copolymer

Abstract

A copolymer according to the present application includes: a silicone macromonomer unit having a specific structure derived from a silicone macromonomer; and a unit derived from another monomer other than the silicone macromonomer. The other monomer includes a site capable of interacting with a π-conjugated filler. The average degree of polymerization of the copolymer is 2.5-10. Additionally, the Hansen solubility parameter (HSP) distance (Ra) between the silicone macromonomer and the other monomer is 5 or more.　The present invention makes it possible to provide a copolymer which has high π-conjugated filler adsorption properties and is capable of improving the fluidity of the π-conjugated filler in a silicone resin.

Description

Copolymer polymer

[0001] The present invention relates to a copolymer polymer.

[0002] In recent years, due to the increasing heat generation associated with the high integration of circuits in electronic devices, heat countermeasures have become important, and the demand for heat dissipation materials for this purpose has been increasing. Heat dissipation materials are generally formed from resin compositions containing resins and fillers. In addition, resin compositions containing resins and fillers are often used for conductive materials for forming conductive layers and the like, and color materials containing pigments.

[0003] Fillers such as boron nitride, graphite, and carbon black are known as fillers having a six-membered ring structure and a conjugated system of π electrons (hereinafter sometimes referred to as π-conjugated fillers), and are utilized in various applications as inks and resin composites. However, since π-conjugated fillers have low affinity for resins, it is common to use dispersants from the viewpoint of improving affinity. Particularly, polymer-based dispersants are often used to enhance the dispersibility of fillers.

[0004] Polymer-based dispersants are generally composed of a site that interacts with the filler (hereinafter sometimes referred to as a filler linker) and a polymer main chain. Examples of using polycyclic aromatic compounds such as pyrene as filler linkers are known. For example, Patent Document 1 describes that a siloxane-modified polymer having a structural unit containing a siloxane structure and a vinyl-based monomer unit containing a polycyclic aromatic group can disperse a carbon nanocomposite well. Patent Document 2 describes a linear compound having a polycyclic aromatic group at the end of a polyorganosiloxane, and it is described that it can be used as a treatment agent for improving the dispersibility of nanocarbon in a silicone resin. Patent Document 3 describes a block or graft copolymer composed of a polyoxyalkylene chain and a polysiloxane chain as a treatment agent for polyorganosilsesquioxane.

[0005] Japanese Unexamined Patent Application Publication No. 2009-227845, Japanese Unexamined Patent Application Publication No. 2018-197300, Japanese Unexamined Patent Application Publication No. 1-266141

[0006] However, when the compounds disclosed in the above-mentioned literature were used as dispersants to disperse π-conjugated fillers such as flaky boron nitride in a silicone resin, the fluidity of the filler in the resin was not sufficiently improved, resulting in a decrease in the flexibility of the resin composition, and there was room for improvement. Therefore, the object of the present invention is to provide a copolymer polymer that has high adsorption properties for π-conjugated fillers such as flaky boron nitride and can improve the fluidity of π-conjugated fillers in a silicone resin.

[0007] The present inventors considered increasing the amount of polycyclic aromatic compound in the dispersant disclosed in Patent Documents 1 and 2 in order to enhance the interaction with π-conjugated fillers. However, in this case, the dispersant self-aggregates intramolecularly or intermolecularly, or its molecular weight becomes too large and it gels, thus failing to function as a dispersant. Furthermore, the present inventors considered that the compound disclosed in Patent Document 3 has polyoxyalkylene chains, which are filler linkers, bonded as side chains to the silicone main chain, which is a resin linker. As a result, the rotational degrees of freedom (free volume of the linkers) of each linker are low, and therefore the effect when added as a dispersant is low.

[0008] The inventors diligently studied to solve the above problems. As a result, they found that the above problems can be solved by a copolymer polymer having a specific silicone macromonomer unit and units derived from other monomers, wherein the other monomer has a site that can interact with a π-conjugated filler, and the average degree of polymerization and HSP distance (Ra) of the copolymer polymer are within a specific range, and thus completed the present invention.

[0009] In other words, the present invention relates to the following [1] to [8]. [1] A copolymer polymer having a silicone macromonomer unit derived from a silicone macromonomer represented by the following formula (1) and a unit derived from other monomers other than the silicone macromonomer, wherein the other monomer has a site that can interact with a π-conjugated filler, the average degree of polymerization of the copolymer polymer is 2.5 or more and 10 or less, and the HSP distance (Ra) of the Hansen solubility parameter between the silicone macromonomer represented by the following formula (A) and the other monomer is 5 or more. (In equation (1), R １ R is a hydrogen atom or a methyl group, ４ and R ５ Each of these is an independent hydrocarbon group having 1 to 6 carbon atoms, and multiple R ４ They may be the same or different, n1 is 10 or greater, X １ (where k is an organic group having 1 to 20 carbon atoms, k is the number of silicone macromonomer units in the copolymer polymer, and k is a value greater than 0.) (In formula (A), dD1, dP1, and dH1 represent the dispersion term, polar term, and hydrogen bonding term of the Hansen solubility parameter of the silicone macromonomer, respectively. dD2, dP2, and dH2 represent the dispersion term, polar term, and hydrogen bonding term of the Hansen solubility parameter of the other monomer, respectively.) [2] The copolymer polymer according to [1] above, wherein the viscosity is 700 mPa·s or less. [3] The copolymer polymer according to [1] or [2] above, wherein the weight ratio of the silicone macromonomer unit represented by the following formula (I) to the unit derived from the other monomer is 5 or more and 80 or less. (Number average molecular weight of silicone macromonomer units × k) / (Number average molecular weight of units derived from other monomers × p) Formula (I) (In Formula (I), p is the number of units derived from other monomers in the copolymer polymer) [4] The copolymer polymer according to any one of [1] to [3] above, wherein the units derived from other monomers are at least one selected from the group consisting of aromatic ring-containing units represented by the following formula (2) and reactive functional group-containing units represented by the following formula (3). (In Formulas (2) and (3), R ２ , R ３ are each independently a hydrogen atom or a methyl group, X ２ , X ３ are each independently an organic group having 1 to 20 carbon atoms, A is a group containing an aromatic ring, B is a group containing a reactive functional group, l represents the number of aromatic ring-containing units in the copolymer polymer, m represents the number of reactive functional group-containing units in the copolymer polymer, and l and m are each values greater than 0.) [5] The copolymer polymer according to any one of [1] to [4] above, wherein the other monomer is a (meth)acrylate-based monomer having a hydroxyl group. [6] A resin composition comprising the copolymer polymer according to any one of [1] to [5] above, a silicone resin, and an inorganic filler. [7] The resin composition according to [6] above, wherein the inorganic filler contains a π-conjugated filler. [8] The resin composition according to [6] or [7] above, wherein the inorganic filler is boron nitride.

[0010] According to the present invention, it is possible to provide a copolymer polymer capable of improving the fluidity of a π-conjugated filler in a silicone resin.

