing compound having a main group include the compound represented by the above formula (h1) and the compound represented by the above formula (h2). The alkenyl group-containing compound having a main group can be produced by a known method or a commercially available product can also be used.

[0283] In the reaction of Step A, an alkenyl group-containing compound other than the alkenyl group-containing compound having a main group may also be used in combination. This alkenyl group-containing compound is referred to as "alkenyl group-containing compound c".

[0284] Examples of the alkenyl group-containing compound c include an alkenyl group compound having 2 to 10 carbon atoms which may have a substituent. Examples of the substituent include a hydroxyl group, an amino group, a carboxyl group, etc. In the alkenyl group compound, the position of the carbon-carbon double bond is not particularly limited. For example, it may be at the terminal of the alkenyl group compound (for example, a 1,2-alkenyl compound). In this case, the above substituent may be present at the opposite terminal. Specific examples of the alkenyl group-containing compound c include 1-pentene, 2-pentene, allyl alcohol, etc. In the case of 1-pentene, the mechanical properties of the composite polymer material are likely to be improved.

[0285] In the reaction of Step A, the above polysiloxane compound is reacted with at least one alkenyl group-containing compound (an alkenyl group-containing compound having a main group). In this reaction, if necessary, the above alkenyl group-containing compound c is also used. In this case, the obtained composite polymer material is likely to have excellent mechanical properties (particularly excellent Young's modulus and toughness), and in addition, the transparency is also likely to be high.

[0286] In the reaction of Step A, the amount of the alkenyl group-containing compound (excluding the alkenyl group-containing compound c) used is not particularly limited. For example, it can be 0.1 mol% to 30 mol% relative to the above polysiloxane compound. Further, in the reaction of Step A, the amount of the alkenyl group-containing compound c used is, for example, 50 mol% to 150 mol% relative to the above polysiloxane compound.

[0287] The reaction of step A can be carried out, for example, in the presence of a photoinitiator. Thereby, the reaction between the polysiloxane compound and the alkenyl compound is easily promoted. Specifically, the reaction (addition reaction) between the -SH group and / or -Si-H group in the polysiloxane compound and the alkenyl group of the alkenyl compound is easily caused. In step A, when the polysiloxane compound has a Si-H group, the polysiloxane compound and the alkenyl compound can also be reacted by using a hydrosilylation reaction using a catalyst.

[0288] When a photoinitiator is used in the reaction of step A, its usage amount is not particularly limited. For example, relative to the above polysiloxane compound, the usage amount of the photoinitiator can be set to 1 mol% to 20 mol%. The reaction of step A can be carried out in various solvents. The type of solvent is not particularly limited, and for example, solvents that have been conventionally used in the addition reaction between an alkenyl compound and a silyl group or the addition reaction between an alkenyl compound and a thiol group can be widely used. Examples of the solvent include hydrocarbon solvents such as benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, and isophorone; alcohol solvents such as tert-butanol, benzyl alcohol, phenoxyethanol, and phenylpropanediol; halogenated hydrocarbon solvents such as dichloromethane and chloroform; ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, and anisole; ester solvents such as ethyl acetate, propyl acetate, ethyl carbitol acetate, and butyl carbitol acetate; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, etc.

[0289] The reaction of step A can be carried out, for example, by a method of irradiating active energy rays to a raw material containing a polysiloxane compound, an alkenyl compound, an alkenyl compound c, a photoinitiator, and a solvent to carry out the reaction, or a method of adjusting the above raw material to a specified temperature to carry out the reaction. Among them, from the aspect of easy reaction, the method of irradiating active energy rays is preferably adopted. Examples of the active energy rays include ultraviolet rays, electron rays, visible light, X-rays, ion rays, etc. Among them, from the aspect of versatility, ultraviolet rays or electron rays are preferably used, and ultraviolet rays are particularly preferred.

[0290] After carrying out the reaction of step A, starting materials (for example, polysiloxane compound, alkenyl compound, alkenyl compound c) etc. can be further added additionally. In this case, it is preferable to add the alkenyl compound c additionally, whereby the unreacted Si-H groups and SH groups in the polysiloxane compound can be consumed.

