Silicone-based polymer compounds and silicone-based polymer materials

Abstract

Provided are a novel silicone-based polymer compound excelling in a mechanical property, and a silicone-based polymer material including the silicone-based polymer compound.　The silicone-based polymer compound of the present invention is a silicone-based polymer compound (H) having a polysiloxane skeleton as a main chain, wherein the polysiloxane skeleton has at least one host group in a side chain, and the host group is a monovalent group wherein one hydrogen atom or hydroxyl group is removed from cyclodextrin or a cyclodextrin derivative.

Description

[Technical Field]

[0001] This invention relates to silicone-based polymer compounds and silicone-based polymer materials. [Background technology]

[0002] Silicone polymer compounds (polysiloxanes), which have siloxane bonds (Si-O bonds) as their main backbone, are known to possess unique properties not found in organic polymers and are used in a variety of fields. Siloxane bonds have stronger bonding strength than the carbon-carbon or carbon-oxygen bonds found in general organic polymers and are chemically stable. Therefore, polysiloxanes, which are formed by repeatedly siloxane bonds, possess excellent heat resistance and weather resistance, for example. Furthermore, because polysiloxanes can form a helical structure with inorganic siloxane bonds on the inside and organic side-chain substituents on the outside, they are flexible, water-repellent, and have low biotoxicity. Consequently, polysiloxanes are highly valuable materials for various applications such as medical devices, rubber, paints, and protective films.

[0003] In recent years, efforts have been made to impart further functionality to materials based on polysiloxanes. For example, Non-Patent Document 1 proposes a technique in which hydrogen-bondable functional groups are introduced into the polysiloxane skeleton, and self-healing properties are exhibited through hydrogen bonding of these functional groups. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Adv.Mater.2018,30,1706846 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Recently, there has been a strong desire to add further functionalities to polysiloxanes in order to apply them to a variety of uses. In particular, silicone materials, such as polysiloxanes, exhibit different properties from general-purpose resins, and are expected to be applied in various fields. Therefore, there is a strong demand from industry for the creation of new silicone materials, and for example, the value of novel silicone polymer compounds with excellent mechanical properties is extremely high.

[0006] The present invention has been made in view of the above, and aims to provide a novel silicone polymer compound with excellent mechanical properties and a silicone polymer material containing the silicone polymer compound. [Means for solving the problem]

[0007] The inventors of this invention conducted extensive research to achieve the above objectives and, as a result, discovered that these objectives can be achieved by introducing specific functional groups into a silicone polymer compound having a polysiloxane skeleton as its main chain, thus completing the present invention.

[0008] In other words, the present invention encompasses, for example, the subject matter described in the following sections. Item 1 A silicone polymer compound (H) having a polysiloxane skeleton as its main chain, The polysiloxane skeleton has at least one host group in its side chain, The host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative, and is a silicone polymer compound. Section 2 A silicone polymer compound (G) having a polysiloxane skeleton as its main chain, The polysiloxane skeleton has at least one guest group in its side chain, The aforementioned guest group is a silicone polymer compound that can be inclusion-forming of cyclodextrin or a cyclodextrin derivative. Section 3 A silicone polymer compound (HG) having a polysiloxane skeleton as its main chain, wherein the polysiloxane skeleton has at least one host group and at least one guest group in its side chains. The host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative. The guest group is a silicone polymer compound that can be inclusion-forming of the cyclodextrin or cyclodextrin derivative. Section 4 The silicone polymer compound according to claim 1 or 3, wherein a thioether bond is formed between the Si in the polysiloxane skeleton and the host group. Section 5 The silicone polymer compound (H) described in item 1 and the silicone polymer compound (G) described in item 2 are included. The host group encapsulates the guest group in a silicone polymer material. Section 6 It contains the silicone polymer compound (HG) described in item 3, A silicone-based polymer material in which host groups and guest groups are bonded between molecules. Section 7 A crosslinked structure comprising the silicone polymer compound (H) described in claim 1, The crosslinked structure is a silicone polymer material having a structure in which the main chain of another silicone polymer compound (H) penetrates at least one of the host groups of the silicone polymer compound (H). Section 8 Furthermore, it contains a chain-like polymer compound (P1), The silicone polymer material according to claim 7, wherein the chain-like polymer compound (P1) penetrates the network of the crosslinked structure. Section 9 The crosslinked structure comprises a silicone polymer compound (H) and a chain polymer compound (P1) as described in item 1, The crosslinked structure is a silicone polymer material having a structure in which the chain polymer compound (P1) penetrates at least one of the host groups of the silicone polymer compound (H). Section 10 The product comprises the silicone polymer compound (H) described in item 1 and a chain-like polymer compound (P2) other than said polymer compound. The chain-like polymer compound (P2) has at least one host group in its side chain, and the host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative. At least one of the host groups of the silicone polymer compound (H) is penetrated by the main chain of another polymer compound (H), A silicone polymer material in which at least one of the host groups of the chain-like polymer compound (P2) is penetrated by the main chain of another chain-like polymer compound (P2). Section 11 An optical material containing a silicone polymer compound as described in any one of items 1 to 4. Section 12 An optical material containing a silicone polymer material as described in any one of items 5 to 10. Section 13 A method for producing silicone polymer compounds as described in items 1 to 4, The process includes a step of reacting a polysiloxane compound with at least one alkenyl group-containing compound, A method for producing a silicone polymer compound having an -SH group and / or a -Si-H group as the polysiloxane compound. [Effects of the Invention]

[0009] The silicone polymer compound according to the present invention has excellent mechanical properties and is suitable as a raw material for manufacturing silicone polymer materials. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic diagram showing the structure (mobile crosslinked structure) of silicone polymer material C. [Figure 2] This is a schematic diagram showing the structure (mobile crosslinked structure) of silicone polymer material C'. [Figure 3]This is a schematic diagram showing the structure of silicone polymer material D. [Figure 4] This is the reaction scheme for producing the silicone polymer compound (H) of Example 1-1. [Figure 5] This is the reaction scheme for producing the silicone polymer compound (H) of Example 3-1. [Figure 6] This is the reaction scheme for producing the silicone polymer compound (H) of Example 4-1. [Figure 7] This is the reaction scheme for producing the silicone polymer compound (HG) of Example 7. [Figure 8] This is the reaction scheme for producing polymer material C in Example 8. [Figure 9] This is the reaction scheme for producing polymer material D in Example 9. [Figure 10] This is the reaction scheme for producing the polymer material of Comparative Example 1-1. [Figure 11] This is the reaction scheme for producing the polymer material of Example 10-1. [Figure 12] These are the results of the tensile test (stroke-test force curve) of polymer material C' obtained in Examples 10-1 and 10-2. [Figure 13] These are the results of the tensile tests (stroke-test force curves) of polymer material C' obtained in Examples 11-1 to 11-3. [Figure 14] This shows the tensile test (stroke-test force curve) results for polymer material C' obtained in Example 12-1. [Figure 15] This is the reaction scheme for producing the polymer material of Example 13-1. [Figure 16] These are the results of the tensile tests (stroke-test force curves) for polymer material C' obtained in Example 13-1 and polymer material obtained in Comparative Example 13-1. [Figure 17] This is the reaction scheme for producing the polymer material of Example 14-1. [Figure 18]These are the results of the tensile tests (stroke-test force curves) for polymer material C' obtained in Example 14-1 and polymer material obtained in Comparative Example 14-1. [Figure 19] This is the reaction scheme for producing the polymer material of Example 15-1. [Figure 20] These are the results of tensile tests (stroke-test force curves) of the polymer materials obtained in Examples 16-1 to 16-3. [Figure 21] These are photographs showing the transparency test results of the polymer materials obtained in Examples 16-1 to 16-3 and Comparative Example 16-1. [Figure 22] These are the results of tensile tests (stroke-test force curves) of the polymer materials obtained in Examples 17-1 to 17-5. [Modes for carrying out the invention]

[0011] Embodiments of the present invention will be described in detail below. In this specification, the expressions "containing" and "including" include the concepts of "containing," "including," "substantially consisting of," and "consisting only of."

[0012] 1. Silicone polymer compounds The silicone polymer compounds according to the present invention are compounds having a polysiloxane skeleton as the main chain. In particular, the silicone polymer compounds according to the present invention include the following three types of silicone polymer compounds (H), silicone polymer compounds (G), and silicone polymer compounds (HG).

[0013] The silicone polymer compound (H) is a silicone polymer compound having a polysiloxane skeleton as its main chain, wherein the polysiloxane skeleton has at least one host group in its side chain. In the silicone polymer compound (H), the host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative.

[0014] Silicone polymer compound (G) is a silicone polymer compound having a polysiloxane skeleton as its main chain, wherein the polysiloxane skeleton has at least one guest group in its side chain. In silicone polymer compound (G), the guest group is a group that can be inclusion-enclosed in cyclodextrin or a cyclodextrin derivative.

[0015] The silicone polymer compound (HG) is a polymer compound having a polysiloxane skeleton as its main chain, wherein the polysiloxane skeleton has at least one host group and at least one guest group in its side chains. In the silicone polymer compound (HG), the host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative, and the guest group is a group that can be inclusion-forming of the cyclodextrin or cyclodextrin derivative.

[0016] Since both silicone polymer compound (H) and silicone polymer compound (HG) have a polysiloxane skeleton with at least one host group in its side chain, the structural units for forming the polysiloxane skeleton in these polymer compounds include at least one siloxane unit having a host group.

[0017] Furthermore, since both silicone polymer compound (G) and silicone polymer compound (HG) have at least one guest group in the side chain of the polysiloxane skeleton, the structural units for forming the polysiloxane skeleton in these polymer compounds include at least one siloxane unit having a guest group.

[0018] First, we will explain the siloxane units having the host group and the siloxane units having the guest group described above.

[0019] (Siloxane units containing a host group) A siloxane unit with a host group is a structural unit having a siloxane bond in the main chain and a host group directly or indirectly covalently bonded to the side chain.

[0020] As described above, the host group is a group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative. Preferably, the host group is a group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin derivative. The host group is not limited to a monovalent group; for example, the host group may be a divalent group. Furthermore, a polymerizable monomer unit containing a host group may contain only one host group, or it may contain two or more host groups.

[0021] The cyclodextrin derivatives, for example, preferably have a structure in which at least one of the hydroxyl groups of the cyclodextrin has a hydrogen atom substituted with a hydrophobic group. In other words, a cyclodextrin derivative is a molecule in which a cyclodextrin molecule has a structure in which another hydrophobic organic group is substituted. However, cyclodextrin derivatives have at least one hydrogen atom or at least one hydroxyl group, and preferably at least one hydroxyl group.

[0022] The hydrophobic group is preferably substituted with at least one group selected from the group consisting of hydrocarbon groups, acyl groups, and -CONHR (where R is a methyl group or an ethyl group). Hereinafter, in this specification, the aforementioned "at least one group selected from the group consisting of hydrocarbon groups, acyl groups, and -CONHR (where R is a methyl group or an ethyl group)" may be referred to as "hydrocarbon groups, etc." for convenience.

[0023] Herein, merely as a note for clarity, the term "cyclodextrin" as used herein means at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Therefore, a cyclodextrin derivative is at least one selected from the group consisting of α-cyclodextrin derivatives, β-cyclodextrin derivatives, and γ-cyclodextrin derivatives.

[0024] The host group is a monovalent or greater group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin derivative, but the hydrogen atom or hydroxyl group removed in the cyclodextrin derivative may be any part of the cyclodextrin or cyclodextrin derivative.

[0025] Here, if we let N be the total number of hydroxyl groups in one cyclodextrin molecule, then α-cyclodextrin has N=18, β-cyclodextrin has N=21, and γ-cyclodextrin has N=24.

[0026] If the host group is a monovalent group obtained by removing one "hydroxyl group" from a cyclodextrin derivative, then the cyclodextrin derivative is formed by substituting up to N-1 hydrogen atoms of hydroxyl groups with hydrocarbon groups or the like per cyclodextrin molecule. On the other hand, if the host group is a monovalent group obtained by removing one "hydrogen atom" from a cyclodextrin derivative, then the cyclodextrin derivative can have up to N hydrogen atoms of hydroxyl groups substituted with hydrocarbon groups or the like per cyclodextrin molecule.

[0027] The host group preferably has a structure in which 70% or more of the hydrogen atoms of the hydroxyl groups present in one cyclodextrin molecule are substituted with the hydrocarbon group or the like. More preferably, 80% or more of the hydrogen atoms of the hydroxyl groups present in one cyclodextrin molecule are substituted with the hydrocarbon group or the like, and particularly preferably, 90% or more of the hydrogen atoms of the hydroxyl groups are substituted with the hydrocarbon group or the like.

[0028] The host group preferably has a structure in which 13 or more hydrogen atoms of the hydroxyl groups present in one α-cyclodextrin molecule are substituted with the hydrocarbon group or the like. More preferably, the host group has 15 or more hydrogen atoms of the hydroxyl groups present in one α-cyclodextrin molecule are substituted with the hydrocarbon group or the like, and it is particularly preferable that 17 hydrogen atoms of the hydroxyl groups present in one α-cyclodextrin molecule are substituted with the hydrocarbon group or the like.

[0029] The host group preferably has a structure in which 15 or more hydrogen atoms of the hydroxyl groups present in one β-cyclodextrin molecule are substituted with the hydrocarbon group or the like. More preferably, the host group has 17 or more hydrogen atoms of the hydroxyl groups present in one β-cyclodextrin molecule are substituted with the hydrocarbon group or the like, and particularly preferably, 19 or more hydrogen atoms of the hydroxyl groups are substituted with the hydrocarbon group or the like.

[0030] The host group preferably has a structure in which 17 or more hydrogen atoms of the hydroxyl groups present in one molecule of γ-cyclodextrin are substituted with the hydrocarbon group or the like. More preferably, the host group has 19 or more hydrogen atoms of the hydroxyl groups present in one molecule of γ-cyclodextrin that are substituted with the hydrocarbon group or the like, and it is particularly preferable that 21 or more hydrogen atoms of the hydroxyl groups present in one molecule of γ-cyclodextrin are substituted with the hydrocarbon group or the like.