[0011] [Copolymer Polymer] The copolymer polymer of the present invention is a copolymer polymer having a silicone macromonomer unit derived from a silicone macromonomer represented by the following formula (1) and a unit derived from another monomer other than the silicone macromonomer. The other monomer has a site capable of interacting with a π-conjugated filler. Further, the average degree of polymerization of the copolymer polymer is 2.5 or more and 10 or less, and the HSP distance (Ra) of the Hansen solubility parameters of the silicone macromonomer and the other monomer represented by the following formula (A) is 5 or more. (In Formula (1), R １ are each independently a hydrogen atom or a methyl group, R ４ and R ５ are each independently a hydrocarbon group having 1 to 6 carbon atoms, and a plurality of R ４ may be the same or different from each other, n1 is 10 or more, X １(where k is an organic group having 1 to 20 carbon atoms, k is the number of silicone macromonomer units in the copolymer polymer, and k is a value greater than 0.) (In equation (A), dD1, dP1, and dH1 represent the dispersion, polarity, and hydrogen bonding terms of the Hansen solubility parameters of the silicone macromonomer, respectively. dD2, dP2, and dH2 represent the dispersion, polarity, and hydrogen bonding terms of the Hansen solubility parameters of the other monomers, respectively.)

[0012] The copolymer polymer of the present invention exhibits high adsorption to π-conjugated fillers, and when incorporated into a composition of silicone resin and π-conjugated fillers, it can improve the fluidity of the π-conjugated fillers. The reason for this is not entirely clear, but it is presumed to be as follows: The copolymer polymer of the present invention has an average degree of polymerization within a certain range and low viscosity, resulting in excellent diffusivity in silicone resins. Furthermore, since the copolymer polymer has units derived from silicone macromonomers, it has good compatibility with silicone resins. Moreover, since the copolymer polymer also has other polymer units that have sites capable of interacting with π-conjugated fillers, it also exhibits high adsorption to π-conjugated fillers. Here, "sites capable of interacting with π-conjugated fillers" include, for example, sites capable of π-π interactions (e.g., groups having aromatic rings such as pyrene, described later), sites capable of Lewis acid-base interactions, and sites capable of interacting through intermolecular forces such as hydrogen bonds. More specifically, "interactable sites" include sites where π-π interactions are possible with the smooth surface (Miller constant 001 plane) of a π-conjugated filler (e.g., boron nitride or boron nitride nanotubes), sites where Lewis acid-base interactions are possible with the smooth surface (Miller constant 001 plane) of a π-conjugated filler, and sites where interactions are possible with the filler end face (Miller constant 100 plane) through intermolecular forces such as hydrogen bonding. Furthermore, in the case of nanocarbon fillers (e.g., carbon nanotubes, carbon black, graphene), examples include sites where π-π interactions are possible with the smooth surface (Miller constant 001 plane) of a π-conjugated filler, and sites where interactions are possible with the filler end face (Miller constant 100 plane) through intermolecular forces such as hydrogen bonding.

[0013] Furthermore, the polysiloxane structure (resin linker) of the silicone macromonomer is introduced as a side chain of the copolymer polymer and is not directly bonded to the sites (filler linkers) of the other monomers that can interact with π-conjugated fillers. In other words, the resin linker and filler linker exist at a certain degree of separation. Combined with the large HSP distance (Ra) of the Hansen solubility parameter of both monomers and their low compatibility, the degree of rotational freedom between the resin linker and filler linker in the copolymer polymer is increased, greatly improving its function as a dispersant, and thereby improving the fluidity of the π-conjugated filler in the silicone resin. The copolymer polymer of the present invention will be described in detail below.

[0014] The copolymer polymer of the present invention is a copolymer polymer having silicone macromonomer units derived from silicone macromonomers and units derived from other monomers other than the silicone macromonomers. The silicone macromonomer refers to the raw material monomers before the copolymer polymer is formed, and the silicone macromonomer units derived from silicone macromonomers refer to the structures in the copolymer polymer formed after the polymerization of the silicone macromonomers. Similarly, other monomers refer to the raw material monomers before the copolymer polymer is formed, and units derived from other monomers refer to the structures in the copolymer polymer formed after the polymerization of the other monomers.

[0015] <Average Degree of Polymerization> The average degree of polymerization of the copolymer polymer of the present invention is 2.5 or more and 10 or less. An average degree of polymerization of 2.5 or more ensures that a certain amount of silicone macromonomer units and other monomer-derived units are present, thereby ensuring compatibility with the silicone resin while increasing adsorption to the π-conjugated filler. Furthermore, an average degree of polymerization of 10 or less improves the diffusivity of the copolymer polymer in the silicone resin. As a result, within the above range of average degree of polymerization, the fluidity of the π-conjugated filler in the silicone resin can be improved. The average degree of polymerization of the copolymer polymer is preferably 2.7 or more and 8 or less, and more preferably 3 or more and 7 or less. Note that the average degree of polymerization of the copolymer polymer is the average value of the total number of units in each copolymer polymer, or in other words, the average value of the total number of monomers forming each copolymer polymer. The average degree of polymerization is the average value of the copolymer polymer １ It can be calculated from the molar ratio of each unit obtained by H-NMR measurement and the number-average molecular weight measured by GPC of the copolymer polymer.

[0016] <Viscosity> The viscosity of the copolymer polymer of the present invention is preferably 700 mPa·s or less. A viscosity of 700 mPa·s or less improves the diffusivity of the copolymer polymer in the silicone resin, thereby improving its function as a dispersant. The viscosity of the copolymer polymer is preferably 500 mPa·s or less, and more preferably 300 mPa·s or less. The lower limit is not particularly limited, but the viscosity of the copolymer polymer is, for example, 30 mPa·s or more. The viscosity can be measured using an E-type viscometer (Toki Sangyo TV-200E) at a rotation speed of 1 rpm and a measurement temperature of 25°C.

[0017] <HSP distance> In the present invention, the HSP distance (Ra) of the Hansen solubility parameter between the silicone macromonomer and the other monomers is 5 or more. Ra is represented by the following formula (A).

[0018] (In equation (A), dD1, dP1, and dH1 represent the dispersion, polarity, and hydrogen bonding terms of the Hansen solubility parameters of the silicone macromonomer, respectively. dD2, dP2, and dH2 represent the dispersion, polarity, and hydrogen bonding terms of the Hansen solubility parameters of the other monomers, respectively.)

[0019] If Ra is less than 5, the compatibility of units derived from both monomers increases, which reduces the dispersant function of the copolymer polymer and worsens the fluidity of the π-conjugated filler in the silicone resin. From the viewpoint of improving fluidity, Ra is preferably 6 or higher, more preferably 7 or higher, preferably 50 or lower, and more preferably 20 or lower.

[0020] Furthermore, if there are two or more other monomers, that is, if there are two or more units derived from other monomers in a copolymer polymer, the Ra values ​​of each other monomer and the silicone macromonomer can be determined separately. It is sufficient if at least one of the obtained Ra values ​​is 5 or higher, but it is preferable that all of the obtained Ra values ​​are 5 or higher.

[0021] The Hansen solubility parameter (HSP) represents solubility in a three-dimensional space consisting of dispersion, polarity, and hydrogen bonding terms. The dispersion term represents the effect of dispersion forces, the polarity term represents the effect of inter-dipole forces, and the hydrogen bonding term represents the effect of hydrogen bonding forces. It is known that the smaller the HSP distance (Ra) calculated by the above equation (A), the higher the compatibility between the two substances.