[0291] After the reaction of Process A is completed, the desired organosilicon polymer Sh can be obtained by appropriate purification means. It should be noted that regarding the organosilicon polymer Sg, in Process A, by using an alkenyl compound having a guest group instead of an alkenyl compound having a host group, the organosilicon polymer Sg can be produced.

[0292] Using the organosilicon polymer Sh produced as described above, a crosslinked polymer can be synthesized. That is, as described above, by synthesizing the polymer Pg in the presence of the organosilicon polymer Sh, a crosslinked polymer can be obtained.

[0293] Specifically, in the presence of the organosilicon polymer Sh, by performing a polymerization reaction of the monomer raw materials for forming the polymer Pg, the polymer Pg can be synthesized.

[0294] As the monomer raw materials for forming the polymer Pg, when the polymer Pg is a vinyl polymer containing a guest group, the above various monomer mixtures (a mixture of the compound represented by the formula (g1) and the compound represented by the formula (a1)) can be used. By subjecting this monomer mixture to a radical polymerization reaction in the presence of the organosilicon polymer Sh, a vinyl polymer containing a guest group can be synthesized. This radical polymerization reaction can, for example, widely use well-known radical polymerization reactions.

[0295] In addition, as the monomer raw materials for forming the polymer Pg, when the polymer Pg is an addition polymer containing a guest group, a raw material mixture containing the above guest molecule, a compound having two isocyanate groups, and a compound having two hydroxyl groups can be used. By subjecting this raw material mixture to an addition polymerization reaction in the presence of the organosilicon polymer Sh, an addition polymer containing a guest group can be synthesized. Such an addition polymerization reaction can, for example, widely use well-known addition polymerization reactions.

[0296] By synthesizing the polymer Pg in the presence of the organosilicon polymer Sh, the guest group is included in the host group on the side chain of the organosilicon polymer Sh, and the polymerization reaction of the polymer Pg is promoted to form a crosslinked polymer of the organosilicon polymer Sh and the polymer Pg.

[0297] The synthesis of polymer Pg in the presence of organosilicon polymer Sh can be carried out in various organic solvents. Examples of the organic solvents include: hydrocarbon solvents such as benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, and isophorone; alcohol solvents such as tert-butanol, benzyl alcohol, phenoxyethanol, and phenylpropanediol; halogenated hydrocarbon solvents such as dichloromethane and chloroform; ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, and anisole; ester solvents such as ethyl acetate, propyl acetate, ethyl carbitol acetate, and butyl carbitol acetate; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, etc.

[0298] As described above, polymer Pg is synthesized in the presence of organosilicon polymer Sh to form a crosslinked polymer based on the host-guest interaction between organosilicon polymer Sh and polymer Pg. The crosslinked polymer is separated, and the composite polymer material of the present invention can also be prepared by combining other materials and additives as needed.

[0299] In addition, when the crosslinked polymer is obtained as a solution, the solution can be used as the composite polymer material of the present invention, and various other components can also be added as needed. By using the solution, for example, a film of the composite polymer material can also be obtained.

[0300] When determining the invention included in the present application, the various structures (properties, structures, functions, etc.) described in each embodiment of the present application can be arbitrarily combined. That is, in the present application, all the themes constituted by all the combinations of the various structures that can be combined described in this specification are included.

[0301] Examples

[0302] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the embodiments.

[0303] (Production Example 1)

