Composition containing a compound having a polyoxyalkylene chain and a thermally conductive filler

Abstract

To provide a composition which has low viscosity and can form a cured product having high breaking strength.SOLUTION: The composition contains a polymerizable component including a compound represented by the formula (1) in the figure, and a thermally conductive filler, where a coupling agent is chemically adsorbed to a surface of the thermally conductive filler. [In the formula (1), R11 and R12 each independently represent a hydrogen atom or methyl group; and R13 represents a divalent group having a polyoxyalkylene chain.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition containing a compound having a polyoxyalkylene chain and a thermally conductive filler. [Background technology]

[0002] Electronic components such as processors and power modules, as well as batteries for electric vehicles, generate heat during use. To protect these components from heat, a means to efficiently dissipate the generated heat is required. Thermal interface materials (TIMs), which are thermally conductive materials (sometimes called heat dissipation materials), are placed between a heat source and a heat dissipation component such as a heat sink. They reduce the thermal resistance between the heat source and the heat dissipation component and promote heat conduction from the heat source. Heat generated from the heat source is efficiently conducted to the cooling component via the TIM, making it easier for the heat to be dissipated from the heat dissipation component.

[0003] Thermally conductive materials are required to have various properties depending on the application (target of application), and various materials are being developed. For example, Patent Document 1 describes that a cured product of a curable composition containing a specific compound having a polyoxyalkylene chain and two (meth)acryloyl groups has excellent elongation, and that the curable composition is suitable for use as a thermally conductive material because it contains a thermally conductive filler. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2021 / 107001 Summary of the Invention [Problem to be solved by the invention]

[0005] According to the studies of the present inventors, there are cases where a composition containing a polymerizable component and a thermally conductive filler is required to have low viscosity and excellent handleability, and to produce a cured product of the composition that has excellent breaking strength.

[0006] Therefore, an object of the present invention is to provide a composition that has a low viscosity and is capable of producing a cured product with high breaking strength. [Means for solving the problem]

[0007] As a result of intensive research, the present inventors have found that by using a specific compound having a polyoxyalkylene chain and two (meth)acryloyl groups together with a thermally conductive filler that has been surface-treated with a coupling agent, a composition can be obtained that has low viscosity and can give a cured product with high breaking strength. In some aspects, the present invention provides the following [1] to

[17] .

[0008] [1] A polymerizable component containing a compound represented by the following formula (1) and a thermally conductive filler, [ka] [In formula (1), R 11 and R 12 each independently represents a hydrogen atom or a methyl group, R 13 represents a divalent group having a polyoxyalkylene chain. A composition in which a coupling agent is chemically adsorbed onto the surface of a thermally conductive filler. [2] The composition according to [1], wherein the coupling agent comprises a silane coupling agent. [3] The composition according to [2], wherein the silane coupling agent has a (meth)acryloyl group. [4] The composition according to any one of [1] to [3], wherein the thermally conductive filler contains aluminum oxide. [5] The composition according to any one of [1] to [4], wherein the polyoxyalkylene chain contains an oxyethylene group. [6] The composition according to any one of [1] to [4], wherein the polyoxyalkylene chain contains an oxypropylene group. [7] The composition according to any one of [1] to [4], wherein the polyoxyalkylene chain is a copolymer chain containing an oxyethylene group and an oxypropylene group. [8] The composition according to [7], wherein the copolymer chain is a random copolymer chain. [9] The composition according to any one of [1] to [8], wherein the weight-average molecular weight of the compound represented by formula (1) is 5,000 or more.

[10] The composition according to any one of [1] to [9], wherein the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more.

[11] The composition according to any one of [1] to

[10] , wherein the viscosity of the compound represented by formula (1) at 25°C is 1000 Pa·s or less.

[12] The composition according to any one of [1] to

[11] , wherein the iron content in the composition is 80 ppm by mass or less based on the total amount of nonvolatile matter in the composition excluding the thermally conductive filler and the coupling agent.

[13] The composition according to any one of [1] to

[12] , wherein the polymerizable component further contains a compound represented by the following formula (2): [ka] [In formula (2), R 21 and R 22 R each independently represents a hydrogen atom or a monovalent organic group, and may be bonded to each other to form a ring. 23 represents a hydrogen atom or a methyl group.

[14] The composition according to any one of [1] to

[13] , wherein the polymerizable component further contains a compound represented by the following formula (3): [ka] [In formula (3), R 31 and R 32 each independently represents a hydrogen atom or a methyl group, R 33represents a divalent group having a poly(meth)acrylate chain.

[15] treating the thermally conductive filler with a coupling agent; and mixing the treated thermally conductive filler with a polymerizable component containing a compound represented by the following formula (1): [ka] [In formula (1), R 11 and R 12 each independently represents a hydrogen atom or a methyl group, R 13 represents a divalent group having a polyoxyalkylene chain.

[16] A cured product of the composition according to any one of [1] to

[14] .

[17] An article comprising a heat source and the cured product according to

[16] in thermal contact with the heat source. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a composition that has a low viscosity and is capable of giving a cured product with high breaking strength. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic cross-sectional view showing one embodiment of an article. [Figure 2] FIG. 10 is a schematic cross-sectional view showing another embodiment of the article. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0012] In this specification, "(meth)acryloyl" means "acryloyl" and its corresponding "methacryloyl", and the same applies to similar expressions such as "(meth)acrylate" and "(meth)acrylic".