[0022] The Hansen solubility parameter for each monomer can be determined using "Solvisation," a software program for calculating Hansen solubility parameters provided by Material Doors Co., Ltd.

[0023] Furthermore, the Hansen solubility parameter for each monomer can also be calculated by the following method: a solubility test is performed using a solvent with a known Hansen solubility parameter, and the results are calculated using the computer software Hansen Solubility Parameters in Practice (HSPiP). Suitable solvents include, for example, ethyl acetate, acetone, toluene, tetrahydrofuran, methanol, ethanol, 2-propanol, 2-ethylhexanal, N-methyl-2-pyrrolidone, oleic acid, water, methyl ethyl ketone, cyclohexanone, diethylene glycol, 1,4-dioxane, γ-butyrolactone, propylene carbonate 1,2-dibromobenzene, phenyl acetate, benzaldehyde, benzyl alcohol, diethyl carbonate, 2-methyl-1-propanol, acetylacetone, and n-hexane. Solubility tests should be performed by adding the sample to each solvent to a concentration of 5% by mass, stirring at 50 rpm for 30 minutes at room temperature (25°C), and then allowing it to stand at room temperature (25°C) for 1 hour.

[0024] <Silicone Macromonomer Unit> The silicone macromonomer unit of the copolymer polymer of the present invention is represented by the following formula (1).

[0025] In equation (1), R １ R is a hydrogen atom or a methyl group, preferably a methyl group. ４ and R ５ Each of these is an independent hydrocarbon group having 1 to 6 carbon atoms, and multiple R ４ These may be the same or different. ４ The group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and even more preferably a methyl group. ５ n1 is preferably an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 3 to 4 carbon atoms, and more preferably a butyl group. n1 is 10 or more. n1 is the siloxane moiety (-Si(R ４ ) ２This is the number of repeating siloxane moieties (-Si(R)) that each of the multiple molecular chains constituting the copolymer has. ４ ) ２ n1 is the average number of repetitions of -O-). From the viewpoint of improving compatibility between the copolymer polymer and the silicone resin, n1 is preferably 30 or more, more preferably 40 or more, and even more preferably 45 or more. Furthermore, from the viewpoint of lowering the viscosity of the copolymer polymer, n1 is preferably 200 or less, and more preferably 100 or less.

[0026] k is the number of silicone macromonomer units represented by formula (1) in the copolymer polymer, and is a value greater than 0. More specifically, k is the average value of the number of silicone macromonomer units that each of the multiple molecular chains constituting the copolymer polymer has. From the viewpoint of improving the compatibility between the copolymer polymer and the silicone resin, k is preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1 or more, even more preferably 1.5 or more, and even more preferably 2 or more. From the viewpoint of reducing the viscosity of the copolymer polymer, k is preferably 9 or less, more preferably 5 or less, and even more preferably 4 or less. k, which represents the number of repetitions of each unit, and l, m, and p, which will be described later, １ It can be measured by H-NMR. Furthermore, the above-mentioned n1 is ２９ It can be measured by Si-NMR.

[0027] X １ This is an organic group having 1 to 20 carbon atoms. This organic group may contain heteroatoms such as oxygen, nitrogen, and sulfur atoms, and may also contain groups such as ether groups, ester groups, amino groups, and amide groups. Among these, X １ It is preferably an organic group having 1 to 20 carbon atoms that contains an ester group, more preferably an organic group having 1 to 10 carbon atoms that contains an ester group, and even more preferably an organic group having 2 to 6 carbon atoms that contains an ester group. In particular, X １ It is preferable that the structure is represented by the following formula (4). R in equation (4) ６This is an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 to 5 carbon atoms, and more preferably an alkylene group having 3 to 4 carbon atoms. *1 is a bond that connects to the main chain of the copolymer polymer, and *2 is a bond that connects to Si in formula (1).

[0028] X １ When the structure is represented by formula (4), the silicone macromonomer unit is a constituent unit derived from a (meth)acrylate monomer having a polysiloxane structure. Note that (meth)acrylate refers to both acrylate and methacrylate.

[0029] <Other Monomers> The copolymer polymer of the present invention has units derived from other monomers other than the silicone macromonomer described above. The other monomers and the units derived from these other monomers have sites that can interact with π-conjugated fillers. The sites that can interact with π-conjugated fillers are not particularly limited, but may include, for example, a group containing a reactive functional group (for example, B in formula (3) described later), a group having an aromatic ring (for example, A in formula (2) described later), or both. Having units derived from other monomers increases the adsorption of the copolymer polymer to the π-conjugated filler.

[0030] Other monomer-derived units are preferably units represented by the following formula (α). (In equation (α), R １０ X is a hydrogen atom or a methyl group, ４ (where is an organic group having 1 to 20 carbon atoms, p is the number of units derived from other monomers in the copolymer polymer, and p is a value greater than 0. C is a site that can interact with π-conjugated fillers.)

[0031] In equation (α), R １０ is a hydrogen atom or a methyl group, preferably a methyl group. ４X is an organic group having 1 to 20 carbon atoms, preferably an organic group having 1 to 10 carbon atoms, and this organic group may contain heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms, and may also contain groups such as ether groups, ester groups, amino groups, and amide groups. ４ It is preferably an organic group having 1 to 20 carbon atoms that contains an ester group, and more preferably an organic group having 1 to 10 carbon atoms that contains an ester group. ４ This is X in equation (2) described later. ２ Either or X in formula (3) described later. ３ It is preferable that it be so.

[0032] In formula (α), C is a site that can interact with the π-conjugated filler, and is not particularly limited as long as it can act or bond with the π-conjugated filler by π-π interaction, hydrogen bonding, covalent bonding, etc., but is preferably a group containing a reactive functional group or a group containing an aromatic ring, and is more preferably A in formula (2) described later, or B in formula (3) described later. p is the number of units derived from other monomers represented by formula (α) in the copolymer polymer, and is a value greater than 0. In particular, p is the average value of the number of units derived from other monomers that each of the multiple molecular chains constituting the copolymer polymer has. From the viewpoint of increasing the interaction between the copolymer polymer and the π-conjugated filler, p is preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1 or more, even more preferably 1.5 or more, and even more preferably 2 or more, and from the viewpoint of reducing the viscosity of the copolymer polymer, it is preferably 9 or less, and more preferably 5 or less.

[0033] The other monomer-derived units may be one type or two or more types. For example, in the above formula (α), two or more units with different C portions may be present in the copolymer polymer.

[0034] The other monomer-derived units are preferably at least one selected from the group consisting of aromatic ring-containing units represented by the following formula (2) and reactive functional group-containing units represented by the following formula (3). (In equations (2) and (3), R ２ , R ３ Each is independently a hydrogen atom or a methyl group, X ２ , X ３ Each of these is an independent organic group having 1 to 20 carbon atoms, where A is a group containing an aromatic ring, B is a group containing a reactive functional group, l represents the number of aromatic ring-containing units in the copolymer polymer, and m represents the number of reactive functional group-containing units in the copolymer polymer. l and m are both values ​​greater than 0.