[0304] Weigh 5 g (3.9 mmol) of β-cyclodextrin, 700 mg (6.9 mmol) of N-hydroxymethylacrylamide, and 95 mg (0.6 mmol) of p-toluenesulfonic acid monohydrate in a 200 mL glass round-bottom flask, and add them to 25 mL of N,N-dimethylformamide to prepare a reaction solution. Heat the solution to 90 °C in an oil bath and stir for 1 hour to obtain a reaction solution. Then, let the reaction solution cool naturally and pour it into 45 mL of vigorously stirred acetone. After filtering and separating the resulting precipitate, wash it 3 times with 10 mL of acetone and dry it under reduced pressure at room temperature for 1 hour to obtain a reactant. Dissolve the reactant in 100 mL of distilled water and adsorb it through a column (apparent density 600 g / L) filled with porous polystyrene resin (Mitsubishi Chemical Diaion HP-20) for 30 minutes. Then, remove the solution components and pass 50 mL of a 10 vol% methanol (or acetonitrile) aqueous solution through the column 3 times newly to wash the polystyrene resin and remove unreacted β-cyclodextrin. Next, pass 500 mL of a 25 vol% methanol aqueous solution through the column 2 times to elute acrylamide methyl β-cyclodextrin (labeled as βCDAAmMe), which is the target product. Remove the solvent under reduced pressure to obtain βCDAAmMe as a white powder. Dissolve 20 g of this βCDAAmMe in 300 mL of pyridine, add 170.133 g of acetic anhydride, and stir at 55 °C for more than 12 hours. Then, add 50 mL of methanol to quench the reaction and concentrate it to a volume of 200 mL using an evaporator. Drop the resulting concentrated solution into 2,000 mL of water and recover the precipitate. Dissolve the precipitate in 200 mL of acetone, drop it into 2,000 mL of water, recover the formed precipitate, and dry it under reduced pressure to separate the host-group-containing vinyl monomer, which is the target product. The obtained host-group-containing vinyl monomer is a compound represented by the following formula (h1-2) (hereinafter, labeled as "TAcβCDAAmMe").

[0305] [Chemical formula 13]

[0306]

[0307] (Example 1-1)

[0308] According to Figure 3According to the reaction route shown in (a), the organosilicon polymer Sh (PDMS-TAcβCD-AAl(x)) was prepared. First, 4,500 mg (5.6 mmol, thiol group equivalent 10 eq., number average molecular weight ~1,000) of polydimethylsiloxane with a thiol group in the side chain (PDMS-SH) was used, 1,200 mg (0.58 mmol, 1 eq.) of TAcβCDAAmMe obtained in Production Example 1, 290 mg (5.0 mmol, 9 eq.) of allyl alcohol (AAl), and 92 mg (0.56 mmol, 1 eq.) of Irgacure 1173 as an ultraviolet photopolymerization initiator were dissolved in ethyl acetate (20 mL) to prepare a 20% by mass solution. After bubbling nitrogen through this solution for 5 minutes, ultraviolet light irradiation was carried out for 1 hour using a mercury lamp with a wavelength of 365 nm to generate PDMS-TAcβCD-AAl(x), which was obtained as a solution of the organosilicon polymer Sh. Here, x represents the proportion (mol%) of the siloxane unit having a host group in the organosilicon polymer Sh, and x = 1.

[0309] Next, according to Figure 3 the reaction route shown in (b), polymer Pg was synthesized in the presence of the organosilicon polymer Sh, thereby synthesizing a crosslinked polymer of the organosilicon polymer Sh and polymer Pg. Specifically, ethyl acrylate (EA), N-(1-adamantyl)acrylamide (AdAAm), and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO) as a visible light polymerization initiator were added to the solution of the organosilicon polymer Sh (PDMS-TAcβCD-AAl(x)) in the compounding amounts shown in Table 1 below to prepare the raw materials. In this raw material, visible light irradiation was carried out for 1 hour using a visible light LED with a wavelength of 420 nm to carry out the polymerization reaction. Then, it was air-dried in a fume hood at room temperature overnight, and then vacuum-dried in a vacuum oven at 80 °C overnight to obtain PDMS-TAcβCD-AAl / PEA-Ad(x,y;w PEA )(wherein, Figure 3 in (b), PEA is denoted as PR (R = EA). Therefore, C = C-R in the figure represents EA). This was used as a crosslinked polymer of the organosilicon polymer Sh and polymer Pg (having the structure of the crosslinked polymer X1 with Figure 1 ). Here, x and y are the proportion (mol%) of the siloxane unit having a host group in the organosilicon polymer Sh and the proportion (mol%) of the vinyl monomer unit containing a guest group in the organosilicon polymer Sh, respectively, and w PEA is the proportion (mass%) of EA in the total amount of the organosilicon polymer Sh and EA, and x = 1, y = 2, and w PEA = 50 were calculated from the addition amounts.