[0031] In cyclodextrin derivatives, the type of hydrocarbon group is not particularly limited. Examples of the hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups.

[0032] The number of carbon atoms in the hydrocarbon group is not particularly limited; for example, the hydrocarbon group preferably has 1 to 4 carbon atoms.

[0033] Specific examples of hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, and butyl groups. When the hydrocarbon group is a propyl or butyl group, it may be in either a linear or branched chain configuration.

[0034] In cyclodextrin derivatives, the acyl group can be an acetyl group, propionyl group, formyl group, etc. The acyl group is preferably an acetyl group because it facilitates the formation of host-guest interactions, allows other polymer chains to easily penetrate the host ring, and makes it easier to obtain polymer materials with excellent toughness and strength.

[0035] In cyclodextrin derivatives, -CONHR (where R is a methyl group or an ethyl group) is a methyl carbamate group or an ethyl carbamate group. -CONHR is preferably an ethyl carbamate group because it facilitates the formation of host-guest interactions, allows other polymer chains to easily penetrate the host ring, and makes it easier to obtain polymer materials with excellent toughness and strength.

[0036] In cyclodextrin derivatives, the hydrocarbon group is preferably an alkyl group or acyl group having 1 to 4 carbon atoms, preferably a methyl group and an acyl group, more preferably a methyl group, an acetyl group and a propionyl group, and particularly preferably a methyl group and an acetyl group.

[0037] The structure of a siloxane unit having a host group is not particularly limited, as long as it has a siloxane bond and a host group. For example, a siloxane unit having a host group is a structural unit represented by the following general formula (1.1).

[0038] [ka]

[0039] In equation (1.1), R H R indicates the host group. 1represents 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 with a substituent, or an aryl group having 6 to 20 carbon atoms which may be substituted with a substituent, R 6 represents an alkylene group which may have a hetero atom intervening therein.

[0040] Alternatively, the siloxane unit having a host group may also include a structural unit represented by the following general formula (1.2).

[0041]

Chemical formula

[0042] In formula (1.2), R H , R 1 is the same as R 5 and R 6 in the above formula (1.1), and R H , R 1 is the same as R 5 and R 6 .

[0043] In formulas (1.1) and (1.2), 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, etc., and preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and particularly preferably a methyl group.

[0044] R 5 If the compound has substituents, such substituents include hydroxyl groups, alkoxy groups, ester groups, cyano groups, nitro groups, sulfo groups, carboxyl groups, aryl groups, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), and so on.

[0045] In equations (1.1) and (1.2), R 1 Examples of substituents include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, halogen atoms, hydroxyl groups, carboxyl groups, nitro groups, sulfo groups, carbonyl groups, aryl groups, cyano groups, and the like.

[0046] In equations (1.1) and (1.2), R 1 If it is a divalent group formed by removing one hydrogen atom from an amino group which may have one substituent, then the nitrogen atom of the amino group is R 6 It can be combined with.

[0047] In equations (1.1) and (1.2), R 1 If it is a divalent group formed by removing one hydrogen atom from an amide group which may have one substituent, then the carbon atom of the amide group is R 6 It can be combined with.

[0048] In equations (1.1) and (1.2), R 1 If it is a divalent group formed by removing one hydrogen atom from an aldehyde group, then the carbon atom of the aldehyde group is R 6 It can be combined with.

[0049] In equations (1.1) and (1.2), R 1 If it is a divalent group formed by removing one hydrogen atom from a carboxyl group, then the carbon atom of the carboxyl group is R 6 It can be combined with.

[0050] In equations (1.1) and (1.2), R 6R is an alkylene group that may have a heteroatom interposed therein. The number of carbon atoms in the alkylene group is not particularly limited and can be, for example, 1 to 10 carbon atoms. 6 In this case, the number of carbon atoms in the alkylene is preferably 1 to 8, and more preferably 2 to 6.

[0051] R 6 R may be an alkylene group with a heteroatom interposed. In this case, R 6 Examples include alkylene groups having a thioether bond, for example, -(CH2) m1 -S-(CH2) m2 -Examples of combinations are shown. Here, m1 and m2 are the same or different numbers from 1 to 10, preferably 1 to 8, more preferably 1 to 5.

[0052] R 6 However, in the case of an alkylene group with a sulfur atom interposed, the silicone polymer compound will have a thioether bond between the Si in the polysiloxane skeleton and the host group.

[0053] (Siloxane unit containing a guest group) A siloxane unit with a guest group is a structural unit having a siloxane bond in the main chain and a guest group directly or indirectly covalently bonded to the side chain.

[0054] A guest group refers to a group that can be inclusion-enclosed in a cyclodextrin or cyclodextrin derivative. That is, the type of guest group is not limited as long as it is a group that can interact with the host group, and especially as long as it is a group that can be inclusion-enclosed in the host group. The guest group is not limited to a monovalent group; for example, the guest group may be a divalent group. Furthermore, a siloxane unit having a guest group may contain only one guest group or two or more guest groups.

[0055] Examples of guest groups include linear or branched hydrocarbon groups having 3 to 30 carbon atoms, cycloalkyl groups, heteroaryl groups, and organometallic complexes, which may have one or more substituents. Examples of substituents are the same as those mentioned above, and include halogen atoms (e.g., fluorine, chlorine, bromine, etc.), hydroxyl groups, carboxyl groups, ester groups, amide groups, and possibly protected hydroxyl groups.

[0056] More specific guest groups include linear or cyclic alkyl groups having 4 to 18 carbon atoms, and groups derived from polycyclic aromatic hydrocarbons. Linear alkyl groups having 4 to 18 carbon atoms may be either linear or branched. Cyclic alkyl groups may have a cage-like structure. Examples of polycyclic aromatic hydrocarbons include π-conjugated compounds formed by at least two aromatic rings, specifically naphthalene, anthracene, tetracene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, and the like.

[0057] Other examples of guest groups include monovalent groups formed by removing one atom (e.g., a hydrogen atom) from a guest molecule, such as at least one selected from the group of guest molecules including alcohol derivatives; aryl compounds; carboxylic acid derivatives; amino derivatives; azobenzene derivatives; azobenzene; naphthalene derivatives; anthracene derivatives; pyrene derivatives; perylene derivatives; carbon atom clusters such as fullerenes; and dansyl compounds.

[0058] Further specific examples of guest groups include t-butyl groups, n-octyl groups, n-dodecyl groups, isobornyl groups, adamantyl groups, pyrene-derived groups, and groups to which the aforementioned substituents are attached.

[0059] The structure of a siloxane unit having a guest group is not particularly limited as long as it has a siloxane bond and a guest group. For example, siloxane units having a guest group include 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).

[0060] [ka]

[0061] In equation (2.1), R G R indicates the guest group. 1 , R 5 and R 6 These are R in equation (1.1) above. 1 is R 5 and R 6 It is synonymous with [the above].

[0062] [ka]

[0063] In equation (2.2), R G , R 1 is R 5 and R 6 R in equation (2.1) above is G , R 1 is R 5 and R 6 It is synonymous with [the above].

[0064] [ka]

[0065] In equation (2.3), R G , and R 5 R in equation (2.1) above is G , R 1 is R 5 and R 6 It is synonymous with [the above].

[0066] In equations (2.1), (2.2), and (2.3), R 5 The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and is particularly preferred if it has 1 or 2 carbon atoms. Specifically, examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc., and is preferably a methyl group, ethyl group, n-propyl group, or isopropyl group, with methyl group being particularly preferred.

[0067] R 5 If the compound has substituents, such substituents include hydroxyl groups, alkoxy groups, ester groups, cyano groups, nitro groups, sulfo groups, carboxyl groups, aryl groups, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), and so on.

[0068] In equations (2.1) and (2.2), R 1 If it is a divalent group formed by removing one hydrogen atom from an amino group which may have one substituent, then the nitrogen atom of the amino group is R 6 It can be combined with.

[0069] In equations (2.1) and (2.2), R 1 If it is a divalent group formed by removing one hydrogen atom from an amide group which may have one substituent, then the carbon atom of the amide group is R 6 It can be combined with.

[0070] In equations (2.1) and (2.2), R 1 If it is a divalent group formed by removing one hydrogen atom from an aldehyde group, then the carbon atom of the aldehyde group is R 6 It can be combined with.

[0071] In equations (2.1) and (2.2), R 1 If it is a divalent group formed by removing one hydrogen atom from a carboxyl group, then the carbon atom of the carboxyl group is R6 It can be combined with.

[0072] In equations (2.1) and (2.2), R 6 The alkylene has 1 to 8 carbon atoms, and more preferably 2 to 6. 6 R may be an alkylene group with a heteroatom interposed. In this case, R 6 Examples include alkylene groups having a thioether bond, for example, -(CH2) m1 -S-(CH2) m2 -Examples of combinations are shown. Here, m1 and m2 are the same or different numbers from 1 to 10, preferably from 1 to 8, more preferably from 1 to 5.

[0073] In equations (2.1) and (2.2), R 6 However, in the case of an alkylene group with a sulfur atom interposed, the silicone polymer compound will have a thioether bond between the Si in the polysiloxane skeleton and the host group.

[0074] (Other siloxane units) The silicone polymer compound of the present invention may contain other siloxane units in addition to siloxane units having a host group and siloxane units having a guest group. For example, the other siloxane units may include a constituent unit represented by the following formula (3.1).

[0075] [ka]

[0076] In formula (3.1), R 3 and R 4 These represent, either identically or distinctly, hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms that may be substituted with substituents, or an aryl group having 6 to 20 carbon atoms that may be substituted with substituents.

[0077] In formula (3.1), the linear or branched alkyl group having 1 to 10 carbon atoms is preferably 1 to 4 carbon atoms, and particularly preferably 1 or 2 carbon atoms. Specifically, examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, and the like.

[0078] In formula (3.1), when a linear or branched alkyl group having 1 to 10 carbon atoms is substituted with a substituent, the number of substituents can be one or two or more. Examples of substituents in this case include hydroxyl groups, alkoxy groups, ester groups, cyano groups, nitro groups, sulfo groups, carboxyl groups, aryl groups, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), etc.

[0079] In formula (3.1), the aryl group having 6 to 20 carbon atoms can be, for example, a phenyl group, a naphthyl group, or a tetrahydronaphthyl group. When the aryl group is substituted with a substituent, the number of substituents can be one or two or more. Examples of substituents in this case include hydroxyl groups, alkoxy groups, ester groups, cyano groups, nitro groups, sulfo groups, carboxyl groups, aryl groups, and halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms).

[0080] In equation (3.1), R 3 and R 4 They may be the same or they may be different. In equation (3.1), R 3 and R 4 These are preferably methyl, ethyl, n-propyl, or isopropyl groups, with methyl groups being particularly preferred. 3 and R 4 If all of them are methyl groups, the polysiloxane skeleton contains polydimethylsiloxane.

[0081] The silicone polymer compound of the present invention may contain, together with, the constituent unit represented by formula (3.1) above, or, in place of the constituent unit represented by formula (3.1), the constituent unit represented by the following formula (3.2).

[0082] [ka]

[0083] In formula (3.2), R 7 R represents hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with substituents, or an aryl group having 6 to 20 carbon atoms which may be substituted with substituents. In formula (3.2), R 8 represents an alkylene group which may have a heteroatom interposed therein. A represents hydrogen, a thiol group, a hydroxyl group, or an amino group.

[0084] In equation (3.2), R 7 The group is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, with a methyl group being particularly preferred.

[0085] In equation (3.2), R 8 R is an alkylene group that may have a heteroatom interposed therein. The number of carbon atoms in the alkylene group is not particularly limited and can be, for example, 1 to 10 carbon atoms. 8 In this case, the number of carbon atoms in the alkylene is preferably 1 to 8, and more preferably 2 to 6.

[0086] R 8 R may be an alkylene group with a heteroatom interposed. In this case, R 8 Examples include alkylene groups having a thioether bond, for example, -(CH2) m1 -S-(CH2) m2 -Examples of combinations are shown. Here, m1 and m2 are the same or different numbers from 1 to 10, preferably from 1 to 8, more preferably from 1 to 5.

[0087] The silicone polymer compound of the present invention, when it includes the constituent unit represented by formula (3.2) along with the constituent unit represented by formula (3.1), exhibits improved mechanical properties, particularly Young's modulus and fracture energy, and also tends to improve transparency. In particular, the R of the constituent unit represented by formula (3.2) 8 However, in the case of alkylene groups with interposed heteroatoms, both the Young's modulus and fracture energy of the silicone polymer compound are further improved, and transparency is particularly likely to improve.

[0088] Furthermore, when the silicone polymer compound of the present invention contains a structural unit represented by formula (3.2), and A is a thiol group, some or all of such thiol groups may be protected by a hydrocarbon group (i.e., the hydrogen of the thiol group may be substituted by another group). In this case, the mechanical properties of the silicone polymer compound and the polymer material formed from the silicone polymer compound are further improved. Examples of hydrocarbon groups include alkyl groups having 1 to 10 carbon atoms, alkenyl groups, etc., and preferably alkyl groups having 3 to 8 carbon atoms.

[0089] The following describes the structures of silicone polymer compounds (H), (G), and (HG).

[0090] (Silicone-based polymer compound (H)) The silicone polymer compound (H) is a polymer compound that may have at least one siloxane unit having the host group in its structural units. One embodiment of the silicone polymer compound (H) has the siloxane unit having the host group and the other siloxane unit. Specifically, the silicone polymer compound (H) has the structural unit represented by formula (1.1) and / or the structural unit represented by formula (1.2), and optionally one or both of the structural unit represented by formula (3.1) and the structural unit represented by formula (3.2). Note that the silicone polymer compound (H) does not have the structural unit represented by formula (2.1) and the structural unit represented by formula (2.2) (i.e., siloxane unit having a guest group).