[0035] In equation (2), R ２ l is a hydrogen atom or a methyl group, preferably a methyl group. In formula (2), l is a value greater than 0. l is the number of aromatic ring-containing units represented by formula (2) in the copolymer polymer, and more specifically, it is the average value of the number of aromatic ring-containing units that each of the multiple molecular chains constituting the copolymer polymer has. From the viewpoint of enhancing interaction with π-conjugated fillers, l is preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1 or more, even more preferably 1.2 or more, and even more preferably 1.5 or more. Also, from the viewpoint of suppressing self-aggregation, it is preferably 5 or less, and more preferably 3 or less.

[0036] In formula (2), A is a group having an aromatic ring. A is not particularly limited, but from the viewpoint of enhancing the π-π interaction with the π-conjugated filler, a structure having a long aromatic ring in a conjugated system is preferred. For example, a fused ring compound in which multiple aromatic rings are fused together, or a structure in which multiple aromatic rings are linked by single, double, or triple bonds is preferred. The aromatic ring may be a heteroaromatic ring containing heteroatoms such as oxygen, nitrogen, or sulfur atoms, and the aromatic ring may have a structure other than a six-membered ring, for example, a five-membered ring. At least one of the hydrogen atoms constituting the aromatic ring may be substituted with a substituent. Examples of substituents include organic groups having 1 to 10 carbon atoms. Among these, a fused ring compound in which multiple aromatic rings (six-membered rings) are fused together is more preferred for A. Examples of the above-mentioned fused ring compounds include naphthalene, anthracene, phenanthrene, triphenylene, pyrene, tetracene, picene, perylene, pentaphene, pentacene, and hexaphene. At least one of the hydrogen atoms constituting the fused ring compound may be substituted with a substituent. Examples of substituents include organic groups having 1 to 10 carbon atoms. Among these, from the viewpoint of improving the dispersibility of π-conjugated fillers, the fused ring compound is preferably a fused ring compound in which four or more six-membered rings are fused together. Furthermore, among fused ring compounds in which four or more six-membered rings are fused together, pyrene is particularly preferred. Examples of structures in which the above-mentioned multiple aromatic rings are linked by single, double, or triple bonds include azobenzene and terthiophene.

[0037] X ２ This is an organic group having 1 to 20 carbon atoms, preferably an organic group having 1 to 10 carbon atoms, which may contain heteroatoms. This organic group may contain heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms, and may also contain groups such as ether groups, ester groups, amino groups, and amide groups. Among these, X ２ It is preferably an organic group having 1 to 20 carbon atoms that contains an ester group, more preferably an organic group having 1 to 10 carbon atoms that contains an ester group, and even more preferably an organic group having 2 to 6 carbon atoms that contains an ester group. In particular, X ２It is preferable that the structure is represented by the following formula (5).

[0038] R in equation (5) ７ is an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 carbon atom. *3 is a bond that connects to the main chain of the copolymer polymer, and *4 is a bond that connects to A in formula (2).

[0039] X ２ When the structure is represented by formula (5), the aromatic ring-containing unit is a constituent unit derived from a (meth)acrylate monomer having an aromatic ring. As the (meth)acrylate monomer having an aromatic ring, the above-mentioned condensed ring compound (meth)acrylate monomer is preferred.

[0040] In equation (3), R ３ m is a hydrogen atom or a methyl group, preferably a methyl group. In formula (3), m is a value greater than 0. m is the number of reactive functional group-containing units represented by formula (3) in the copolymer polymer, and more specifically, it is the average value of the number of reactive functional group-containing units that each of the multiple molecular chains constituting the copolymer polymer has. From the viewpoint of enhancing interaction with π-conjugated fillers, m is preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1 or more, even more preferably 1.1 or more, and even more preferably 1.3 or more. Also, from the viewpoint of reducing the viscosity of the copolymer polymer, m is preferably 9 or less, more preferably 5 or less, and even more preferably 3 or less.

[0041] B is a group containing a reactive functional group. The reactive functional group is not particularly limited, but it is preferably one or more selected from the group consisting of vinyl group, acid anhydride group, carboxyl group, amino group, hydroxyl group, isocyanate group, urethane group, oxazoline group, oxetane group, cyanate group, phenol group, hydrazide group, alkoxysilyl group, and phenol group. As a reactive functional group, it is preferable that it has hydrogen bonding properties because it readily interacts with the functional groups on the filler surface. Examples of functional groups with hydrogen bonding properties include acid anhydride group, carboxyl group, amino group, hydroxyl group, phenol group, alkoxysilyl group, and amide group, with the hydroxyl group being preferred.

[0042] If B is a group containing a hydroxyl group, it is preferable that B has a polyoxyalkylene structure from the viewpoint of enhancing interaction with the filler. From this viewpoint, it is preferable that B has the structure shown in the following formula (6).

[0043] In equation (6), R ８ is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group. Also, n ２ is an oxyalkylene group (R ８ -O) represents the number of repetitions, which is 1 to 50, preferably 2 to 20, and more preferably 4 to 10. In formula (6), *5 is X in formula (3). ３ This is a bonding operation that connects to [another bond].

[0044] X in equation (3) ３ This is an organic group having 1 to 20 carbon atoms, preferably an organic group having 1 to 10 carbon atoms. This organic group may contain heteroatoms such as oxygen, nitrogen, and sulfur atoms, and may also contain groups such as ether groups, ester groups, amino groups, and amide groups. Among these, X ３ It is preferably an organic group containing an ester group, and more preferably a structure represented by the following formula (7).

[0045] In equation (7), R ９R is a single bond or an alkylene group having 1 to 5 carbon atoms, and a single bond is preferred. *6 is a bond that connects to the main chain of the copolymer polymer, and *7 is a bond that connects to B in formula (3). ９ If it is a single bond, then formula (7) becomes an ester group. That is, X ３ It is preferable that it is an ester group.

[0046] X ３ When the structure is represented by formula (7), the reactive functional group-containing unit is a constituent unit derived from a (meth)acrylate monomer having a reactive functional group. As the (meth)acrylate monomer having a reactive functional group, a (meth)acrylate monomer having a hydroxyl group is preferred, and a (meth)acrylate monomer having a polyoxyalkylene structure is more preferred.

[0047] As described above, in the copolymer polymer of the present invention, X １ Equation (4), X ２ Equation (5), X ３ The structure of formula (7) is preferred, in which case the copolymer polymer is a polymer having a (meth)acrylate-derived backbone.

[0048] <Weight Ratio of Units> The copolymer polymer of the present invention has a weight ratio of silicone macromonomer units represented by the following formula (I) to units derived from other monomers of 5 to 80. (Number average molecular weight of silicone macromonomer units × k) / (Number average molecular weight of units derived from other monomers × p) Formula (I) (In formula (I), p is the number of units derived from other monomers in the copolymer polymer)

[0049] If the weight ratio shown in formula (I) is above the lower limit, the compatibility of the copolymer polymer with the silicone resin is further enhanced. If the weight ratio shown in formula (I) is below the upper limit, the viscosity increase of the copolymer polymer is more easily suppressed. As a result, if the weight ratio shown in formula (I) is within the above numerical range, the dispersibility of the π-conjugated filler in the silicone resin is further enhanced, and the fluidity can be further improved. If there are two or more types of other monomer-derived units, the weight ratio of formula (I) must be determined for each type of unit, and formula (I) must be satisfied for all types of units.