[0310] (Example 1-2)

[0311] Except for preparing the raw materials by changing to the compounding amounts shown in Table 1, PDMS-TAcβCD-AAl / PEA-Ad(x,y;w PEA ) was obtained by the same method as in Example 1-1. Regarding it as the cross-linked polymer of the silicone-based polymer Sh and the polymer Pg, it was calculated that x = 1, y = 5, w PEA = 50.

[0312] (Comparative Example 1-1)

[0313] Except for preparing the raw materials by changing to the compounding amounts shown in Table 1, PDMS-TAcβCD-AAl / PEA(x,y;wPEA) was obtained by the same method as in Example 1-1. Regarding it as the mixture of the silicone-based polymer Sh and the polymer without a guest group, it was calculated that x = 1, y = 0, w PEA = 50.

[0314] [Table 1]

[0315]

[0316] (Comparative Example 1-2)

[0317] TAcβCDAAmMe was not used. In addition, the usage amount of allyl alcohol was changed to 290 mg. Except for this, the polymerization reaction was carried out by the same method as in Example 1-1. Thus, a mixture of a polysiloxane without a host group and a vinyl polymer containing a guest group was obtained.

[0318] (Comparative Example 1-3)

[0319] Except for not using AdAAm, the polymerization reaction was carried out by the same method as in Comparative Example 1-2. Thus, a mixture of a polysiloxane without a host group and a vinyl polymer without a guest group was obtained.

[0320] (Evaluation Result 1)

[0321] Regarding the cross-linked polymers obtained in each example as composite polymer materials, evaluations were carried out.

[0322] The mixture obtained in Comparative Example 1-3 became turbid, and the mixture obtained in Comparative Example 1-2 was colorless and transparent, and oil droplets of 0.1 mm level were visible. The composite polymer materials obtained in Comparative Example 1-1 and Examples 1-1 to 1-2 were colorless and transparent. In Comparative Example 1-1, it was formed by mobile cross-linking, while in Examples 1-1 to 1-2, it was formed by reversible cross-linking. It can be considered that the compatibility of the two polymers was improved.

[0323] Figure 4 (a) and (b) in Figure 4 show the results of the tensile tests of the crosslinked polymers obtained in Examples 1-2. For comparison, the results of the same tests for Comparative Examples 1-1, 1-2, and 1-3 are shown in Figure 4 . In addition, Figure 4 (a) in Figure 4 represents the stress-strain curve, and (b) represents the correlation between Young's modulus and toughness. From Figure 4 , it can be seen that the crosslinked polymer obtained in Example 1-2 exhibits the highest fracture stress, fracture strain, and toughness.

[0324] Figure 5 (a) and (b) in Figure 5 show the results of the tensile tests of the crosslinked polymers obtained in Example 1-2. In addition, Figure 5 (a) in Figure 5 represents the stress-strain curve, and (b) represents the correlation between Young's modulus and toughness. From these results, it can be seen that the crosslinked polymer obtained in Example 1-2 has a high fracture stress and Young's modulus. In addition, if the content ratio of the guest groups increases, the fracture strain and toughness increase. By increasing the guest groups, reversible crosslinking recombination during stretching is likely to occur, so it can be said that stress dispersion is effectively carried out, and the extensibility and toughness are improved.

[0325] Figure 6 is the result obtained by cutting the center of a sample identical to the sample used in the tensile test in half, bringing the two halves into contact again, and conducting the tensile test of the test piece after "standing at room temperature for 24 hours" or "standing at 70 °C for 12 hours", and calculating the healing efficiency according to the following formula (10).

[0326] Healing efficiency (%) = [Toughness of the healed test piece] ÷ [Toughness of the initial (before cutting) test piece] × 100% (10)

[0327] Specifically, Figure 6 (a) in Figure 6 is the stress-strain curve of the tensile test of the test piece after the above "standing at room temperature for 24 hours", Figure 6 (b) in Figure 6 is the stress-strain curve of the tensile test of the test piece after the above "standing at 70 °C for 12 hours", Figure 6 (c) in Figure 6 is the result of the healing efficiency (%). For each example, the left bar graph is for the test piece after "standing at room temperature for 24 hours", and the right bar graph is for the healing efficiency of the test piece after "standing at 70 °C for 12 hours". The room temperature is 25 °C.