[0091] The content of siloxane units having the host group in the total structural units of the silicone polymer compound (H) is, for example, 0.1 mol% or more and 30 mol% or less. In terms of facilitating the formation of polymer materials with improved mechanical properties, the content of siloxane units having the host group in the total structural units of the silicone polymer compound (H) is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, even more preferably 0.8 mol% or more, and particularly preferably 1 mol% or more. Furthermore, in terms of facilitating the formation of polymer materials with improved mechanical properties, the content of siloxane units having the host group in the total structural units of the silicone polymer compound (H) is preferably 20 mol% or less, more preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0092] The content of the other siloxane units in the total structural units of the silicone polymer compound (H) is, for example, 70 mol% or more and 99.9 mol% or less. In terms of facilitating the formation of polymer materials with improved mechanical properties, the content of the other siloxane units in the total structural units of the silicone polymer compound (H) is preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more. Furthermore, in terms of facilitating the formation of polymer materials with improved mechanical properties, the content of the other siloxane units in the total structural units of the silicone polymer compound (H) is preferably 99.8 mol% or less, more preferably 99.5 mol% or less, even more preferably 99.2 mol% or less, and particularly preferably 99 mol% or less.

[0093] When the silicone polymer compound (H) contains structural units represented by formula (3.1) as other siloxane units, the content of these units is preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, of the total structural units of the silicone polymer compound (H). Furthermore, when the silicone polymer compound (H) contains structural units represented by formula (3.1) as other siloxane units, the content of these units is preferably 99.8 mol% or less, more preferably 99.5 mol% or less, even more preferably 99.2 mol% or less, and particularly preferably 99 mol% or less, of the total structural units of the silicone polymer compound (H).

[0094] When the silicone polymer compound (H) contains structural units represented by formula (3.2) as other siloxane units, the content of these units is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, even more preferably 0.8 mol% or more, and particularly preferably 1 mol% or more, of the total structural units of the silicone polymer compound (H). Furthermore, when the silicone polymer compound (H) contains structural units represented by formula (3.1) as other siloxane units, the content of these units is preferably 20 mol% or less, more preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less, of the total structural units of the silicone polymer compound (H).

[0095] When the silicone polymer compound (H) contains the constituent unit represented by formula (3.2), the mechanical properties (in particular, both Young's modulus and fracture energy) are improved, and transparency is also easily improved, especially the R of the constituent unit represented by formula (3.2). 8 However, in the case of an alkylene group with a heteroatom interposed, the mechanical properties (H) of the silicone polymer compound (H) are further improved (especially both Young's modulus and fracture energy), and transparency is particularly likely to improve.

[0096] The silicone polymer compound (H) may have structural units (hereinafter referred to as structural unit S) in addition to the constituent units represented by formulas (1.1), (1.2), (3.1), and (3,2). The content of structural unit S is 5 mol% or less, preferably 1 mol% or less, more preferably 0.1 mol% or less, and may be 0 mol% of the total structural units of the silicone polymer compound (H).

[0097] (Silicone-based polymer compound (G)) Silicone polymer compound (G) is a polymer compound that may have at least one siloxane unit having the guest group in its structural units. One embodiment of silicone polymer compound (G) has the siloxane unit having the guest group and the other siloxane unit. Specifically, silicone polymer compound (G) has at least one of the structural units represented by formula (2.1), formula (2.2), and formula (2.3), and optionally one or both of the structural units represented by formula (3.1) and formula (3.2). Silicone polymer compound (H) does not have the structural units represented by formula (1.1) and formula (1.2) (i.e., siloxane units having a host group).

[0098] In the total structural units of the silicone polymer compound (G), the content of siloxane units having the guest group is, for example, 0.1 mol% or more and 30 mol% or less. In terms of facilitating the formation of polymer materials with improved mechanical properties, the content of siloxane units having the guest group in the total structural units of the silicone polymer compound (G) is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, even more preferably 0.8 mol% or more, and particularly preferably 1 mol% or more. Furthermore, in terms of facilitating the formation of polymer materials with improved mechanical properties, the content of siloxane units having the guest group in the total structural units of the silicone polymer compound (G) is preferably 20 mol% or less, more preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0099] The content of the other siloxane units in the total structural units of the silicone polymer compound (G) is, for example, 70 mol% or more and 99.9 mol% or less. In terms of facilitating the formation of polymer materials with improved mechanical properties, the content of the other siloxane units in the total structural units of the silicone polymer compound (G) is preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more. Furthermore, in terms of facilitating the formation of polymer materials with improved mechanical properties, the content of the other siloxane units in the total structural units of the silicone polymer compound (G) is preferably 99.8 mol% or less, more preferably 99.5 mol% or less, even more preferably 99.2 mol% or less, and particularly preferably 99 mol% or less.

[0100] When the silicone polymer compound (G) contains structural units represented by formula (3.1) as other siloxane units, the content of these units is preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, of the total structural units of the silicone polymer compound (G). Furthermore, when the silicone polymer compound (G) contains structural units represented by formula (3.1) as other siloxane units, the content of these units is preferably 99.8 mol% or less, more preferably 99.5 mol% or less, even more preferably 99.2 mol% or less, and particularly preferably 99 mol% or less, of the total structural units of the silicone polymer compound (G).

[0101] When the silicone polymer compound (G) contains structural units represented by formula (3.2) as other siloxane units, the content of these units is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, even more preferably 0.8 mol% or more, and particularly preferably 1 mol% or more, of the total structural units of the silicone polymer compound (G). Furthermore, when the silicone polymer compound (G) contains structural units represented by formula (3.1) as other siloxane units, the content of these units is preferably 20 mol% or less, more preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less, of the total structural units of the silicone polymer compound (G).

[0102] The silicone polymer compound (G) may have structural units S in addition to the constituent units represented by formulas (2.1), (2.2), (2.3), (3.1), and (3,2). The content of structural units S is 5 mol% or less, preferably 1 mol% or less, more preferably 0.1 mol% or less, and may be 0 mol% of the total structural units of the silicone polymer compound (H).

[0103] (Silicone-based polymer compounds (HG)) A silicone polymer compound (HG) is a polymer compound that may have at least a siloxane unit having a host group and at least a guest group siloxane unit in its structural units. One embodiment of a silicone polymer compound (HG) has a siloxane unit having a host group, a siloxane unit having a guest group, and the other siloxane units. Specifically, a silicone polymer compound (HG) has a structural unit represented by formula (1.1) and / or a structural unit represented by formula (1.2), at least one of the structural units represented by formula (2.1), the structural unit represented by formula (2.2), and the structural unit represented by formula (2.3), and optionally one or both of the structural units represented by formula (3.1) and the structural unit represented by formula (3.2).

[0104] In the total structural units of the silicone polymer compound (HG), the content of siloxane units having the host group is, for example, 0.1 mol% or more and 30 mol% or less. In terms of facilitating the formation of polymer materials with improved mechanical properties, the content of siloxane units having the host group in the total structural units of the silicone polymer compound (HG) is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, even more preferably 0.8 mol% or more, and particularly preferably 1 mol% or more. Furthermore, in terms of facilitating the formation of polymer materials with improved mechanical properties, the content of siloxane units having the host group in the total structural units of the silicone polymer compound (HG) is preferably 20 mol% or less, more preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0105] In the total structural units of the silicone polymer compound (HG), the content of siloxane units having the guest group is, for example, 0.1 mol% or more and 30 mol% or less. In terms of facilitating the formation of polymer materials with improved mechanical properties, the content of siloxane units having the guest group in the total structural units of the silicone polymer compound (HG) is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, even more preferably 0.8 mol% or more, and particularly preferably 1 mol% or more. Furthermore, in terms of facilitating the formation of polymer materials with improved mechanical properties, the content of siloxane units having the guest group in the total structural units of the silicone polymer compound (HG) is preferably 20 mol% or less, more preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0106] The content of the other siloxane units in the total structural units of the silicone polymer compound (HG) is, for example, 70 mol% or more and 99.9 mol% or less. In terms of facilitating the formation of polymer materials with improved mechanical properties, the content of the other siloxane units in the total structural units of the silicone polymer compound (HG) is preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more. Furthermore, in terms of facilitating the formation of polymer materials with improved mechanical properties, the content of the other siloxane units in the total structural units of the silicone polymer compound (HG) is preferably 99.8 mol% or less, more preferably 99.5 mol% or less, even more preferably 99.2 mol% or less, and particularly preferably 99 mol% or less.

[0107] When the silicone polymer compound (HG) contains structural units represented by formula (3.1) as other siloxane units, the content of these units is preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, of the total structural units of the silicone polymer compound (HG). Furthermore, when the silicone polymer compound (HG) contains structural units represented by formula (3.1) as other siloxane units, the content of these units is preferably 99.8 mol% or less, more preferably 99.5 mol% or less, even more preferably 99.2 mol% or less, and particularly preferably 99 mol% or less, of the total structural units of the silicone polymer compound (HG).

[0108] When the silicone polymer compound (HG) contains structural units represented by formula (3.2) as other siloxane units, the content of these units is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, even more preferably 0.8 mol% or more, and particularly preferably 1 mol% or more, of the total structural units of the silicone polymer compound (HG). Furthermore, when the silicone polymer compound (HG) contains structural units represented by formula (3.1) as other siloxane units, the content of these units is preferably 20 mol% or less, more preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less, of the total structural units of the silicone polymer compound (HG).

[0109] The silicone polymer compound (HG) may have structural units S in addition to the constituent units represented by formulas (1.1), (1.2), (2.1), (2.2), (2.3), (3.1), and (3,2). The content of structural units S is 5 mol% or less, preferably 1 mol% or less, more preferably 0.1 mol% or less, and may be 0 mol% of the total structural units of the silicone polymer compound (H).

[0110] (Silicone-based polymer compounds) The silicone polymer compounds according to the present invention include the silicone polymer compound (H), silicone polymer compound (G), and silicone polymer compound (HG). The silicone polymer compound may have any structure, such as a random polymer or a block polymer, and for example, a random polymer is preferred because it is easy to manufacture.

[0111] The mass-average molecular weight of the silicone polymer compound is not particularly limited, ranging from 1,000 to 1,000,000, preferably 5,000 to 800,000, and more preferably 10,000 to 600,000. The mass-average molecular weight referred to here is the number-average molecular weight in terms of any standard substance (polystyrene) measured by gel permeation chromatography (GPC).

[0112] The silicone polymer compound according to the present invention can form various silicone polymer materials as described below, such as silicone polymer materials having a reversible crosslinking structure and silicone polymer materials having a movable crosslinking structure. Furthermore, the silicone polymer compound according to the present invention also exhibits excellent photorepair performance.

[0113] (Method for producing silicone polymer compounds) The method for producing silicone polymer compounds is not particularly limited and can be done by various methods. For example, a host group and / or a guest group can be introduced into the side chains of a polysiloxane skeleton by reacting a host group-containing compound and / or a guest group-containing compound with a polysiloxane. The type of reaction is not particularly limited and, for example, an addition reaction can be cited.

[0114] One embodiment of a method for producing a silicone polymer compound is a manufacturing method comprising the following step A. Step A: A step of reacting a polysiloxane compound with at least one alkenyl group-containing compound.

[0115] In step A, a polysiloxane compound having an -SH group and / or a -Si-H group in its side chain can be used. This polysiloxane compound can be added to the alkenyl group-containing compound. As a result, for example, if the alkenyl group-containing compound has a host group, the host group can be covalently introduced into the side chain of the polysiloxane skeleton, and if the alkenyl group-containing compound has a guest group, the guest group can be covalently introduced into the side chain of the polysiloxane skeleton.

[0116] The type of the polysiloxane compound used in Process A is not particularly limited as long as it has a -SH group and / or a -Si-H group. For example, the polysiloxane compound used in Process 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".

[0117] When polysiloxane compound a does not have a -SH group, for example, at least one of R 3 and R 4 in the above formula (3.1) is hydrogen. When both R 3 and R 4 in the above formula (3.1) are not hydrogen, R 3 and R 4 are preferably the same or different and are a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and a methyl group is particularly preferred.

[0118] In polysiloxane compound a, in the above formula (3.2), R 7 is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and a methyl group is particularly preferred. Further, when R 8 is an alkylene group with an intervening heteroatom, examples of R 8 include an alkylene group or an alkylene group having a thioether bond, for example, -(CH2) m1 - or -(CH2) m1 -S-(CH2) m2 -. In these, m1 and m2 are numbers from 1 to 10, preferably 1 to 8, more preferably 1 to 5. m1 and m2 may be the same or different.

[0119] When polysiloxane compound a does not have a -SH group, in the above formula (3.2), A is a group other than a thiol group. When polysiloxane compound a has a -SH group and R 3 and R 4If neither of them is hydrogen, then A is a thiol group.

[0120] The content of the structural unit represented by formula (3.1) in the total structural units of polysiloxane compound a can be, for example, 70 mol% or more, preferably 75 mol% or more, more preferably 80 mol% or more, even more preferably 85 mol% or more, and particularly preferably 90 mol% or more. Alternatively, the content of the structural unit represented by formula (3.1) in the total structural units of polysiloxane compound a can be, for example, 99.9 mol% or less, preferably 99 mol% or less, more preferably 98 mol% or less, even more preferably 96 mol% or less, and particularly preferably 95 mol% or less.

[0121] The content of the structural unit represented by formula (3.2) in the total structural units of polysiloxane compound a can be, for example, 0.1 mol% or more, preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 4 mol% or more, and particularly preferably 5 mol% or more. Alternatively, the content of the structural unit represented by formula (3.2) in the total structural units of polysiloxane compound a can be, for example, 30 mol% or less, preferably 25 mol% or less, more preferably 20 mol% or less, even more preferably 15 mol% or less, and particularly preferably 10 mol% or less.

[0122] The alkenyl group-containing compounds used in step A include alkenyl group-containing compounds having a host group and alkenyl group-containing compounds having a guest group. Specifically, when producing the silicone polymer compound (H), an alkenyl group-containing compound having a host group is used as the alkenyl group-containing compound; when producing the silicone polymer compound (G), an alkenyl group-containing compound having a guest group is used as the alkenyl group-containing compound; and when producing the silicone polymer compound (HG), both an alkenyl group-containing compound having a host group and an alkenyl group-containing compound having a guest group are used as the alkenyl group-containing compound.