[0050] The number-average molecular weight of each unit in a copolymer polymer can be calculated by gel permeation chromatography (GPC) and NMR measurements of the copolymer polymer. The number-average molecular weight (Mn) of a silicone macromonomer unit can be calculated by gel permeation chromatography (GPC) and NMR measurements of the copolymer polymer. That is, the number-average molecular weight (Mn) of the copolymer polymer can be determined by GPC measurement. １ ¹H-NMR measurement allows for the determination of the molar ratio of each unit in the copolymer polymer and the repeating number n1 in the silicone macromonomer unit. From this information, the number-average molecular weight (Mn) of the silicone macromonomer unit can be calculated. Alternatively, since the number-average molecular weight (Mn) of the silicone macromonomer unit corresponds to the number-average molecular weight of the monomers used during polymerization to form the silicone macromonomer unit, the number-average molecular weight of these monomers can also be measured by GPC.

[0051] The number-average molecular weight of units derived from other monomers can also be calculated by GPC and NMR measurements of the copolymer polymer, similar to the number-average molecular weight of silicone macromonomer units. Alternatively, since the number-average molecular weight of units derived from other monomers corresponds to the number-average molecular weight of other monomers used in polymerization to form the units derived from other monomers, the number-average molecular weight of those monomers may be measured by GPC. In this specification, the number-average molecular weight measured by GPC is the value on a standard polystyrene basis.

[0052] The copolymer polymer of the present invention may have units other than silicone macromonomer units that do not have a site capable of interacting with the π-conjugated filler, to the extent that they do not impede the effects of the present invention. The number of units other than silicone macromonomer units that do not have a site capable of interacting with the π-conjugated filler is preferably small from the viewpoint of interaction with the π-conjugated filler and compatibility with the silicone resin, and is preferably 5% or less, more preferably 3% or less, and even more preferably 0% of the total number of units.

[0053] The copolymer polymer of the present invention can also be represented by the following formula (8).

[0054] In equation (8), R １ , R ４ , R ５ , R １０ , X １ , X ４ C, k, p, and n1 are equivalent to those in formulas (1) and (α) described above. In formula (8), Y represents the terminal structure of the copolymer polymer, and the two Ys may be the same or different. Y is a group derived from a reagent (polymerization initiator, chain transfer agent, etc.) used when polymerizing the copolymer polymer, and is usually an organic group having 1 to 20 carbon atoms.

[0055] The arrangement of the silicone macromonomer units, aromatic ring-containing units, and reactive functional group-containing units in the copolymer polymer is not particularly limited and may be in a blocky arrangement or a random arrangement.

[0056] The number-average molecular weight (Mn) of the copolymer polymer of the present invention is not particularly limited, but is preferably 10,000 to 30,000, and more preferably 10,000 to 27,000. When the number-average molecular weight of the copolymer polymer is above these lower limits, the compatibility with silicone resin is improved, and the dispersibility of fillers is enhanced. When the number-average molecular weight of the copolymer polymer is below these upper limits, the viscosity of the copolymer polymer is reduced, and the diffusivity to silicone resin is improved, making it easier to enhance the dispersibility of fillers. The molecular weight distribution (Mw / Mn) of the copolymer polymer of the present invention is preferably 5 or less, more preferably 4.5 or less, and even more preferably 4.0 or less, from the viewpoint of lowering the viscosity of the copolymer polymer and improving the dispersibility of π-conjugated fillers. The lower limit of the molecular weight distribution (Mw / Mn) is 1. The molecular weight distribution is the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn). The number-average molecular weight and weight-average molecular weight are standard polystyrene equivalent values ​​obtained by GPC measurement.

[0057] The molecular structure of the copolymer polymer of the present invention is not limited to a structure having linear dimethylsiloxane units (D-isomer), but may also include branched trimethylsiloxane units (T-isomer) or tetrafunctional siloxane units (Q-isomer).

[0058] <Method for producing copolymer polymers> The method for producing copolymer polymers of the present invention is not particularly limited, but includes polymerizing a monomer composition containing a monomer represented by formula (a1) and a monomer represented by formula (α'). In the above equations (a1) and (α'), R １ , R ４ , R ５ , R １０ , X １ , X ４C and n1 are equivalent to those in equations (1) and (α) described above.

[0059] Furthermore, the monomer represented by (α') above is preferably either the monomer represented by formula (a2), the monomer represented by formula (a3), or both, as shown below. In the above equations (a2) and (a3), R ２ , R ３ , X ２ , X ３ A and B are equivalent to those in equations (2) and (3) above.

[0060] Furthermore, as a copolymer polymer, X １ ~X ３ Since it is preferable that each of these has the respective structures of formula (4), formula (5), and formula (7), it is preferable to use (meth)acrylate monomers as monomers when polymerizing the copolymer polymer. That is, it is preferable to polymerize a monomer composition containing a monomer represented by the following formula (b1) and at least one monomer selected from the monomer represented by formula (b2) and the monomer represented by formula (b3) in order to polymerize the copolymer polymer of the present invention. Among these, it is more preferable to polymerize a monomer composition containing at least the monomer represented by the following formula (b1) and the monomer represented by formula (b3). When polymerizing, polymerization initiators, chain transfer agents, etc. that are used for polymerizing general (meth)acrylate monomers can be used. In the above equations (b1), (b2), and (b3), R １ ~R ５ A, B, and n1 are equivalent to those in equations (1) to (3) above. Also, R ６ , R ７ , R ９ This is equivalent to the formulas (4), (5), and (7) described above.

[0061] <Resin Composition> In the present invention, a resin composition comprising the copolymer polymer described above, a silicone resin, and an inorganic filler can be provided.

[0062] (Silicone Resin) A specific example of a silicone resin is a curable silicone resin. The curable silicone resin may be either a condensation-curing silicone resin or an addition-reaction-curing silicone resin, but an addition-reaction-curing silicone resin is preferred. The curable silicone resin preferably consists of a silicone resin that constitutes the main component and a silicone resin that constitutes the curing agent for curing the main component. In the case of an addition-reaction-curing silicone resin, the silicone resin used as the main component is preferably an organopolysiloxane having alkenyl groups. The organopolysiloxane having alkenyl groups is more preferably having two or more alkenyl groups. The alkenyl group is not particularly limited, but examples include those having 2 to 8 carbon atoms, such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl groups, and among these, the vinyl group is preferred from the viewpoint of ease of synthesis and reactivity. Furthermore, the alkenyl group is preferably an alkenyl group directly bonded to a silicon atom. Examples of organopolysiloxanes having alkenyl groups include vinyl-terminated polydimethylsiloxanes, vinyl-terminated polyphenylmethylsiloxanes, vinyl-terminated dimethylsiloxane-diphenylsiloxane copolymers, vinyl-terminated dimethylsiloxane-phenylmethylsiloxane copolymers, and vinyl-terminated dimethylsiloxane-diethylsiloxane copolymers.