[0328] According to Figure 6As a result, in the test pieces after repairing at room temperature for 24 hours, the breaking strain increased as the content ratio of the guest group increased. In addition, the repair rate also increased as the content ratio of the guest group increased. Even when repairing at 70 °C for 12 hours, the breaking stress, breaking strain, and repair rate also increased as the content ratio of the guest group increased. In particular, in the test pieces after repair in Example 1-2, high extensibility with a strain elongation of more than 1,000% was exhibited. It is considered that if the amount of the guest group increases, the reformation of the host-guest complex dissociated by material cutting can be effectively carried out, so the self-healing property is improved.

[0329] (Example 2-1)

[0330] Instead of EA, 900 mg (7.0 mmol) of n-butyl acrylate (BA) was changed, and the amount of BAPO used was changed to 15 mg (0.035 mmol). Except for this, PDMS-TAcβCD-AAl / PBA-Ad(x,y;w was obtained by the same method as in Example 1-2 PBA ). Regarding it as a cross-linked polymer of the silicone-based polymer Sh and the polymer Pg, it was calculated that x = 1, y = 5, w PBA = 50.

[0331] (Example 3-1)

[0332] Instead of EA, 900 mg (4.9 mmol) of 2-ethylhexyl acrylate (EHA) was changed, and the amount of BAPO used was changed to 10 mg (0.024 mmol). Except for this, PDMS-TAcβCD-AAl / PEHA-Ad(x,y;w was obtained by the same method as in Example 1-2 PEHA ). Regarding it as a cross-linked polymer of the silicone-based polymer Sh and the polymer Pg, it was calculated as x = 1, y = 5, w PEHA = 50.

[0333] (Evaluation result 2)

[0334] The cross-linked polymers obtained in each example were used as composite polymer materials for evaluation.

[0335] The composite polymer materials obtained in Example 2-1 and Example 3-1 were colorless and transparent.

[0336] Figure 7 (a) and (b) show the results of the tensile tests of the cross-linked polymers obtained in each example. In addition, Figure 7(a) shows the stress-strain curve, and (b) shows the correlation between Young's modulus and toughness. It can be seen that the crosslinked polymers of Example 2-1 and Example 3-1 also have high fracture stress and Young's modulus, and are composite polymer materials with excellent mechanical properties.

[0337] Figure 8 This is the result obtained by cutting the center of a sample identical to the sample used in the tensile test in half with a cutter, then bringing them into contact again, and performing a tensile test on the test piece after "standing at 70 °C for 12 hours", and calculating the healing efficiency according to the above formula (10). From Figure 8 it can be seen that the fracture stress increases in the order of Example 1-2, Example 2-1, and Example 3-1. In addition, the healing efficiency shows 57% in Example 2-1 and is the maximum.

[0338] (Example 4-1)

[0339] Instead of EA, 900 mg (7.8 mmol) of 2-hydroxyethyl acrylate (HEA) was changed, and the amount of BAPO used was changed to 16 mg (0.039 mmol). Except for this, PDMS-TAcβCD-AAl / PHEA-Ad(x,y;w PHEA ) was obtained by the same method as in Example 1-2. Regarding it as a crosslinked polymer of the silicone-based polymer Sh and the polymer Pg, it was calculated that x = 1, y = 5, w PHEA = 50.

[0340] (Example 5-1)

[0341] Except for changing to the compounding amounts shown in Table 2 to prepare the raw materials, PDMS-TAcβCD-AAl / P(EA-HEA)-Ad(x,y;w PEA ;w PHEA ) was obtained by the same method as in Example 1-1. Here, x and y are the ratios (mol%) of the siloxane unit having a host group and the vinyl monomer unit containing a guest group to the silicone-based polymer Sh, respectively, and w PEA is the content ratio (mass%) of EA to the total amount of the silicone-based polymer Sh and EA, and w PHEA represents the content ratio (mass%) of HEA to the total amount of the silicone-based polymer Sh and HEA. It was calculated from the addition amounts that x = 1, y = 1, w PEA = 37.5, w PHEA = 12.5.

[0342] (Example 5-2)

[0343] Except for preparing the raw materials by changing to the compounding amounts shown in Table 2, PDMS-TAcβCD-AAl / P(EA-HEA)-Ad(x, y; w PEA ; w PHEA ) was obtained by the same method as in Examples 1-2. Regarding it as the crosslinked polymer of the silicone-based polymer Sh and the polymer Pg, it was calculated that x = 1, y = 2, w PEA = 25, w PHEA = 25.