[0123] In the alkenyl group-containing compound used in step A, examples of the alkenyl group include vinyl groups, allyl groups, and the like.

[0124] The types of alkenyl group-containing compounds having a host group and alkenyl group-containing compounds having a guest group are not particularly limited, and for example, known compounds can be widely used.

[0125] Specific examples of alkenyl group-containing compounds having a host group include compounds represented by the following general formula (h1).

[0126] [ka]

[0127] In formula (h1), Ra represents a hydrogen atom or a methyl group, and R H R represents the host group, 1 R in equation (1.1) above is 1 It is synonymous with [the above].

[0128] Other specific examples of alkenyl group-containing compounds with a host group include compounds represented by the following general formula (h2).

[0129] [ka]

[0130] In formula (h2), Ra, R H and R 1 These are Ra and R in equation (h1), respectively. H and R 1 It is synonymous with [the above].

[0131] Specific examples of alkenyl group-containing compounds having a guest group include compounds represented by the following general formula (g1).

[0132] [ka]

[0133] In formula (g1), Ra represents a hydrogen atom or a methyl group, and R G R represents the guest group, 2 R in equation (1.1) above is 1 This is synonymous with the above. Specific examples of alkenyl group-containing compounds having a guest group include n-hexyl (meth)acrylate, n-octyl (meth)acrylate, n-dodecyl (meth)acrylate, adamantyl (meth)acrylate, hydroxyadamantyl (meth)acrylate, 1-adamantane (meth)acrylamide, 2-ethyl-2-adamantyl (meth)acrylate, N-dodecyl (meth)acrylamide, t-butyl (meth)acrylate, 1-adamantane (acrylamide), N-(1-adamantyl)(meth)acrylamide, N-benzyl (meth)acrylamide, N-1-naphthylmethyl (meth)acrylamide, ethoxylated O-phenylphenol acrylate, phenoxypolyethylene glycol acrylate, isostearyl acrylate, nonylphenol EO adduct acrylate, isobornyl (meth)acrylate, (meth)acrylate having a pyrene moiety, and (meth)acrylamide having a pyrene moiety.

[0134] In this specification, "(meth)acrylic" means "acrylic" or "methacrylic," "(meth)acrylate" means "acrylate" or "methacrylate," and "(meth)allyl" means "allyl" or "methallyl."

[0135] Alkenyl group-containing compounds having a host group and alkenyl group-containing compounds having a guest group can be manufactured by known methods, or commercially available products can be used.

[0136] In the reaction of step A, alkenyl group-containing compounds other than those containing a host group and alkenyl group-containing compounds containing a guest group can also be used in combination. Such alkenyl group-containing compounds will be denoted as "alkenyl group-containing compound c".

[0137] Examples of alkenyl group-containing compound c include C2-C10 alkenyl compounds which may have substituents. Examples of substituents include hydroxyl groups, amino groups, carboxyl groups, etc. In alkenyl compounds, the position of the carbon-carbon double bond is not particularly limited and can be, for example, at the end of the alkenyl compound (e.g., a 1,2-alkenyl compound), in which case the substituent can be at the opposite end. Specific examples of alkenyl group-containing compound c include 1-pentene, 2-pentene, and allyl alcohol, and in the case of 1-pentene, the mechanical properties of the polymer material tend to be improved.

[0138] In the reaction of step A, the polysiloxane compound is reacted with at least one alkenyl group-containing compound (an alkenyl group-containing compound having a host group and / or an alkenyl group-containing compound having a guest group). In this reaction, the alkenyl group-containing compound c is also used as needed. In this case, the resulting polymer tends to have excellent mechanical properties (particularly excellent Young's modulus and fracture energy) and also tends to have high transparency.

[0139] In the reaction of step A, the amount of alkenyl group-containing compound (excluding alkenyl group-containing compound c) used is not particularly limited and can be, for example, 0.1 to 30 mol% relative to the polysiloxane compound. Also, in the reaction of step A, the amount of alkenyl group-containing compound c used can be, for example, 50 to 150 mol% relative to the polysiloxane compound.

[0140] The reaction in step A can be carried out, for example, in the presence of a photopolymerization initiator. This facilitates the reaction between the polysiloxane compound and the alkenyl group-containing compound. Specifically, it facilitates the reaction (addition reaction) between the -SH group and / or -Si-H group in the polysiloxane compound and the alkenyl group in the alkenyl group-containing compound.

[0141] When a photopolymerization initiator is used in the reaction of step A, the amount used is not particularly limited and can be, for example, 1 to 20 mol% relative to the polysiloxane compound.

[0142] The reaction in step A can be carried out in various solvents. The type of solvent is not particularly limited, and a wide range of solvents conventionally used in addition reactions between alkenyl compounds and silyl groups or between alkenyl compounds and thiol groups can be applied. Examples of 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-butyl alcohol, benzyl alcohol, phenoxyethanol, and phenylpropylene glycol; halogenated hydrocarbon solvents such as methylene chloride 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; and amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide.

[0143] The reaction in step A can be carried out by, for example, irradiating a raw material containing a polysiloxane compound, an alkenyl group-containing compound, alkenyl group-containing compound c, a photopolymerization initiator, and a solvent with active energy rays to allow the reaction to proceed, or by adjusting the raw material to a predetermined temperature to allow the reaction to proceed. Among these, the method of irradiating with active energy rays is preferred because the reaction proceeds easily. Examples of active energy rays include ultraviolet rays, electron beams, visible light, X-rays, and ion beams, and among these, ultraviolet rays or electron beams are preferred in terms of versatility, and ultraviolet rays are particularly preferred.

[0144] After carrying out the reaction in step A, additional starting materials (e.g., polysiloxane compound, alkenyl group-containing compound, alkenyl group-containing compound c, etc.) can be added. In this case, it is preferable to add alkenyl group-containing compound c, which makes it possible to consume unreacted Si-H groups and SH groups in the polysiloxane compound.

[0145] After the reaction in step A is complete, the desired silicone polymer compound can be obtained by appropriate purification methods.

[0146] 2. Silicone-based polymer materials The silicone polymer materials of the present invention include the following silicone polymer materials A, B, C, C', and D.

[0147] (Silicone-based polymer material A) Silicone polymer material A comprises the silicone polymer compound (H) and the silicone polymer compound (G), wherein the host group in the silicone polymer compound (H) encapsulates the guest group of the silicone polymer compound (G).

[0148] Specifically, in silicone polymer material A, at least one host group of the silicone polymer compound (H) and at least one guest group of the silicone polymer compound (G) form a host-guest interaction. In short, in silicone polymer material A, reversible host-guest interactions occur between molecules, thereby forming a reversible crosslinked structure.

[0149] In silicone polymer material A, the combination of host group and guest group is not particularly limited, and the aforementioned host group and guest group can be arbitrarily combined. In particular, in terms of easily improving the mechanical properties of silicone polymer material A, when the host group is derived from α-cyclodextrin or its derivative, at least one guest group selected from the group consisting of octyl group and dodecyl group is preferred. For similar reasons, when the host group is derived from β-cyclodextrin or its derivative, at least one guest group selected from the group consisting of adamantyl group and isobornyl group is preferred, and when the host group is derived from γ-cyclodextrin or its derivative, at least one guest group selected from the group consisting of octyl group, dodecyl group, cyclododecyl group and adamantyl group is preferred.

[0150] Silicone polymer material A can also possess self-healing properties because host-guest interactions are formed between molecules. For example, even if silicone polymer material A is cut, the cut surfaces can be re-bonded, and host-guest interactions are re-formed at the bonding surface. As a result, re-bonding occurs, leading to self-healing.

[0151] In silicone polymer material A, the content ratio of silicone polymer compound (H) and silicone polymer compound (G) is not particularly limited. For example, in terms of facilitating host-guest interactions, the content ratio of silicone polymer compound (H) to the total mass of silicone polymer compound (H) and silicone polymer compound (G) is 30 to 80% by mass, preferably 40 to 60% by mass, and the two may be in equal amounts.

[0152] Silicone polymer material A may contain other additives besides silicone polymer compound (H) and silicone polymer compound (G), or silicone polymer material A may be formed solely from silicone polymer compound (H) and silicone polymer compound (G).

[0153] The method for producing silicone polymer material A is not particularly limited, and for example, known methods can be widely employed. For example, silicone polymer material A can be obtained by mixing silicone polymer compound (H) and silicone polymer compound (G) using a known mixing means. A wide range of known mixers can be used as the mixing means, for example, a ball mill or the like. Mixing may be carried out dry or wet. In the case of wet mixing, for example, a method can be used in which a solution containing silicone polymer compound (H) and silicone polymer compound (G) is mixed with a conductive material. The solvent of the solution is not particularly limited, and various organic solvents in which both silicone polymer compound (H) and silicone polymer compound (G) are dissolved can be used.

[0154] (Silicone-based polymer material B) Silicone polymer material B contains the aforementioned silicone polymer compound (HG), and intermolecular bonds exist between host groups and guest groups.

[0155] In silicone polymer material B, each silicone polymer compound (HG) contains at least one host group and at least one guest group, allowing the silicone polymer compounds (HG) to form intermolecular host-guest interactions. Specifically, at least one host group of one silicone polymer compound (HG) can be encapsulated by at least one guest group of another silicone polymer compound (HG), thereby forming a reversible intermolecular host-guest interaction. Consequently, silicone polymer material B, like silicone polymer material A, also forms a reversible crosslinked structure.

[0156] Such intermolecular host-guest interactions improve the mechanical properties of silicone polymer material B, particularly its Young's modulus and fracture energy, resulting in a material that is both tough and highly flexible.

[0157] In silicone polymer material B, the combination of host group and guest group is not particularly limited, and the aforementioned host group and guest group can be arbitrarily combined. In particular, in terms of easily improving the mechanical properties of silicone polymer material B, when the host group of the silicone polymer compound (HG) is derived from α-cyclodextrin or its derivative, at least one guest group selected from the group consisting of octyl group and dodecyl group is preferred. For similar reasons, when the host group of the silicone polymer compound (HG) is derived from β-cyclodextrin or its derivative, at least one guest group selected from the group consisting of adamantyl group and isobornyl group is preferred, and when the host group of the silicone polymer compound (HG) is derived from γ-cyclodextrin or its derivative, at least one guest group selected from the group consisting of octyl group, dodecyl group, cyclododecyl group and adamantyl group is preferred.

[0158] Silicone polymer material B can also possess self-healing properties because host-guest interactions are formed between its molecules. For example, even if silicone polymer material B is cut, the cut surfaces can be re-bonded, and host-guest interactions are re-formed at the bonding surface. As a result, re-bonding occurs, leading to self-healing.

[0159] Silicone polymer material B may contain other additives besides the silicone polymer compound (HG), or silicone polymer material B may be formed solely from the silicone polymer compound (HG).

[0160] The method for producing silicone polymer material B is not particularly limited, and known methods can be widely employed. For example, silicone polymer material B can be produced using a solution of silicone polymer compound (HG).

[0161] (Silicone-based polymer material C) The silicone polymer material C comprises a crosslinked structure containing the silicone polymer compound (H), wherein the crosslinked structure has a structure in which the main chain of another silicone polymer compound (H) penetrates at least one of the host groups of the silicone polymer compound (H).

[0162] Figure 1 schematically shows a structure in which the main chain of another silicone polymer compound (H) penetrates at least one host group of another silicone polymer compound (H). The penetration of the main chain of the other silicone polymer compound (H) through the host group of the silicone polymer compound (H) forms a crosslinked structure, and the polymer chain penetrating the host group ring becomes slidable. In other words, the silicone polymer compound (H) forms a so-called mobile crosslinked structure (mobile crosslinked structure). This crosslinked structure can also be called a single cross network. This crosslinked structure improves the mechanical properties of the silicone polymer compound (H) (particularly both Young's modulus and fracture energy), allowing it to be tough yet possess excellent flexibility. Furthermore, since the silicone polymer compound (H) penetrating the host group also has a host group, this host group acts as a so-called stopper, preventing detachment.

[0163] As shown in Figure 1, the silicone polymer material C may further contain a chain-like polymer compound (P1). The chain-like polymer compound (P1) penetrates the network of the crosslinked structure. The network of the crosslinked structure referred to here means a movable crosslinked structure formed by the main chain of another silicone polymer compound (H) penetrating the host group of the aforementioned silicone polymer compound (H).

[0164] In silicone polymer material C, the presence of chain-like polymer compounds (P1) penetrating the network of the cross-linked structure further enhances the mechanical properties of silicone polymer material C.

[0165] The chain-like polymer compound (P1) is a polymer compound that does not have a host group, and examples include polymers formed by the polymerization of various polymerizable monomers M. Examples of polymerizable monomers M include various (meth)acrylic ester monomers such as alkyl (meth)acrylate, alkyl (meth)acrylate having a hydroxyl group, and (meth)acrylic acid monomers having a carboxyl group. Specific examples of polymerizable monomers M include (meth)acrylic acid, allylamine, maleic anhydride; alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, and n-octyl (meth)acrylate; alkyl (meth)acrylates such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N,N-dimethyl(meth)acrylamide. Examples include (meth)acrylamides or derivatives thereof such as acrylamide, N-isopropyl(meth)acrylamide, and N-hydroxymethyl(meth)acrylamide; hydroxyl group-containing (meth)acrylic acid esters such as hydroxymethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylamide, and 2-hydroxyethyl(meth)acrylate; ethoxydiethylene glycol(meth)acrylate, methoxytriethylene glycol(meth)acrylate, methoxypolyethylene glycol(meth)acrylate, and styrene.