[0063] The silicone resin used as a curing agent in addition-curing type silicone resins is not particularly limited as long as it can cure the silicone resin that is the main component as described above, but organohydrogenpolysiloxane, which is an organopolysiloxane having hydrosilyl groups (SiH), is preferred. The organohydrogenpolysiloxane preferably has two or more hydrosilyl groups.

[0064] Examples of organohydrogenpolysiloxanes include methylhydrosiloxane-dimethylsiloxane copolymer, polymethylhydrosiloxane, polyethylhydrosiloxane, and methylhydrosiloxane-phenylmethylsiloxane copolymer. These may or may not contain hydrosilyl groups at their terminal ends.

[0065] Furthermore, the silicone resin may be, for example, silicone oil. Examples of silicone oils include methylphenyl silicone oil, dimethyl silicone oil, and modified silicone oil. Silicone oil is liquid at room temperature and atmospheric pressure when compounded, and remains liquid or gel-like when used. In other words, silicone oil is not cured by curing agents, and even if it is cured, it remains liquid or gel-like after curing, making it substantially non-curable. Therefore, when silicone oil is used alone as a resin component, or in a relatively high compounding ratio, it can be used to create paste-like heat dissipation members and other materials formed from the resin composition.

[0066] The silicone resin contained in the resin composition preferably has a viscosity at 25°C of 5 mPa·s to 1000 mPa·s, more preferably 30 mPa·s to 700 mPa·s, and even more preferably 100 mPa·s to 600 mPa·s. The viscosity of the silicone resin is preferably measured using a viscometer (BROOKFIELD rotational viscometer DV-E) with a rotor of spindle No. 14, at a rotation speed of 5 rpm and a measurement temperature of 25°C. By setting the viscosity range of the silicone resin within the above range, the viscosity of the resin composition can be set within a predetermined range, improving the coatability of the resin composition while maintaining a constant shape after coating, making it easy to place on electronic components and the like.

[0067] Furthermore, if the resin composition is a two-component curing type and consists of either one or two components, it may contain either a silicone resin as the main component or a silicone resin as the curing agent, as described above. More specifically, it is preferable that the resin composition contains either an organopolysiloxane having an alkenyl group or an organohydrogenpolysiloxane. However, even if it consists of either one or two components of a two-component curing type, the silicone resin may contain, in addition to the organopolysiloxane having an alkenyl group or organohydrogenpolysiloxane, an organohydrogenpolysiloxane or an organopolysiloxane having an alkenyl group, as long as curing does not progress.

[0068] Furthermore, in the case of a one-component curing type, or in the case of a two-component curing type where the one-component and two-component components are mixed, the resin composition may contain both the main component silicone resin and the curing agent silicone resin. That is, in the case of a one-component curing type, or in the case of a two-component curing type where the one-component and two-component components are mixed, it is preferable that the resin composition contains both an organopolysiloxane having an alkenyl group and an organohydrogenpolysiloxane.

[0069] Furthermore, the curable resin composition may contain a non-curable organopolysiloxane as the silicone resin. For example, in addition to the above-mentioned organopolysiloxane having an alkenyl group or an organopolysiloxane having a hydrosilyl group, it may also contain silicone oil. Of course, the resin composition may also be a non-curable silicone resin composition, in which case, for example, silicone oil may be used alone as the silicone resin.

[0070] (Inorganic Fillers) Inorganic fillers are not particularly limited, but examples include oxides, nitrides, carbides, carbon-based materials, and metal hydroxides. Examples of oxides include metal oxides such as iron oxide, zinc oxide, alumina, magnesium oxide, titanium oxide, cerium oxide, and zirconium oxide, and oxides other than metal oxides such as silicon oxide (silica). Examples of nitrides include metal nitrides such as aluminum nitride, gallium nitride, chromium nitride, tungsten nitride, magnesium nitride, molybdenum nitride, and lithium nitride, and nitrides other than metal nitrides such as silicon nitride and boron nitride. Examples of carbides include metal carbides such as aluminum carbide, titanium carbide, and tungsten carbide, and carbides other than metal carbides such as silicon carbide and boron carbide. Examples of carbon-based materials include carbon black, graphite, carbon fiber, graphene, fullerene, carbon nanotubes, carbon nanofibers, and diamond. Examples of metal hydroxides include aluminum hydroxide, calcium hydroxide, and magnesium hydroxide.

[0071] The copolymer polymer of the present invention can disperse π-conjugated fillers well in a silicone resin and improve fluidity; therefore, it is preferable that the inorganic filler contains a π-conjugated filler. The π-conjugated filler is a filler having a π-electron conjugation system such as a six-membered ring structure, and examples include boron nitride and carbon-based materials. Examples of boron nitride include boron nitride nanotubes, boron nitride nanosheets, and hexagonal boron nitride (flaky boron nitride). Examples of carbon-based materials include graphite, carbon black, carbon fibers, and carbon nanotubes. One type of inorganic filler may be used alone, or two or more types may be used in combination.

[0072] The average particle size of the inorganic filler is not particularly limited, but is, for example, 0.5 to 100 μm, preferably 1 to 50 μm, and more preferably 1 to 10 μm. The average particle size refers to the particle size at which the volume integration is 50% (D50) in the particle size distribution of insulating fine particles determined by laser diffraction and scattering.

[0073] The amount of inorganic filler in the resin composition is not particularly limited and can be adjusted as appropriate depending on the application, but is, for example, 400 to 1000 parts by mass, preferably 500 to 900 parts by mass, per 100 parts by mass of silicone resin.

[0074] (Copolymer polymers and other dispersants) Copolymer polymers function as dispersants for dispersing inorganic fillers in silicone resin. The structure of copolymer polymers is as described above, so a detailed explanation is omitted here. The content of copolymer polymers in the resin composition is not particularly limited, but is, for example, 5 to 50 parts by mass, preferably 15 to 40 parts by mass, per 100 parts by mass of silicone resin.

[0075] The resin composition may contain dispersants other than the copolymer polymer described above. Examples of other dispersants include functional group-containing polymer dispersants having a structure different from that of the copolymer polymer. Examples of functional groups in the functional group-containing polymer dispersants include carboxyl groups, phosphate groups, sulfonic acid groups, carboxylic acid ester groups, phosphate ester groups, sulfonic acid ester groups, hydroxyl groups, amino groups, quaternary ammonium bases, amide groups, etc. Examples of polymers in the functional group-containing polymer dispersants include acrylic, vinyl, polyester, polyurethane, polyether, epoxy, polystyrene, and amino types.

[0076] Furthermore, other dispersants do not have to be polymers; for example, alkoxysilane compounds can also be used. An alkoxysilane compound is a compound having a structure in which one to three of the four bonds of a silicon atom (Si) are bonded to an alkoxy group, and the remaining bond is bonded to an organic substituent. The alkoxy group of an alkoxysilane compound is a hydrolyzable group, and examples include a methoxy group, ethoxy group, protoxy group, butoxy group, pentoxy group, and hexatoxy group. Among these, alkoxysilane compounds having a methoxy group or an ethoxy group are preferred. From the viewpoint of increasing affinity with inorganic fillers, the number of alkoxy groups in an alkoxysilane compound is preferably three. Therefore, it is more preferable that the alkoxysilane compound is at least one selected from trimethoxysilane compounds and triethoxysilane compounds.