[0344] (Example 5-3)

[0345] Except for preparing the raw materials by changing to the compounding amounts shown in Table 2, PDMS-TAcβCD-AAl / P(EA-HEA)-Ad(x, y; w PEA ; w PHEA ) was obtained by the same method as in Examples 1-2. Regarding it as the crosslinked polymer of the silicone-based polymer Sh and the polymer Pg, it was calculated that x = 1, y = 5, w PEA = 12.5, w PHEA = 37.5.

[0346] [Table 2]

[0347]

[0348] (Evaluation Results 3)

[0349] Regarding the crosslinked polymers obtained in each example as composite polymer materials, evaluations were carried out. The composite polymer materials obtained in Example 5-1 and Example 5-3 were colorless and transparent, and those obtained in Example 4-1 and Example 5-2 were slightly turbid but had high transparency, and no oil droplets were observed.

[0350] Figure 9 (a) and (b) of represent the results of the tensile tests of the crosslinked polymers obtained in each example. In addition, Figure 9 (a) of represents the stress-strain curve, and (b) represents the correlation between the Young's modulus and toughness. As can be seen from Figure 9 , the crosslinked polymer obtained in Example 5-3 showed the highest breaking stress, breaking strain, and toughness. In particular, compared with Examples 1-2, it was speculated that the mechanical properties of other examples were all improved, and thus the mechanical properties were improved by the hydrogen bond-based interaction.

[0351] Figure 10The result was obtained by cutting the center of a sample identical to the one used in the tensile test in half with a cutter, bringing the two halves back into contact, and performing a tensile test on the test piece after "standing at room temperature for 24 hours" or "standing at 70 °C for 12 hours", and calculating the healing efficiency using the above formula (10).

[0352] Specifically, Figure 10 (a) in is the stress-strain curve of the tensile test of the test piece after "standing at room temperature for 24 hours" as described above, Figure 10 (b) in is the stress-strain curve of the tensile test of the test piece after "standing at 70 °C for 12 hours" as described above, Figure 10 (c) in is the result of the healing efficiency (%). The left bar graph in each example is for the test piece after "standing at room temperature for 24 hours", and the right bar graph is for the healing efficiency of the test piece after "standing at 70 °C for 12 hours". The room temperature was 25 °C. According to Figure 10 the results, all have self-healing properties.

[0353] (Example 6-1)

[0354] According to Figure 11 the reaction route shown, a crosslinked polymer of a silicone-based polymer Sh and a polymer Pg was synthesized. First, according to the formulation table shown in Table 3 below, polydimethylsiloxane with a thiol group in the side chain (PDMS-SH), TAcβCDAAmMe obtained in Production Example 1, 1-adamantylamine (AdAm), 1-pentene (Pen), Irgacure1173 (1173) as a UV polymerization initiator, polytetramethylene ether glycol (PTHF), and 1,3-propanediol (PDO) were dissolved in dichloromethane (DCM) (10 mL) to prepare a solution. After bubbling nitrogen through this solution for 5 minutes, it was irradiated with UV light using a mercury lamp with a wavelength of 365 nm for 1 hour to generate PDMS-TAcβCD-AAl(x), which was obtained as a silicone-based polymer Sh solution. Here, x represents the proportion (mol%) of the siloxane unit having a host group in the silicone-based polymer Sh, and x = 1. In the solution of the silicone-based polymer Sh (PDMS-TAcβCD-AAl(x)), hexamethylene diisocyanate (HDI) and the polycondensation catalyst dibutyltin diacetate (DBTDA) were added in the amounts shown in Table 3, and the solution was stirred at 25 °C for 24 hours to carry out an addition polymerization reaction to generate polyurethane (PU). Then, it was air-dried in a fume hood at room temperature overnight and then vacuum-dried in a vacuum oven at 40 °C overnight to obtain PDMS-βCD / PU-Ad(x,y;w PU ). This was used as a crosslinked polymer of a silicone-based polymer Sh and a polymer Pg (having Figure 2(Structure of the crosslinked polymer X2). In the above PDMS-βCD / PU-Ad(x,y;w PU ), x represents the proportion (mol%) of the siloxane units having the host group in the organosilicon polymer Sh, y represents the content (mol%) of the guest group relative to the organosilicon polymer Sh, and w PU represents the content ratio (mass%) of PU relative to the organosilicon polymer Sh and PU (total amount of PTHF, PDO, HDI), and the values of x, y, and w PU are calculated from the addition amounts, x = 1, y = 0.5, w PU = 20.