[0166] The chain-like polymer compound (P1) is preferably a polymer of (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, or a derivative thereof, in that it is likely to penetrate the network of the crosslinked structure, and is more preferably a polymer containing alkyl (meth)acrylate units such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. If the chain-like polymer compound (P1) has aqueous-binding functional groups such as hydroxyl groups and carboxyl groups, its mechanical properties are easily improved by intermolecular hydrogen bonding, so it is particularly preferable that the chain-like polymer compound (P1) has aqueous-binding functional groups. From this viewpoint, the chain-like polymer compound (P1) is preferably a copolymer of the alkyl (meth)acrylate and the hydroxyl group-containing (meth)acrylic ester, or the chain-like polymer compound (P1) may be a homopolymer of the hydroxyl group-containing (meth)acrylic ester. When the chain-like polymer compound (P1) is a copolymer of the alkyl (meth)acrylate and the hydroxyl group-containing (meth)acrylic ester, the content ratio of the two is not particularly limited. For example, the content ratio of the hydroxyl group-containing (meth)acrylic ester can be 5 to 80% by mass, preferably 10 to 60% by mass.

[0167] Further examples of chain-like polymer compounds (P1) include polyaddition polymer compounds such as polyurethane and polycondensation polymer compounds, as described below.

[0168] The mass-average molecular weight (Mw) of the chain-like polymer compound (P1) is not particularly limited and can be, for example, 10,000 to 2,000,000, preferably 20,000 to 1,000,000. The chain-like polymer compound (P1) can have structures such as homopolymers and random polymers, and can be linear, branched structures and crosslinked structures, as long as the effects of the present invention are not hindered.

[0169] In silicone polymer material C, the content ratio of silicone polymer compound (H) and chain polymer compound (P1) is not particularly limited. For example, in terms of easily improving mechanical properties, the content ratio of silicone polymer compound (H) to the total mass of silicone polymer compound (H) and chain polymer compound (P1) can be, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. Also in terms of easily improving mechanical properties, the content ratio of silicone polymer compound (H) to the total mass of silicone polymer compound (H) and chain polymer compound (P1) can be 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less.

[0170] The silicone polymer material C may contain other additives besides the silicone polymer compound (H) and the chain polymer compound (P1), or it may be formed solely from the silicone polymer compound (H) and the chain polymer compound (P1).

[0171] The method for producing the silicone polymer material C is not particularly limited, and for example, known methods can be widely employed. For example, in the process of preparing a solution in which a silicone polymer compound (H) is dissolved in a solvent and drying the solvent, the main chain of another silicone polymer compound (H) may penetrate at least one of the host groups of the silicone polymer compound (H). This forms a crosslinked structure (the aforementioned movable crosslinked structure), and the silicone polymer material C is obtained. Alternatively, in step A, when the polysiloxane compound a reacts with the alkenyl compound having a host group, the polysiloxane compound a may penetrate the host group, so the silicone polymer material C can be produced directly by step A.

[0172] Furthermore, by performing a polymerization reaction to obtain a chain-like polymer compound (P1) in the presence of a silicone polymer compound (H) on which a movable crosslinked structure has been formed, a silicone polymer material C can be produced in which the chain-like polymer compound (P1) penetrates the network of the crosslinked structure. Specifically, the silicone polymer material C can be obtained by performing a polymerization reaction of the polymerizable monomer M in the presence of a silicone polymer compound (H). In this manufacturing method, since the silicone polymer compound (H) has a movable crosslinked structure, swelling of the silicone polymer compound (H) is likely to occur due to the polymerizable monomer M, and as a result, the growth chains of the polymerizable monomer M are more likely to penetrate the network of the movable crosslinked structure.

[0173] (Silicone polymer material C') The silicone polymer material C' comprises a crosslinked structure containing a silicone polymer compound (H) and a chain polymer compound (P1), wherein the crosslinked structure has a structure in which the chain polymer compound (P1) penetrates at least one of the host groups of the silicone polymer compound (H).

[0174] Figure 2 schematically shows the structure of the silicone polymer material C'. By having a chain polymer compound (P1) penetrate the host group of the silicone polymer compound (H), a mobile crosslinked structure is formed. This improves the mechanical properties of the silicone polymer compound (H) (particularly both Young's modulus and fracture energy), allowing it to be tough yet highly flexible.

[0175] In silicone polymer material C', the chain polymer compound (P1) is the same as the chain polymer compound (P1) in silicone polymer material C. Because the chain polymer compound (P1) readily penetrates host groups, it is preferable that the chain polymer compound (P1) is a polymer of (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, or a derivative thereof, and more preferably a polymer of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, etc.

[0176] In the silicone polymer material C', if the chain polymer compound (P1) has aqueous-binding functional groups such as hydroxyl groups and carboxyl groups, the mechanical properties are easily improved by intermolecular hydrogen bonding. Therefore, it is particularly preferable that the chain polymer compound (P1) has aqueous-binding functional groups. From this viewpoint, it is preferable that the chain polymer compound (P1) is a copolymer of the alkyl (meth)acrylate and the hydroxyl group-containing (meth)acrylic ester, or the chain polymer compound (P1) may be a homopolymer of the hydroxyl group-containing (meth)acrylic ester. When the chain polymer compound (P1) is a copolymer of the alkyl (meth)acrylate and the hydroxyl group-containing (meth)acrylic ester, the content ratio of the two is not particularly limited. For example, the content ratio of the hydroxyl group-containing (meth)acrylic ester can be 5 to 80% by mass, preferably 10 to 60% by mass.

[0177] In silicone polymer materials C', other examples of chain polymer compounds (P1) include the aforementioned polyaddition polymer compounds such as polyurethane and polycondensation polymer compounds. These polymer compounds are produced by a polymerization reaction using two or more compounds selected from the group consisting of compounds having one or two amino groups, compounds having one or two hydroxyl groups, compounds having one or two carboxyl groups, compounds having one or two epoxy groups, compounds having one or two isocyanate groups, compounds having one or two thiol groups, and compounds having one or two carboxylate chlorides (hereinafter referred to as "polyaddition compounds"). Among these, urethane resins and epoxy resins are preferred as chain polymer compounds (P1) for polyaddition polymer compounds and polycondensation polymer compounds.

[0178] Examples of compounds having one or two amino groups include 1-adamantanamine, benzylamine, tert-butylamine, butylamine, 1-aminopyrene, aminoferrocene, 4-aminoazobenzene, 4-aminostilbene, cyclohexylamine, hexylamine, 4,7,10-trioxa-4,6-1,13-tridecanediamine, 4,4'-diaminodiphenylmethane, p-xylylenediamine, diaminoferrocene, 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 Examples include 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, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-amine]propane, 1,1-bis(4-aminophenyl)-3,3,5-trimethylcyclohexane, and 1,1-bis(4-aminophenyl)cyclohexane.

[0179] Examples of compounds having one or two hydroxyl groups include 1-hydroxyadamantane, benzyl alcohol, tert-butyl alcohol, butyl alcohol, 1-hydroxypyrene, 1-hydroxymethylferrocene, 4-hydroxyazobenzene, 4-hydroxystilbene, cyclohexanol, hexanol, 4,4'-dihydroxydiphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 1,4-benzenedimethanol, 1,1'-dihydroxymethylferrocene, 4,4'-dihydroxyazobenzene, 4,4'-dihydroxystilbene, 1,3-propanediol, polytetrahydrofuran, 1,4-cyclohexenol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and 2,2-bis(4-hydroxyphenyl)hexafluoropropyl Examples include bis(4-hydroxyphenyl)propane, 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, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-hydroxy]propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bisphenol A, etc. Among these, propanediol (POD) and polytetrahydrofuran (PTHF) are preferred, and they may be used in combination, but tetrahydrofuran (PTHF) is particularly preferred to be used alone.

[0180] Examples of compounds having one or two carboxyl groups include 1-carboxyadamantane, benzoic acid, pivalic acid, butanoic acid, 1-carboxypyrene, 1-carboxyferrocene, 4-carboxyazobenzene, 4-carboxystilbene, cyclohexanoic acid, hexanoic acid, 4,4'-dicarboxydiphenylmethane, 1,4-benzenedicarboxylic acid, 1,4-phenylenediacetic acid, 1,1'-dicarboxyferrocene, 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, and 2,2-bis(4-carboxyphenyl)hexafluoro Examples include propane, 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-carboxy3-isopropylphenyl)propane, 1,3-bis(2-(4-carboxyphenyl)-2-propyl)benzene, bis(4-carboxyphenyl)sulfone, 1,4-bis(2-(4-carboxyphenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-carboxy]propane, 1,1-bis(4-carboxyphenyl)-3,3,5-trimethylcyclohexane, and 1,1-bis(4-carboxyphenyl)cyclohexane.

[0181] Examples of compounds having one or two carboxylic acid chlorides include 1-adamantane carbonyl chloride, terephthaloyl chloride, trimethylacetyl chloride, butyryl chloride, 1-pyrene carbonyl chloride, 1-ferrocene carbonyl chloride, 4-azobenzene carbonyl chloride, 4-stilbene carbonyl chloride, cyclohexane carbonyl chloride, hexyl chloride, 4,4'-diphenylmethane dicarbonyl chloride, 1,4-benzene dicarbonyl chloride, and 1,4-phenylene Dicarbonyl chloride, 1,1'-ferrocene dicarbonyl chloride, 4,4'-azobenzene dicarbonyl chloride, 4,4'-stilbene carbonyl chloride, 1,4-cyclohexane dicarbonyl chloride, 1,6-hexane dicarbonyl chloride, α,ω-polyethylene glycol dicarbonyl chloride, α,ω-polypropylene glycol 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- Examples include (4-phenylcarbonyl chloride)-2-propyl)benzene, bis(4-phenylcarbonyl chloride)sulfone, 1,4-bis(2-(4-phenylcarbonyl chloride)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-carbonyl chloride]propane, 1,1-bis(4-phenylcarbonyl chloride)-3,3,5-trimethylcyclohexane, and 1,1-bis(4-phenylcarbonyl chloride)cyclohexane.

[0182] Examples of compounds having one or two epoxy groups include adamantane oxide, styrene oxide, 1,2-epoxybutane, 1-epoxypyrene, epoxyferrocene, 4-epoxyazobenzene, 4-epoxystilbene, cyclohexyl oxide, 1,2-epoxyhexane, 2,2'-bis(4-glycidyloxyphenyl)propane, p-diglycidyloxybenzene, diglycidyloxyferrocene, 4,4'-diglycidyloxyazobenzene, 4,4'-diglycidyloxyferrocene, 1,4-diglycidyloxycyclohexane, 1,6-diglycidyloxycyclohexane, α,ω-diglycidyloxypolyethylene glycol, α,ω-diglycidyloxypolypropylene glycol, 1,1-bis(4-glycidyloxyphenyl)-1-phenylethane, 2,2-bis(4-glycidyloxyphenyl)hexafluoropropane, 2,2-bis(4-glycidyloxyphenyl) (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 Examples include benzene, bis(4-glycidyloxyphenyl)sulfone, 1,4-bis(2-(4-glycidyloxyphenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-glycidyloxy]propane, 1,1-bis(4-glycidyloxyphenyl)-3,3,5-trimethylcyclohexane, and 1,1-bis(4-glycidyloxyphenyl)cyclohexane.

[0183] Examples of compounds 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, hexamethylene diisocyanate, and 4,4'-diisocyanate phenylmethane. p-benzene 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-F Examples include phenylisocyanate-)-2-propyl)benzene, bis(4-phenylisocyanate-)sulfone, 1,4-bis(2-(4-phenylisocyanate-)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-isocyanate]propane, 1,1-bis(4-phenylisocyanate-)-3,3,5-trimethylcyclohexane, and 1,1-bis(4-phenylisocyanate-)cyclohexane.

[0184] Examples of compounds having one or two thiol groups include 1-adamantanethol, benzylthiol, tert-mercaptan, butanethiol, 1-thiolpyrene, ferrocentiol, 4-thioazobenzene, 4-thiostylbene, cyclohexylthiol, hexanethiol, 4,4'-dithiophenylmethane, p-benzenedithiol, 1,1'-dithioferocene, 4,4'-dithioazobenzene, 4,4'-dithiostylbene, 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 Examples include 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(4-thio3-isopropylphenyl)propane, 1,3-bis(2-(4-thiophenyl)-2-propyl)benzene, bis(4-thiophenyl)sulfone, 1,4-bis(2-(4-thiophenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-thiol]propane, 1,1-bis(4-thiophenyl)-3,3,5-trimethylcyclohexane, and 1,1-bis(4-thiophenyl)cyclohexane.

[0185] When the chain-like polymer compound (P1) is a polyaddition-type polymer compound or a polycondensation-type polymer compound, the chain-like polymer compound (P1) is preferably a urethane resin or an epoxy resin. In the case of a urethane resin, it is preferably a polymer of a compound having two hydroxyl groups and a compound having two isocyanates. In particular, it is more preferably a polymer of propanediol (POD), polytetrahydrofuran (PTHF, number average molecular weight about 1000), and hexamethylene diisocyanate (HDI), and especially preferably a polymer of polytetrahydrofuran (PTHF, number average molecular weight about 1000) and hexamethylene diisocyanate (HDI).

[0186] In the silicone polymer material C', the content ratio of the silicone polymer compound (H) and the chain polymer compound (P1) is not particularly limited. For example, in terms of easily improving mechanical properties, the content ratio of the silicone polymer compound (H) to the total mass of the silicone polymer compound (H) and the chain polymer compound (P1) can be, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. Also, in terms of easily improving mechanical properties, the content ratio of the silicone polymer compound (H) to the total mass of the silicone polymer compound (H) and the chain polymer compound (P1) can be 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less.

[0187] The silicone polymer material C' may contain other additives besides the silicone polymer compound (H) and the chain polymer compound (P1), or it may be formed solely from the silicone polymer compound (H) and the chain polymer compound (P1).