[0077] Examples of functional groups included in the organic substituents of alkoxysilane compounds include acryloyl groups, alkyl groups, carboxyl groups, vinyl groups, methacrylic groups, aromatic groups, amino groups, isocyanate groups, isocyanurate groups, epoxy groups, hydroxyl groups, and mercapto groups.

[0078] Alkylalkoxysilane compounds are preferred because they readily blend with silicone resins and improve the dispersibility of inorganic fillers, and they have an alkyl group bonded to a silicon atom. The alkyl group bonded to the silicon atom preferably has four or more carbon atoms. Furthermore, the alkyl group bonded to the silicon atom preferably has 16 or fewer carbon atoms, from the viewpoint of keeping the viscosity of the resin composition low, as the viscosity of the alkoxysilane compound itself is relatively low.

[0079] Preferred alkylalkoxysilane compounds include n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, and n-decyltrimethoxysilane. Other alkoxysilane compounds besides alkylalkoxysilanes include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, and 3-phenylaminopropyltrimethoxysilane.

[0080] The content of other dispersants in the resin composition is, for example, 5 parts by mass or less, preferably 1 part by mass or less, and more preferably 0 parts by mass, per 100 parts by mass of silicone resin.

[0081] The resin composition of the present invention can be applied to various uses depending on the type of inorganic filler. For example, if the inorganic filler is a thermally conductive filler, the resin composition of the present invention can be used as a heat dissipation material; if the inorganic filler is electrically conductive, it can be used as a conductive material; and if the inorganic filler is colorable, such as a pigment, it can be used as a coloring material. As described above, the copolymer polymer in the present invention can improve the fluidity of the filler in the silicone resin, so it is possible to provide a flexible and easy-to-handle resin composition while increasing the content of various fillers.

[0082] The present invention will be clarified below by providing specific examples and comparative examples of the present invention. However, the present invention is not limited to the following examples.

[0083] [Molecular Weight] The measurement conditions for number-average molecular weight and weight-average molecular weight by GPC were as follows: A Waters ACQUITY APC system was used as the GPC instrument, an LF-604 6.0 × 150 mm column was used, and THF was used as the solvent. Measurements were taken at a flow rate of 0.3 mL / min and a temperature of 40°C. A polystyrene standard was used as the standard sample.

[0084] [１ 1H-NMR １ In the 1H-NMR measurement, measurement was carried out using a "ECX-400" manufactured by JEOL, with deuterated chloroform as the solvent, a sample concentration of 1% by weight, at 25 °C, a measurement frequency of 400 MHz, and an integration number of 8 times.

[0085] [Ra] For the Hansen solubility parameters of each monomer, dD, dP, and dH were determined from the molecular structure of each monomer using "Soluvision", which is a calculation software for Hansen solubility parameters provided by Material Doors Co., Ltd. Table 1 shows Ra for each monomer used in each example and comparative example.

[0086] [Evaluation of piercing load] 3 parts by mass of silicone resin ("KF96-100cs" manufactured by Shin-Etsu Chemical Co., Ltd.) and 1 part by mass of the copolymer polymer described in each example and comparative example were added to a container and stirred at 2000 rpm for 2 minutes using a planetary stirrer. Then, 4.57 parts by mass of alumina with an average particle size of 0.5 μm ("AA05N" manufactured by Sumitomo Chemical) and 6.855 parts by mass of alumina with an average particle size of 3 μm ("AA3" manufactured by Sumitomo Chemical) were added and stirred at 2000 rpm for 2 minutes using a planetary stirrer. Further, 4.57 parts by mass of flaky boron nitride with an average particle size of 50 μm ("HSPD50" manufactured by Dandong Chemical Engineering Institute) was added and stirred at 2000 rpm for 2 minutes using a planetary stirrer to obtain a resin composition. After defoaming with a rotation / revolution mixer Awatori Renkatora (vacuum type, manufactured by Shinki Co., Ltd.), a piercing rod (rod diameter 1 mm) having a disk-shaped member with a diameter of 3 mm and a thickness of 1 mm at the tip was pressed against the resin composition introduced into the container from the tip side of the piercing rod at a speed of 10 mm / min (piercing speed). The load (mN) when the tip of the piercing rod reached a depth of 10 mm from the liquid surface was measured. The material of the piercing rod was stainless steel. The measurement was carried out at 25 °C. It was evaluated according to the following criteria. Note that the lower the value of the piercing load (mN), the higher the fluidity of the filler. (Evaluation criteria) AAA 15 mN or less AA More than 15 mN and 30 mN or less A More than 30 mN and 40 mN or less B More than 40 mN

[0087] <Example 1> 19 g of silicone macromonomer (Shin-Etsu Chemical Co., Ltd. "KF2012") and 1.08 g of polyethylene glycol methacrylate (Tokyo Chemical Industries, Ltd. "PEGMA360") were completely dissolved in 36 g of toluene in a three-necked flask. Then, the mixture was purged with nitrogen for 10 minutes using a syringe needle, heated to 80°C, and then 0.84 g of azo polymerization initiator (V-601) was added. The mixture was heated and stirred at 80°C for 18 hours. After the reaction was complete, 70 mL of methanol was added to the beaker containing the solution and stirred for about 5 minutes. After standing for 30 minutes to 1 hour, the liquid separated into two layers, and the supernatant was discarded. This process was repeated three times, and the solvent was completely removed to obtain 17 g of the copolymer polymer product. Various structures of the copolymer polymer were analyzed by GPC and NMR. The results are shown in Table 2.

[0088] The structures of the monomers used in polymerization in Example 1 are as follows: Silicone macromonomer (left), polyethylene glycol methacrylate (right).

[0089] <Example 2> A copolymer polymer was obtained in the same manner as in Example 1, except that polyethylene glycol methacrylate was replaced with the following (PEGMA500, manufactured by Tokyo Chemical Industry Co., Ltd.) and the amount of monomer used was changed to 2.25 g. The results are shown in Table 2.

[0090] <Example 3> A copolymer polymer was obtained in the same manner as in Example 1, except that 0.9 g of the following pyrene methyl methacrylate (manufactured by Angene International Limited) was used instead of polyethylene glycol methacrylate. The results are shown in Table 2.

[0091] <Example 4> A copolymer polymer was obtained in the same manner as in Example 1, except that 0.9 g of pyrene methyl methacrylate, which was used in Example 3, was added in addition to the monomer used in Example 1. The results are shown in Table 2.

[0092] <Example 5> A copolymer polymer was obtained in the same manner as in Example 1, except that 0.9 g of the following catechol monomer (CM03, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used instead of polyethylene glycol methacrylate, and the solvent was changed to ethyl acetate. The results are shown in Table 2.

[0093] <Example 6> A copolymer polymer was obtained in the same manner as in Example 1, except that 0.45 g of the following glycerin monomethacrylate ("Bremmer GLM-R" manufactured by NOF Corporation) was used instead of polyethylene glycol methacrylate. The results are shown in Table 2.