[0355] (Comparative Example 6-1)

[0356] According to the formulation table shown in Table 3, a mixture of a polysiloxane without a host group and a polymer without a guest group was obtained.

[0357] [Table 3]

[0358]

[0359] (Evaluation Result 4)

[0360] The crosslinked polymers obtained in each example were used as composite polymer materials for evaluation.

[0361] The composite polymer material obtained in Example 6-1 was slightly turbid but had high transparency, and no oil droplets were observed. On the other hand, Comparative Example 6-1 became turbid and cracked severely during the drying process.

[0362] Figure 12 (a) and (b) of represent the results of the tensile test of the crosslinked polymer obtained in Example 6-1. In addition, Figure 12 (a) of represents the stress-strain curve, and (b) represents the correlation between Young's modulus and toughness. As can be seen from Figure 12 , the crosslinked polymer obtained in Example 6-1 showed excellent fracture stress, fracture strain, and toughness. It is considered that the mechanical properties are improved by the reversible host-guest interaction between the PDMS main chain and the PU main chain.

[0363] In addition, although not shown in the figure, it was confirmed that the composite polymer material obtained in Example 6-1 had self-healing properties.

[0364] (Evaluation Method of Mechanical Properties)

[0365] The mechanical properties of the composite polymer material were evaluated by using a tensile test (stroke-test force curve) ("AUTOGRAPH" (model: AGX-plus) manufactured by Shimadzu Corporation) to observe the breaking point of the composite polymer material (crosslinked polymer). Taking this breaking point as the end point, the maximum stress up to the end point was taken as the breaking stress of the polymer material. This tensile test was carried out by the method of moving the upper fixture: the lower end of the composite polymer material formed into a film shape with a thickness of 200 to 400 μm was fixed, and the upper end was operated at a tensile speed of 1 mm / second. The Young's modulus and toughness of the composite polymer material were calculated based on this measurement. The film-shaped composite polymer material was produced by casting the solution obtained in each example.

Claims

1. A composite polymer material, characterized in that, it contains a crosslinked polymer formed by crosslinking a silicone-based polymer S and a polymer P, the silicone-based polymer S has a polysiloxane backbone as the main chain, and the polymer P has a backbone other than the polysiloxane backbone as the main chain, a host-guest interaction based on a host group and a guest group is formed between the silicone-based polymer S and the polymer P, the host group is a monovalent group obtained by removing one hydrogen atom or one hydroxyl group from cyclodextrin or a cyclodextrin derivative.

2. The composite polymer material according to claim 1, wherein, the host-guest interaction is formed between the side chain of the silicone-based polymer S and the side chain of the polymer P.

3. The composite polymer material according to claim 1, wherein, the host-guest interaction is formed between the side chain of the silicone-based polymer S and the end of the polymer P.

4. The composite polymer material according to claim 2, wherein, the polymer P is a vinyl-based polymer.

5. The composite polymer material according to claim 3, wherein, the polymer P is one or more selected from the group consisting of addition polymerization polymers and condensation polymerization polymers.

6. The composite polymer material according to claim 1, wherein, the silicone-based polymer S has at least one of the host groups, and the polymer P has at least one of the guest groups.

7. The composite polymer material according to claim 1, wherein, a hydrogen bond is further formed between the silicone-based polymer S and the polymer P.

8. An optical material, characterized in that, it contains the composite polymer material according to any one of claims 1 to 7.

9. A method for manufacturing a composite polymer material, characterized in that, it is a method for manufacturing the composite polymer material according to any one of claims 1 to 7, the manufacturing method includes a step of forming the crosslinked polymer by synthesizing the polymer P in the presence of the silicone-based polymer S.

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