[0188] The method for producing the silicone polymer material C' is not particularly limited, and for example, a wide range of known methods can be employed. In the production of silicone polymer material C, as described above, a crosslinked structure (mobile crosslinked structure) of the silicone polymer compound (H) was prepared in the process of drying the solution of the silicone polymer compound (H). However, in the production of silicone polymer material C', it is not necessarily required to form a crosslinked structure of the silicone polymer compound (H). Therefore, in the production of silicone polymer material C', the step of drying the solution of the silicone polymer compound (H) can be omitted. Specifically, silicone polymer material C' can be produced by carrying out a polymerization reaction of a chain polymer compound (P1) in a solution of silicone polymer compound (H). In the polymerization process of the chain polymer compound (P1), the chain polymer compound (P1) that extends penetrates the host group in the silicone polymer compound (H).

[0189] Furthermore, in the production of the silicone polymer material C', it is also possible to employ a method in which a monomer is impregnated into a film formed by drying a solution of the silicone polymer compound (H) to form a chain-like polymer compound (P1) and then subjected to a polymerization reaction. This method is preferably used when the silicone polymer compound (H) contains the structural units represented by formula (3.2) and has a structure in which some or all of the thiol groups of A are substituted with alkyl groups having 3 to 8 carbon atoms.

[0190] When the chain-like polymer compound (P1) is a polyaddition polymer compound such as polyurethane or a polycondensation polymer compound, a method for producing the silicone polymer material C' can be as follows: First, in a solution containing the polysiloxane compound a, an alkenyl compound c having a host group, and at least two of the polyaddition compounds, an addition reaction between the polysiloxane compound a and the alkenyl compound c having a host group is carried out in the same manner as in step A, and then the polymerization reaction of the polyaddition compound is carried out to produce the silicone polymer material C'. During the polymerization process of the chain-like polymer compound (P1), the elongated chain-like polymer compound (P1) penetrates the host group in the silicone polymer compound (H). The polymerization reaction of the polyaddition compound can be carried out under conditions similar to those of known methods, and known catalysts can be used as needed.

[0191] (Silicone-based polymer material D) The silicone polymer material D comprises a silicone polymer compound (H) and a chain-like polymer compound (P2) other than the silicone polymer compound, wherein the chain-like polymer compound (P2) has at least one host group in its side chain, and the host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from cyclodextrin or a cyclodextrin derivative, and the main chain of the other polymer compound H penetrates at least one of the host groups of the silicone polymer compound (H), and the main chain of the other chain-like polymer compound (P2) penetrates at least one of the host groups of the chain-like polymer compound (P2).

[0192] Figure 3 schematically shows the structure of silicone polymer material D. As shown in this figure, silicone polymer material D is composed of a movable crosslinked structure formed by a silicone polymer compound (H) and a movable crosslinked structure formed by a chain polymer compound (P2). This crosslinked structure can also be called a double cross network. Due to this crosslinked structure, silicone polymer material D has excellent mechanical properties (in particular, both Young's modulus and fracture energy are improved), and can be tough yet highly flexible.

[0193] The chain-like polymer compound (P2) is not particularly limited as long as it is a polymer having a host group in its side chain, and a wide range of known polymers having a host group can be applied. For example, polymers having a structural unit based on the compound represented by formula (h1) or a structural unit based on the compound represented by formula (h2) can be broadly cited. The chain-like polymer compound (P2) can be, for example, a copolymer of the compound represented by formula (h1) or the compound represented by formula (h2) with various polymerizable monomers.

[0194] The polymerizable monomer referred to herein is, for example, the same as the polymerizable monomer M used to obtain the chain-like polymer compound (P1) described above, and is preferably methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, etc.

[0195] In the chain-like polymer compound (P2), the host group content is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, even more preferably 0.8 mol% or more, and particularly preferably 1 mol% or more, relative to the total structural units of the chain-like polymer compound (P2). Furthermore, it is preferably 20 mol% or less, more preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less.

[0196] The mass-average molecular weight (Mw) of the chain-like polymer compound (P2) is not particularly limited and can be, for example, 10,000 to 2,000,000, preferably 20,000 to 1,000,000. The chain-like polymer compound (P2) can have structures such as homopolymers and random polymers, and the chain-like polymer compound P can be linear, and can also have branched and crosslinked structures as long as the effects of the present invention are not hindered.

[0197] In silicone polymer material D, the content ratio of silicone polymer compound (H) and chain polymer compound (P2) is not particularly limited. For example, in terms of easily improving mechanical properties, the content ratio of silicone polymer compound (H) to the total mass of silicone polymer compound (H) and chain polymer compound (P2) can be, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. Also in terms of easily improving mechanical properties, the content ratio of silicone polymer compound (H) to the total mass of silicone polymer compound (H) and chain polymer compound (P2) can be 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less.

[0198] The silicone polymer material D may contain other additives besides the silicone polymer compound (H) and the chain polymer compound (P1), or it may be formed solely from the silicone polymer compound (H) and the chain polymer compound (P2).

[0199] The method for producing the silicone polymer material D is not particularly limited, and for example, known methods can be widely employed. For example, the silicone polymer material D can be produced by carrying out a polymerization reaction to obtain a chain-like polymer compound (P2) in the presence of a silicone polymer compound (H) on which a movable crosslinked structure has been formed. Specifically, the silicone polymer material D can be obtained by carrying out a polymerization reaction of the polymerizable monomer M and a structural unit based on the compound represented by formula (h1) or a compound mixture represented by formula (h2) in the presence of a silicone polymer compound (H) on which a movable crosslinked structure has been formed. In this production method, since the silicone polymer compound (H) has a movable crosslinked structure, swelling of the silicone polymer compound (H) is likely to occur due to the polymerizable monomer M, and as a result, the growth chains of the polymerizable monomer M can easily penetrate the network of the movable crosslinked structure.

[0200] (Silicone-based polymer materials) As described above, the polymer materials of the present invention include polymer material A, polymer material B, polymer material C, polymer material C', and polymer material D.

[0201] The shape of the silicone polymer material is not particularly limited and may be a molded body such as a film, sheet, plate, or block, or it may be in the form of parts, fibers, granules, pellets, etc.

[0202] When manufacturing molded articles of silicone polymer materials, the manufacturing method is not particularly limited. For example, known molding methods can be widely employed, specifically including casting, press molding, extrusion molding, injection molding, and the like.

[0203] The silicone polymer material of the present invention exhibits excellent mechanical properties, particularly improved Young's modulus and fracture energy, resulting in a flexible yet tough material. Furthermore, the silicone polymer material of the present invention can also possess high transparency.

[0204] Therefore, the silicone-based polymer material of the present invention can be used for various applications. Among them, because of its high transparency, it can also be preferably used as an optical material.

[0205] As long as the optical material contains the silicone-based polymer material of the present invention, it can also contain other additives. The manufacturing method of the optical material is not particularly limited, and the known manufacturing methods of optical materials can be widely adopted.

[0206] Since the optical material contains the silicone-based polymer material of the present invention, it can exhibit excellent transparency while being tough, and is suitable for use in various fields where transparency is required.

Examples

[0207] Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the embodiments of these examples.

[0208] (Production Example 1) 5 g (3.9 mmol) of γ-cyclodextrin, 700 mg (6.9 mmol) of N-hydroxymethylacrylamide, and 95 mg (0.6 mmol) of p-toluenesulfonic acid monohydrate were weighed into a 200 mL glass round-bottom flask, and these were added to 25 mL of N,N-dimethylformamide to prepare the reaction solution. The solution was heated to 90°C in an oil bath and stirred for 1 hour to obtain the reaction solution. The reaction solution was then allowed to cool and poured into 45 mL of acetone that was being vigorously stirred. After filtering off the resulting precipitate, the product was washed three times with 10 mL of acetone and dried under reduced pressure at room temperature for 1 hour to obtain the reaction product. The reaction product was dissolved in 100 mL of distilled water and passed through a column packed with porous polystyrene resin (Mitsubishi Chemical Diaion HP-20) (apparent density 600 g / L) for 30 minutes to allow adsorption. Subsequently, the solution components were removed, and the polystyrene resin was washed by passing 50 mL of a fresh 10% methanol (or acetonitrile) aqueous solution through the column three times to remove unreacted γ-cyclodextrin. Next, 500 mL of a 25% methanol aqueous solution was passed through the column twice to elute the target product, acrylamidemethyl γ-cyclodextrin (denoted as γCDAAmMe). By removing the solvent under reduced pressure, γCDAAmMe was obtained as a white powder.

[0209] 20 g of γCDAAmMe was dissolved in 300 mL of pyridine, 170.133 g of acetic anhydride was added, and the mixture was stirred at 55°C for at least 12 hours. Then, 50 mL of methanol was added to quench the mixture, and the solution was concentrated in an evaporator until the volume was 200 mL. The resulting concentrate was added dropwise to 2000 mL of water, and the precipitate was collected. The precipitate was dissolved in 200 mL of acetone, added dropwise to 2000 mL of water, and the resulting precipitate was collected. The target product, a host group-containing polymerizable monomer, was isolated by vacuum drying. The obtained host group-containing polymerizable monomer was a compound represented by the following formula (h1-2) (hereinafter referred to as "PAcγCDAAmMe").

[0210] [ka]

[0211] (Example 1-1) A silicone polymer compound (H) was produced according to the reaction scheme shown in Figure 4. First, PDMS-SH, PAcγCDAAmMe obtained in Production Example 1, and 1-pentene were dissolved in chloroform to prepare a solution. To this solution, Irgacure184®, a photopolymerization initiator, was added in an amount of 0.1 eq. relative to the SH groups in PDMS-SH to prepare the raw material. Note that PDMS-SH is composed of constituent units (R) represented by formula (3.1). 3 =R 4 =CH3)90 mol%, and the constituent unit (R) represented by formula (3.2) 7 =CH3, R 8 This is a polysiloxane compound a containing -(CH2)3- and A=SH) 10 mol%. PDMS-SH was prepared by a known manufacturing method. The amounts of PDMS-SH, PAcγCDAAmMe, and 1-pentene used were adjusted so that the total amount of SH groups in PDMS-SH and the alkenyl groups of PAcγCDAAmMe and 1-pentene were equal. The amount of chloroform used was 1 mL per 100 mg of PDMS-SH. In addition, the amount of PAcγCDAAmMe used was adjusted so that x was 1 in the silicone polymer compound (H) shown in the reaction scheme in Figure 4.

[0212] The aforementioned raw materials were irradiated with an Hg lamp for 30 minutes to allow the reaction to proceed and obtain a reaction solution. An excess amount of 1-pentene was added to this reaction solution and the reaction was continued for another 30 minutes to obtain a solution. The obtained solution was placed in a mold made from a Teflon® sheet, air-dried, and then further dried in a 70°C vacuum oven to produce a silicone polymer compound (H) in the form of a film with a thickness of 200-400 μm.

[0213] (Examples 1-2) A silicone polymer compound (H) was produced in the same manner as in Example 1-1, except that the amount of PAcγCDAAmMe used was adjusted so that x was 0.5.

[0214] (Examples 1-3) A silicone polymer compound (H) was produced in the same manner as in Example 1-1, except that the amount of PAcγCDAAmMe used was adjusted so that x equaled 2.

[0215] (Examples 1-4) A silicone polymer compound (H) was produced in the same manner as in Example 1-1, except that 1-pentene was not used.

[0216] (Example 2-1) A silicone polymer compound (H) was produced in the same manner as in Example 1-1, except that the photopolymerization initiator was changed to Irgacure1173(registered trademark).

[0217] (Example 2-2) A silicone polymer compound (H) was produced in the same manner as in Examples 1-2, except that the photopolymerization initiator was changed to Irgacure1173(registered trademark).

[0218] (Examples 2-3) Silicone polymer compound (H) was produced in the same manner as in Examples 1-3, except that the photopolymerization initiator was changed to Irgacure1173(registered trademark).

[0219] (Example 3-1) A silicone polymer compound (H) was produced according to the reaction scheme shown in Figure 5. Specifically, the silicone polymer compound (H) was produced in the same manner as in Example 1-1, except that 1-pentene was not used.

[0220] (Example 3-2) A silicone polymer compound (H) was produced in the same manner as in Example 1-2, except that 1-pentene was not used.

[0221] (Example 3-3) Silicone polymer compound (H) was produced in the same manner as in Examples 1-3, except that 1-pentene was not used.

[0222] (Example 4-1) According to the reaction scheme shown in Fig. 6, a silicone-based polymer compound (H) was produced. Specifically, the silicone-based polymer compound (H) was produced in the same manner as in Example 1-1, except that allyl alcohol was used instead of 1-pentene.

[0223] (Example 4-2) The silicone-based polymer compound (H) was produced in the same manner as in Example 1-2, except that allyl alcohol was used instead of 1-pentene.

[0224] (Example 4-3) The silicone-based polymer compound (H) was produced in the same manner as in Example 1-3, except that allyl alcohol was used instead of 1-pentene.

[0225] (Example 5) The silicone-based polymer compound (G) was produced in the same manner as in Example 4-3, except that 2-ethyl-2-adamantyl acrylate (AdEtA) was used as the alkenyl group-containing compound having a guest group instead of PAcγCDAAmMe.

[0226] (Example 6) The chloroform solution of the silicone-based polymer compound (H) obtained in Example 4-3 and the chloroform solution of the silicone-based polymer compound (G) obtained in Example 5 were mixed and stirred for 30 minutes, then placed in a circular Teflon (registered trademark) mold (radius 3 cm), air-dried overnight, and further dried in a vacuum oven at 70 °C to obtain a polymer material A in the form of a film with a thickness of 200 - 400 μm.

[0227] (Example 7) A silicone polymer compound (HG) was prepared according to the reaction scheme shown in Figure 7. First, PDMS-SH, PAcγCDAAmMe obtained in Production Example 1, AdEtA, and allyl alcohol were dissolved in chloroform to prepare a solution. To this solution, Irgacure184®, a photopolymerization initiator, was added in an amount of 0.1 eq. relative to the SH groups in PDMS-SH to prepare the raw materials. PDMS-SH was prepared by a known manufacturing method. The amounts of PDMS-SH, PAcγCDAAmMe, AdEtA, and 1-pentene used were adjusted so that the total amount of SH groups in PDMS-SH and the alkenyl groups of PAcγCDAAmMe, AdEtA, and 1-pentene were equal. The amount of chloroform used was 1 mL per 100 mg of PDMS-SH. In addition, the amounts of PAcγCDAAmMe and AdEtA used were adjusted so that x and y were 2 in the silicone polymer compound (HG) shown in the reaction scheme in Figure 7.