[0094] <Example 7> A copolymer polymer was obtained in the same manner as in Example 1, except that 1.14 g of a monomer with the following structure (PPGMA380, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the polyethylene glycol methacrylate used in Example 1. The results are shown in Table 2.

[0095] <Example 8> A copolymer polymer was obtained in the same manner as in Example 1, except that the amount of PEGMA360 was changed to 2.16 g. The results are shown in Table 2.

[0096] <Example 9> A copolymer polymer was obtained in the same manner as in Example 1, except that the amount of PEGMA360 was changed to 3.24 g. The results are shown in Table 2.

[0097] <Example 10> A copolymer polymer was obtained in the same manner as in Example 2, except that the amount of PEGMA500 was changed to 1.5 g. The results are shown in Table 2.

[0098] <Example 11> A copolymer polymer was obtained in the same manner as in Example 2, except that the amount of PEGMA500 was changed to 3.0 g. The results are shown in Table 2.

[0099] <Example 12> A copolymer polymer was obtained in the same manner as in Example 1, except that V-601 was changed to 1.26 g. The results are shown in Table 2.

[0100] <Example 13> A copolymer polymer was obtained in the same manner as in Example 2, except that V-601 was changed to 0.42 g. The results are shown in Table 2.

[0101] <Example 14> A copolymer polymer was obtained in the same manner as in Example 1, except that V-601 was changed to 0.21 g. The results are shown in Table 2.

[0102] <Example 15> A copolymer polymer was obtained in the same manner as in Example 1, except that the amount of PEGMA360 was changed to 3.24 g and V-601 to 0.21 g. The results are shown in Table 2.

[0103] <Example 16> A copolymer polymer was obtained in the same manner as in Example 1, except that the silicone macromonomer was "X-22-174BX" manufactured by Shin-Etsu Chemical Co., Ltd., and 8.5 g of it was used. The results are shown in Table 2.

[0104] <Example 17> A copolymer polymer was obtained in the same manner as in Example 1, except that the silicone macromonomer used in Example 16 was used instead of the silicone macromonomer used in Example 1, and PEGMA 360 was changed to PEGMA 500. The results are shown in Table 2.

[0105] <Example 18> A copolymer polymer was obtained in the same manner as in Example 1, except that the amount of PEGMA360 was changed to 0.54 g. The results are shown in Table 2.

[0106] <Example 19> A copolymer polymer was obtained in the same manner as in Example 1, except that the silicone macromonomer was changed to "X-22-2404" manufactured by Shin-Etsu Chemical Co., Ltd., and 18.9 g of it was used. The results are shown in Table 2.

[0107] <Example 20> A copolymer polymer was obtained in the same manner as in Example 4, except that 0.75 g of a monomer with the following structure (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of polyethylene glycol methacrylate. The results are shown in Table 2.

[0108] <Comparative Example 1> A copolymer polymer was obtained in the same manner as in Example 1, except that 0.35 g of vinyl oxazoline (manufactured by Sigma-Aldrich) shown below was used instead of the polyethylene glycol methacrylate used in Example 1. The results are shown in Table 2.

[0109] <Comparative Example 2> A copolymer polymer was obtained in the same manner as in Example 2, except that PEGMA500 was changed to 0.75 g and V-601 to 1.05 g. The results are shown in Table 2.

[0110] <Comparative Example 3> A copolymer polymer was obtained in the same manner as in Example 1, except that the amount of V-601 was changed to 0.21 g and the reaction temperature was changed to 60°C. The results are shown in Table 2.

[0111]

[0112]

[0113] The copolymer polymer in each example is a copolymer polymer having a silicone macromonomer unit derived from a silicone macromonomer represented by formula (1) and a unit derived from other monomers other than the silicone macromonomer, the other monomers having sites that can interact with π-conjugated fillers. Furthermore, the copolymer polymer in each example has an average degree of polymerization of 2.5 or more and 10 or less, and an HSP distance (Ra) of 5 or more. It was found that by using the copolymer polymer of the example that satisfies each requirement of the present invention in this way, the puncture load value of the resin composition is reduced, the dispersibility of the π-conjugated filler in the silicone resin is improved, and the fluidity is increased. In contrast, the copolymer polymer of Comparative Example 1 is an example with a small Ra, and Comparative Examples 2 and 3 are examples where the average degree of polymerization of the copolymer polymer is outside the predetermined range, and in all cases the puncture load value was high and the fluidity was low.

Claims

1. A copolymer polymer having a silicone macromonomer unit derived from a silicone macromonomer represented by the following formula (1) and a unit derived from other monomers other than the silicone macromonomer, wherein the other monomer has a site capable of interacting with a π-conjugated filler, the average degree of polymerization of the copolymer polymer is 2.5 or more and 10 or less, and the HSP distance (Ra) of the Hansen solubility parameter between the silicone macromonomer represented by the following formula (A) and the other monomer is 5 or more. (In equation (1), R １ R is a hydrogen atom or a methyl group, ４ and R ５ Each of these is an independent hydrocarbon group having 1 to 6 carbon atoms, and multiple R ４ They may be the same or different, n1 is 10 or greater, X １ (where k is an organic group having 1 to 20 carbon atoms, k is the number of silicone macromonomer units in the copolymer polymer, and k is a value greater than 0.) (In equation (A), dD1, dP1, and dH1 represent the dispersion, polarity, and hydrogen bonding terms of the Hansen solubility parameters of the silicone macromonomer, respectively. dD2, dP2, and dH2 represent the dispersion, polarity, and hydrogen bonding terms of the Hansen solubility parameters of the other monomers, respectively.) 2. The copolymer polymer according to claim 1, wherein the viscosity is 700 mPa·s or less.

3. The copolymer polymer according to claim 1 or 2, wherein the weight ratio of the silicone macromonomer unit represented by the following formula (I) to the units derived from other monomers is 5 or more and 80 or less. (Number average molecular weight of the silicone macromonomer unit × k) / (Number average molecular weight of the units derived from other monomers × p) Formula (I) (In formula (I), p is the number of units derived from other monomers in the copolymer polymer) 4. The unit derived from the other monomer is at least one selected from the group consisting of an aromatic ring-containing unit represented by the following formula (2) and a reactive functional group-containing unit represented by the following formula (3), and the copolymer polymer according to claim 1 or 2. (In formulas (2) and (3), R ２ , R ３ are each independently a hydrogen atom or a methyl group, X ２ , X ３ are each independently an organic group having 1 to 20 carbon atoms, A is a group containing an aromatic ring, B is a group containing a reactive functional group, l represents the number of aromatic ring-containing units in the copolymer polymer, m represents the number of reactive functional group-containing units in the copolymer polymer, and l and m are each values exceeding 0.) 5. The copolymer polymer according to claim 1 or 2, wherein the other monomer is a (meth)acrylate monomer having a hydroxyl group.

6. A resin composition comprising the copolymer polymer according to claim 1 or 2, a silicone resin, and an inorganic filler.

7. The resin composition according to claim 6, wherein the inorganic filler comprises a π-conjugated filler.

8. The resin composition according to claim 6, wherein the inorganic filler is boron nitride.

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