[0228] The aforementioned raw materials were irradiated with an Hg lamp for 30 minutes to allow the reaction to proceed and obtain a reaction solution. The obtained reaction solution was placed in a mold made from a Teflon® sheet, air-dried, and then further dried in a vacuum oven at 70°C to obtain polymer material B, which is formed from a silicone-based polymer compound (HG) in the form of a film with a thickness of 200-400 μm.

[0229] (Example 8) Polymer material C was produced according to the reaction scheme shown in Figure 8. Specifically, a solution was prepared by dissolving ethyl acrylate (EA) and 0.002 equivalents of Irgacure 184 (registered trademark) relative to the EA in chloroform. To this solution, the silicone polymer compound (H) obtained in Example 4-3 was added in a mass ratio of 1:1 between the silicone polymer compound (H) and ethyl acrylate (EA), and the solution was left to stand for 1 hour to swell the silicone polymer compound (H) obtained in Example 4-3. The resulting gel was sandwiched between a pair of polypropylene plates, and the gel was irradiated with an Hg lamp for 30 minutes to polymerize the EA and obtain an elastomer. The obtained elastomer was dried overnight in a vacuum oven at 70°C to obtain polymer material C in the form of a film with a thickness of 200-400 μm. This polymer material D had a movable crosslinked structure as shown in Figure 1.

[0230] (Example 9) Polymer material D was produced according to the reaction scheme shown in Figure 9. Specifically, a solution was prepared by dissolving ethyl acrylate (EA), 0.01 equivalents of PAcγCDAAmM relative to EA, and 0.002 equivalents of Irgacure184® in chloroform. To this solution, the silicone polymer compound (H) obtained in Example 4-3 was added in a ratio of silicone polymer compound (H):ethyl acrylate (EA) and PAcγCDAAmM = 1:1 (mass ratio), and the solution was left to stand for 1 hour to swell the silicone polymer compound (H) obtained in Example 4-3. The resulting gel was sandwiched between a pair of polypropylene plates, and the gel was irradiated with an Hg lamp for 30 minutes to polymerize EA and PAcγCDAAmM and obtain an elastomer. The obtained elastomer was dried overnight in a vacuum oven at 70°C to obtain polymer material D in the form of a film with a thickness of 200-400 μm. This polymer material D had a movable crosslinked structure as shown in Figure 3.

[0231] (Comparative Example 1-1) A comparative polysiloxane was prepared according to the reaction scheme shown in Figure 10. First, PDMS-SH, BDA, and 1-pentene were weighed, and 0.1 equivalents of Irgacure 1173 (registered trademark) relative to SH were kneaded without a solvent to obtain a mixture. At this time, the amounts used were adjusted so that the SH groups in PDMS-SH and the alkenyl groups of BDA and Pen were equal in volume. The mixture was placed in a circular Teflon (registered trademark) mold and irradiated with an Hg lamp for 30 minutes, and then 2 mL of 1-pentene was added and reacted for another 30 minutes. The resulting elastomer was dried in a vacuum oven at 70°C to obtain a comparative polysiloxane.

[0232] (Comparative Example 1-2) A comparative polysiloxane was obtained in the same manner as in Comparative Example 1-1, except that the amount of alkenyl groups of BDA and Pen relative to the SH groups in PDMS-SH was set to 0.5 equivalents.

[0233] (Comparative Examples 1-3) A comparative polysiloxane was obtained in the same manner as in Comparative Example 1-1, except that the amount of alkenyl groups of BDA and Pen relative to the SH group in PDMS-SH was set to 2 equivalents.

[0234] (Comparative Example 2) A polymer material described in Example 1 of International Publication No. 2021 / 045203 was prepared.

[0235] [Table 1]

[0236] (Example 10-1) First, a silicone polymer compound (H) was prepared according to the reaction scheme shown in Figure 11. PDMS-SH (5.61 mmol, 10 eq.) used in Example 1, PAcγCDAAmMe (0.55 mmol, 1 eq.) obtained in Production Example 1, and allyl alcohol (5.0 mmol, 9 eq.) were dissolved in 20 mL of ethyl acetate to prepare a solution. To this solution, Irgacure1173®, a photopolymerization initiator, was added in an amount equal to 0.1 eq. relative to the SH groups in PDMS-SH. The reaction was then carried out by irradiation with an Hg lamp for 60 minutes to obtain a solution containing the silicone polymer compound (H). The amounts of PDMS-SH, PAcγCDAAmMe, and allyl alcohol used were adjusted so that the total amount of SH groups in PDMS-SH and the alkenyl groups of PAcγCDAAmMe and allyl alcohol were equal.

[0237] To the solution containing the obtained silicone polymer compound (H), ethyl acrylate (EA) was added in an amount of 50% by mass relative to the total mass of the silicone polymer compound (H) and EA. BAPO (Irgacure819®) was then added, and the solution was transferred to a mold. The mold was then irradiated with a 420 nm LED for 1 hour. The resulting polymer was air-dried overnight in a fume hood, and finally vacuum-dried overnight in an 80°C vacuum oven to obtain a polymer material C' in the form of a 200-400 μm thick film. This polymer material C' possessed a movable crosslinked structure as shown in Figure 2.

[0238] (Example 10-2) Polymer material C' was obtained in the same manner as in Example 10-1, except that the amount of EA used was changed to 20% by mass relative to the total mass of the silicone polymer compound (H) and EA.

[0239] The polymer materials C' obtained in Examples 10-1 and 10-2 both exhibited high transparency, with the polymer material C' obtained in Example 10-1 being particularly superior in transparency.

[0240] Figure 12 shows the results of the tensile test (stroke-test force curve) of polymer material C' obtained in Examples 10-1 and 10-2. In Figure 12(a), "PDMS-TAcyγCD-AAI" and in Figure 12(b), "PDMS-TAcyγCD-AAI(1)" both represent the measurement results of the silicone polymer compound (H) obtained during the manufacturing process of Example 10-1.

[0241] The silicone polymer materials obtained in Examples 10-1 and 10-2 all exhibited excellent mechanical properties and were found to be tough materials. Figure 12(b) shows the results of verifying the stress distribution characteristics by tracking the change in stress over time when the strain of the silicone polymer material was stretched to 400% and fixed. From these results, it was found that the silicone polymer material obtained in Example 10-1 also exhibited excellent stress distribution.

[0242] In the obtained time-stress curve (Figure 12(b)), when σ(t) is the stress that changes with time t, the following Kohlausch-Williams-Watts equation (KWW equation) is obtained.

[0243]

number

[0244] As a result, as shown in Table 2, the time constant τ was 557 s for "PDMS-TAcyγCD-AAI(1)" and 33 s for the polymer material of Example 10-1 (PDMS-TAcyCD-AAl⊃PEA(1;50))), and the residual stress component σ∞ was 0.12 MPa for "PDMS-TAcyγCD-AAI(1)" and 0.01 MPa for the polymer material of Example 10-1. The small time constant τ and residual stress component σ∞ indicate that the polymer material of Example 10-1 relaxes stress faster and more effectively. Furthermore, Figure 12(c) shows the relationship between the stretching speed (10 mm / s and 1 mm / s) and the mechanical properties of the polymer material of Example 10-1. From these results, it was found that when the stretching speed of the polymer material of Example 10-1 is increased tenfold, both the fracture strain and fracture stress increase.

[0245] [Table 2]

[0246] (Example 11-1) Polymer material C' was obtained in the same manner as in Example 10-1, except that EA was replaced with 2-hydroxyethyl methacrylate (HEMA).

[0247] (Example 11-2) Polymer material C' was obtained in the same manner as in Example 10-1, except that EA was replaced with a mixture in which the mass ratio of EA to HEMA was 12.5:37.5 (EA:HEMA).

[0248] (Example 11-3) Polymer material C' was obtained in the same manner as in Example 10-1, except that EA was replaced with a mixture of EA and HEMA in a mass ratio of 37.5:12.5 (EA:HEMA).

[0249] Figure 13 shows the results of tensile tests (stroke-test force curves) of polymer material C' obtained in Examples 11-1 to 11-3. In Figure 13(a), "PDMS-TAcyγCD-AAI" refers to the silicone-based polymer compound (H) obtained during the manufacturing process of Example 10-1, and "PDMS-TAcγCD-AAl⊃PHEMA(50)" refers to polymer material C' obtained in Example 11-1.

[0250] Figures 13(a) and (b) show that the polymer material C' obtained in Examples 11-1 to 11-3 also exhibits excellent mechanical properties and is a tough material. It is presumed that the chain-like polymer compound (P1) penetrating the host group has hydroxyl groups (i.e., hydrogen-bonding functional groups), which enables hydrogen bonding between molecules and improves the mechanical properties.

[0251] (Example 12-1) Polymer material C' was obtained in the same manner as in Example 11-2, except that allyl alcohol was replaced with 1-pentene.

[0252] Figure 14 shows the results of tensile tests (stroke-test force curves) for polymer material C' obtained in Examples 12-1 and 11-2. From these results, it was found that polymer material C' obtained in Example 12-1 also has excellent mechanical properties and is a tough material. Polymer material C' obtained in Example 12-1 has even better mechanical properties than polymer material C' obtained in Example 11-2. From these results, it is thought that the mechanical properties are improved when the SH of the PDMS moiety of the silicone polymer compound (H) is capped with an alkyl group such as a pentyl group.

[0253] (Example 13-1) Polymer material C' having a movable crosslinked structure as shown in Figure 2 was prepared according to the reaction scheme shown in Figure 15. 123 mg of PDMS-SH, 36 mg of PAcγCDAAmMe obtained in Production Example 1, 76 mg (1 mmol) of propanediol (POD), and 1000 mg (1 mmol) of polytetrahydrofuran (PTHF, number average molecular weight approximately 1000) were dissolved in 10 mL of dichloromethane (DCM), and 2.5 mg of IRGACURE1173 (registered trademark) was added to prepare the starting material solution. Polymerization was carried out by irradiating this starting material solution with a mercury lamp at 25°C for 1 hour while stirring. Subsequently, DBTDA (dibutyltin dilaurate), a tin catalyst, and 353 mg (2.1 mmol) of hexamethylene diisocyanate (HDI) were added, and the mixture was stirred at 25°C for 24 hours. The resulting polymerization mixture was poured into a Teflon® cube mold (size: 50mm x 50mm x 20mm) and allowed to stand and dry at 25°C for more than 16 hours. This yielded a polymer material C' having a movable crosslinked structure as shown in Figure 2. In such polymer material C', the chain polymer compound (P1) is a urethane resin.

[0254] (Example 13-2) Polymer material C' having a movable crosslinked structure as shown in Figure 2 was prepared according to the reaction scheme shown in Figure 15. 1002 mg of PDMS-SH, 293 mg of PAcγCDAAmMe obtained in Production Example 1, 8 mg (0.1 mmol) of propanediol (POD), and 100 mg (0.1 mmol) of polytetrahydrofuran (PTHF, number average molecular weight approximately 1000) were dissolved in 10 mL of dichloromethane (DCM), and 21 mg of IRGACURE1173 (registered trademark) was added to prepare the starting material solution. Polymerization was carried out by irradiating this starting material solution with a mercury lamp at 25°C for 1 hour while stirring. Subsequently, DBTDA (dibutyltin dilaurate), a tin catalyst, and 35 mg (0.21 mmol) of hexamethylene diisocyanate (HDI) were added, and the mixture was stirred at 25°C for 24 hours. The resulting polymerization mixture was poured into a Teflon® cube mold (size: 50mm x 50mm x 20mm) and allowed to stand and dry at 25°C for more than 16 hours. This yielded polymer material C' having a movable crosslinked structure as shown in Figure 2.

[0255] (Comparative Example 13-1) A starting material was prepared by dissolving 1429 mg of PDMS-SH, 76 mg (1 mmol) of propanediol (POD), and 1000 mg (1 mmol) of polytetrahydrofuran (PTHF, number average molecular weight approximately 1000) in 10 mL of dichloromethane (DCM). To this starting material, DBTDA (dibutyltin dilaurate), a tin catalyst, and 353 mg (2.1 mmol) of hexamethylene diisocyanate (HDI) were added, and the mixture was stirred at 25°C for 24 hours. The resulting polymerization mixture was poured into a Teflon® cube mold (size: 50 mm × 50 mm × 20 mm) and allowed to stand and dry at 25°C for at least 16 hours. This yielded a polymer material that did not contain movable crosslinked structures.

[0256] Figures 16(a) and (b) show the results of tensile tests (stroke-test force curves) for polymer material C' obtained in Example 13-1 and polymer material obtained in Comparative Example 13-1. In Figure 16, "PDMS-CD(10)⊃PU" refers to polymer material C' obtained in Example 13-1, "PDMS-CD(90)⊃PU" refers to polymer material C' obtained in Example 13-2, and "PDMS(50) / PU" refers to polymer material obtained in Comparative Example 13-1.

[0257] Table 3 summarizes the results shown in Figure 16. From the results in Table 3 and Figure 16, it was found that the polymer material C' obtained in Examples 13-1 and 13-2 has superior mechanical properties compared to the polymer material of Comparative Example 1, which does not have a host group (i.e., a polymer material that does not form a movable crosslinked structure), and is a tough material.

[0258] [Table 3]

[0259] (Example 14-1) A polymer material C' having a movable crosslinked structure as shown in Figure 2 was prepared according to the reaction scheme shown in Figure 17. PDMS-SH (5.61 mmol, 10 eq.) used in Example 1, PAcγCDAAmMe (0.55 mmol, 1 eq.) obtained in Production Example 1, and pentene (5.0 mmol, 9 eq.) were dissolved in 20 mL of ethyl acetate to prepare a solution. Irgacure1173®, a photopolymerization initiator, was added to this solution in an amount of 0.1 eq. relative to the SH groups in PDMS-SH. The reaction was then carried out by irradiation with an Hg lamp for 60 minutes to obtain a solution containing a silicone polymer compound (H). This solution was dried in a 70°C windy oven for 8 hours and in an 80°C vacuum oven for 12 hours to form a film, thereby obtaining a film of the silicone polymer compound (H).

[0260] Next, a solution was prepared by adding 104 mg of polyethylene glycol (PEG-GLY, number average molecular weight 500, 0.21 mmol) and 46 mg of 4,7,10-trioxa-4,6-1,13-tridecanediamine (DEG, 0.21 mmol) to 150 ml of toluene, and this solution was impregnated into 150 mg of a film of the aforementioned silicone polymer compound (H). After two days, a polyaddition reaction was carried out by standing an organogel containing a portion of the solution in a 70°C windy oven for 8 hours. Subsequently, it was dried in an 80°C vacuum oven for 12 hours. This yielded polymer material C' having a movable crosslinked structure as shown in Figure 2. Since the yield of the obtained polymer material C' was 198 mg, the mass ratio of the silicone polymer compound (H) to the chain polymer compound (P1) (epoxy resin) penetrating the host group was 3:1.

[0261] (Comparative Example 14-1) A polymer material was produced in the same manner as in Example 14-1, except that the polyaddition reaction of PEG-GLY and DEG was carried out without producing a film of the silicone polymer compound (H).

[0262] Figure 18 shows the results of the tensile test (stroke-test force curve) of polymer material C' obtained in Example 14-1. In Figure 18(a), "PDMS-TAcyγCD-Pen(1)" refers to the silicone polymer compound (H) obtained during the manufacturing process of Example 14-1, "PDMS-TAcγCD⊃Epoxy(1;25)" refers to polymer material C' obtained in Example 14-1, and "Epoxy" refers to the epoxy resin of Comparative Example 14-1.

[0263] Figure 18 shows that the polymer material C' obtained in Example 14-1 has excellent mechanical properties and is a tough material.

[0264] (Example 15-1) A polymer material C' having a movable crosslinked structure as shown in Figure 2 was produced according to the reaction scheme shown in Figure 19. PDMS-SH used in Example 1, PAcγCDAAmMe obtained in Production Example 1, pentene, propanediol (POD), and polytetrahydrofuran (PTHF, number average molecular weight approximately 1000) were dissolved in 10 mL of dichloromethane (DCM) to prepare the starting material solution. Irgacure1173®, a photopolymerization initiator, was added to this solution at a concentration of 0.1 eq. relative to the SH groups in PDMS-SH. The reaction was then allowed to proceed by irradiating with an Hg lamp for 60 minutes. Subsequently, DBTDA (dibutyltin dilaurate) and hexamethylene diisocyanate (HDI), both tin catalysts, were added, and the mixture was stirred at 25°C for 24 hours. The resulting polymerization mixture was poured into a Teflon® cube mold (size: 50mm x 50mm x 20mm) and allowed to stand and dry at 25°C for more than 16 hours to obtain polymer material C' having a movable crosslinked structure as shown in Figure 2.

[0265] (Examples 15-2 to 15-5) A polymer material C' (chain polymer compound (P1) = urethane resin) having a movable crosslinked structure as shown in Figure 2 was obtained in the same manner as in Example 15-1, except that the amount of each raw material used was changed according to the formulation table shown in Table 4.

[0266] [Table 4]

[0267] Table 5 summarizes the results of the mechanical properties for Examples 15-1 to 15-5. These results show that the mechanical properties can be controlled by adjusting the ratio of the silicone polymer compound (H) and the chain polymer compound (P1), and that toughness dramatically improves, especially when the silicone polymer compound (H) is 70% by mass and 80% by mass.

[0268] [Table 5]

[0269] (Example 16-1) Polymer material C' was prepared in the same manner as in Example 15-1, such that the silicone polymer compound (H) (other than urethane resin) was 80% by mass and the chain polymer compound (P1) (urethane resin) was 20% by mass. In this case, the equivalent amount x of PAcγCDAAmMe (product of Production Example 1) contained in the silicone polymer compound (H) with respect to the SH group of PDMS-SH was set to 1.

[0270] (Example 16-2) Polymer material C' was produced in the same manner as in Example 16-1, except that the equivalent amount x was changed to 2.

[0271] (Example 16-3) Polymer material C' was produced in the same manner as in Example 16-1, except that the equivalent amount x was changed to 3.

[0272] (Comparative Example 16-1) Polymer material C' was produced in the same manner as in Example 16-1, except that the equivalent amount x was changed to 0.

[0273] Table 6 shows the manufacturing conditions for the polymer materials obtained in Examples 16-1 to 16-3 and Comparative Example 16-1 (x=0 is Comparative Example 16-1, and x=1, 2, and 3 are Examples 16-1, 16-2, and 16-3, respectively).

[0274] [Table 6]

[0275] Figure 20 shows the results of the mechanical properties for Examples 16-1 to 16-3, and Table 7 summarizes the results of Figure 20. From these results, it can be seen that as the equivalent amount x adjusted during manufacturing increases, the fracture strain decreases and the elastic modulus (Young's modulus) increases. This is presumed to be because the formation of movable crosslinks between the silicone polymer compound (H) and the chain polymer compound (P1) contributes to the mechanical properties. Furthermore, despite the increase in Young's modulus, the toughness (i.e., fracture energy) remained almost constant.

[0276] [Table 7]

[0277] As shown in Figure 21, in Comparative Example 16-1 where x=0 (i.e., without PAcγCDAAmMe), the resulting polymer material underwent phase separation, becoming opaque and unsuitable for tensile testing. On the other hand, in Examples 16-1 to 16-3 where x=1, 2, and 3 (i.e., with PAcγCDAAmMe), as shown in Figure 21, transparency improved, and improved compatibility due to the formation of movable crosslinks was also demonstrated.

[0278] (Example 17-1) Polymer material C' was prepared in the same manner as in Example 15-1, such that it contained 80% by mass of silicone polymer compound (H) (other than urethane resin) and 20% by mass of chain polymer compound (P1) (urethane resin). In this case, the equivalent amount x of the PDMS-SH in PAcγCDAAmMe (Production Example 1) contained in the silicone polymer compound (H) with respect to the SH group was set to 2, and the molar ratio y of PTHF to POD (value of POD / (POD+PTHF), the same applies hereafter) was set to 0.

[0279] (Example 17-2) Polymer material C' was produced in the same manner as in Example 17-1, except that the molar ratio y was changed to 33.

[0280] (Example 17-3) Polymer material C' was produced in the same manner as in Example 17-1, except that the molar ratio y was changed to 50.

[0281] (Example 17-4) Polymer material C' was produced in the same manner as in Example 17-1, except that the molar ratio y was changed to 64.

[0282] (Example 17-5) Polymer material C' was produced in the same manner as in Example 17-1, except that the molar ratio y was changed to 75.

[0283] Table 8 shows the manufacturing conditions for the polymer materials obtained in Examples 17-1 to 17-5 (y=0, 33, 50, 64, and 75, respectively).

[0284] [Table 8]

[0285] Figure 22 shows the results of the mechanical properties for Examples 17-1 to 17-5, and Table 9 summarizes Figure 22. From these results, a clear difference in mechanical properties due to the difference in y (i.e., the molar ratio of PTHF to POD) was confirmed. When y was 0, the toughness (fracture energy) improved by approximately 5 times while maintaining a similar Young's modulus compared to Example 15-1.

[0286] [Table 9]

[0287] From the above results, all of the silicone-based polymer materials obtained in the examples exhibited excellent mechanical properties. Regarding transparency, Table 1 shows the results only for the polymer materials of Examples 1-3, 3-3, and 16-1 to 16-3. From these results, it can be said that all polymer materials obtained in the examples shown in Table 1 exhibited high transparency, demonstrating superior transparency compared to Comparative Example 2. In addition, although the results are not shown in the figures, it was found that the polymer materials obtained in Examples 10-1 and 11-3 also exhibited excellent transparency.

[0288] (Method for evaluating mechanical properties) The mechanical properties of polymer materials were evaluated by observing the fracture point of the polymer material using a tensile test (stroke-force curve) (Shimadzu Corporation "AUTOGRAPH" (model: AGX-plus)). This fracture point was defined as the endpoint, and the maximum stress up to this endpoint was defined as the fracture stress of the polymer material. This tensile test was performed using an upward method, where the lower end of a film-like polymer material molded to a thickness of 200-400 μm was fixed, and the upper end was moved at a tensile speed of 1 mm / second. From this measurement, the Young's modulus and fracture energy of the polymer material were calculated.

[0289] (Transparency assessment) Films of polymer material formed to a thickness of 200-400 μm were created, and their transparency was evaluated according to the following criteria. <Evaluation Criteria> ○: Visual inspection confirmed the film's high transparency, and the text seen through the film was clearly recognizable. ×: The film had low transparency and a yellowish tint upon visual inspection, or the text seen through the film could not be clearly recognized.

[0290] (Photorepairability evaluation) The photorepairability of films of silicone polymer compounds (H) was evaluated using the following procedure. The films obtained in Examples 1-4 and 4-1 were used as measurement samples. An acetone solution of Irgacure184® was added dropwise to each sample, and the samples were allowed to swell overnight. The concentration and amount of Irgacure184 added were adjusted to 5% by mass relative to the film. After swelling, the films were dried overnight in a fume hood, then vacuum-dried overnight in a 35°C vacuum oven. An "X" shaped cut was made in the dried film using a utility knife, and the cut was irradiated with a mercury lamp to check if it disappeared.

[0291] As a result, the film samples of silicone polymer compound (H) obtained in Examples 1-4 showed clearly thinner incisions, while the film samples of silicone polymer compound (H) obtained in Example 4-1 showed complete disappearance of incisions. The same trend was observed even when the same test was performed by dropping acetone without Irgacure184® onto the samples. Therefore, it was found that silicone polymer compound (H) exhibits excellent photorepair properties, and in particular, silicone polymer compound (H) without SH groups exhibits superior photorepair properties.

Claims

1. A silicone polymer compound (H) having a polysiloxane skeleton as its main chain, The polysiloxane skeleton has at least one host group in its side chain, The host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative. A silicone polymer compound having a thioether bond between Si in the polysiloxane skeleton and the host group.

2. A silicone polymer compound (HG) having a polysiloxane skeleton as its main chain, The polysiloxane skeleton has at least one host group and at least one guest group in its side chain. The host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative. The guest group is a group that can be inclusion-formed into the cyclodextrin or cyclodextrin derivative. A silicone polymer compound having a thioether bond between Si in the polysiloxane skeleton and the host group.

3. The silicone polymer compound (H) and the silicone polymer compound (G) described in claim 1 are included. The silicone polymer compound (G) has a polysiloxane skeleton as its main chain, and the polysiloxane skeleton has at least one guest group in its side chain, and the guest group is a group that can be inclusioned with cyclodextrin or a cyclodextrin derivative. The host group encapsulates the guest group in a silicone polymer material.

4. The silicone polymer compound (HG) described in claim 2 is included, A silicone-based polymer material in which host groups and guest groups are bonded between molecules.

5. A crosslinked structure comprising the silicone polymer compound (H) described in claim 1, The crosslinked structure is a silicone polymer material having a structure in which the main chain of another silicone polymer compound (H) penetrates at least one of the host groups of the silicone polymer compound (H).

6. Furthermore, it contains a chain-like polymer compound (P1), The silicone polymer material according to claim 5, wherein the chain-like polymer compound (P1) penetrates the network of the crosslinked structure.

7. The crosslinked structure comprises a silicone polymer compound (H) and a chain polymer compound (P1) as described in claim 1, The crosslinked structure is a silicone polymer material having a structure in which the chain polymer compound (P1) penetrates at least one of the host groups of the silicone polymer compound (H).

8. The material comprises the silicone polymer compound (H) described in claim 1 and a chain-like polymer compound (P2) other than the polymer compound, The chain-like polymer compound (P2) has at least one host group in its side chain, and the host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative. At least one of the host groups of the silicone polymer compound (H) is penetrated by the main chain of another polymer compound (H), A silicone polymer material in which at least one of the host groups of the chain-like polymer compound (P2) is penetrated by the main chain of another chain-like polymer compound (P2).

9. An optical material containing the silicone polymer compound described in claim 1 or 2.

10. An optical material containing the silicone polymer material described in any one of claims 3 to 8.

11. A method for producing a silicone polymer compound, The aforementioned silicone polymer compound is a silicone polymer compound (H) having a polysiloxane skeleton as its main chain, the polysiloxane skeleton having at least one host group in its side chain, and the host group is a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative. The process includes a step of reacting a polysiloxane compound with at least one alkenyl group-containing compound, A method for producing a silicone polymer compound having an -SH group and / or a -Si-H group as the polysiloxane compound.

12. A method for producing a silicone polymer compound, The aforementioned silicone polymer compound is a silicone polymer compound (G) having a polysiloxane skeleton as its main chain, wherein the polysiloxane skeleton has at least one guest group in its side chain, and the guest group is a group that can be inclusioned with cyclodextrin or a cyclodextrin derivative. The process includes a step of reacting a polysiloxane compound with at least one alkenyl group-containing compound, A method for producing a silicone polymer compound having an -SH group and / or a -Si-H group as the polysiloxane compound.

13. A method for producing a silicone polymer compound, The silicone polymer compound is a silicone polymer compound (HG) having a polysiloxane skeleton as its main chain, wherein the polysiloxane skeleton has at least one host group and at least one guest group in its side chain, the host group being a monovalent group obtained by removing one hydrogen atom or hydroxyl group from a cyclodextrin or cyclodextrin derivative, and the guest group being a group that can be inclusion-forming of the cyclodextrin or cyclodextrin derivative. The process includes a step of reacting a polysiloxane compound with at least one alkenyl group-containing compound, A method for producing a silicone polymer compound having an -SH group and / or a -Si-H group as the polysiloxane compound.

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