[0013] The weight average molecular weight (Mw) and the ratio of weight average molecular weight to number average molecular weight (Mw / Mn) in this specification refer to values ​​measured using gel permeation chromatography (GPC) under the following conditions and determined using polystyrene as a standard substance. Measuring equipment: HLC-8320GPC (product name, manufactured by Tosoh Corporation) Analytical column: TSKgel SuperMultipore HZ-H (3 columns connected) (product name, manufactured by Tosoh Corporation) Guard column: TSKguardcolumn SuperMP(HZ)-H (product name, manufactured by Tosoh Corporation) ·Eluent:THF ·Measurement temperature: 25℃

[0014] [Composition] A composition according to one embodiment of the present invention contains a polymerizable component containing a compound represented by the following formula (1): [ka] In formula (1), R 11 and R 12 each independently represents a hydrogen atom or a methyl group, R 13 represents a divalent group having a polyoxyalkylene chain.

[0015] In one embodiment, R 11 and R 12 One of R may be a hydrogen atom and the other may be a methyl group, and in another embodiment, R 11 and R 12 and R may both be hydrogen atoms, and in another embodiment, R 11 and R 12 may both be methyl groups.

[0016] In one embodiment, the polyoxyalkylene chain contains a structural unit represented by the following formula (1a): This makes it possible to further suppress an increase in the viscosity of the composition while further increasing the strength (for example, breaking strength) of the cured product. [ka]

[0017] In this case, R 13 may be a divalent group having a polyoxyethylene chain, and the compound represented by formula (1) is preferably a compound represented by the following formula (1-2) (polyethylene glycol di(meth)acrylate). [ka] In formula (1-2), R 11 and R 12 is R in Eq. (1) 11 and R 12 and m is an integer of 2 or more.

[0018] In another embodiment, the polyoxyalkylene chain contains a structural unit represented by the following formula (1b): This can make the composition easier to handle. [ka]

[0019] In this case, R 13 may be a divalent group having a polyoxypropylene chain, and the compound represented by formula (1) is preferably a compound represented by the following formula (1-3) (polypropylene glycol di(meth)acrylate). [ka] In formula (1-3), R 11 and R 12 is R in Eq. (1) 11 and R 12 and n is an integer of 2 or more.

[0020] In another embodiment, the polyoxyalkylene chain is preferably a copolymer chain containing the structural unit represented by formula (1a) and the structural unit represented by formula (1b) described above, from the viewpoint of easily achieving both the strength of the cured product and the ease of handling of the composition. The copolymer chain may be any of an alternating copolymer chain, a block copolymer chain, and a random copolymer chain. The copolymer chain is preferably a random copolymer chain, from the viewpoint of further reducing the crystallinity of the compound represented by formula (1) and further facilitating the handling of the composition.

[0021] In each of the above-described embodiments, the polyoxyalkylene chain may have, in addition to the structural unit represented by formula (1a) and the structural unit represented by formula (1b), an oxyalkylene group having 4 to 5 carbon atoms, such as an oxytetramethylene group, an oxybutylene group, or an oxypentylene group, as a structural unit.

[0022] R 13 may be a divalent group having, in addition to the polyoxyalkylene chain, another organic group. The other organic group may be a chain-like group other than a polyoxyalkylene chain, such as a methylene chain (a chain having -CH2- as a structural unit), a polyester chain (a chain containing -COO- in a structural unit), or a polyurethane chain (a chain containing -OCON- in a structural unit).

[0023] For example, the compound represented by formula (1) may be a compound represented by the following formula (1-4). [ka] In formula (1-4), R 11 and R 12 is R in Eq. (1) 11 and R 12 are synonymous with R 14 and R 15 are each independently an alkylene group having 2 to 5 carbon atoms, and k1, k2, and k3 are each independently an integer of 2 or greater. k2 may be, for example, an integer of 16 or less.

[0024] Multiple Rs 14 and R 15 may be the same as or different from each other. 14 and R 15 Each of R preferably contains an ethylene group and a propylene group. That is, 14 O) k1 and a polyoxyalkylene chain represented by (R 15 O) k3 The polyoxyalkylene chains represented by the formula (1a) and (1b) are preferably copolymer chains containing an oxyethylene group (structural unit represented by the formula (1a)) and an oxypropylene group (structural unit represented by the formula (1b)).

[0025] In each of the above-described embodiments, the number of oxyalkylene groups in the polyoxyalkylene chain is preferably 100 or more. When the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more, the main chain of the compound represented by formula (1) becomes longer, thereby enabling the cured product to have excellent elongation and further increased strength. The number of oxyalkylene groups corresponds to m in formula (1-2), n in formula (1-3), and k1 and k3 in formula (1-4).

[0026] The number of oxyalkylene groups in the polyoxyalkylene chain is more preferably 130 or more, 180 or more, 200 or more, 220 or more, 250 or more, 270 or more, 300 or more, or 320 or more. The number of oxyalkylene groups in the polyoxyalkylene chain may be 600 or less, 570 or less, or 530 or less.

[0027] The weight average molecular weight of the compound represented by formula (1) is preferably 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, 9,000 or more, 10,000 or more, 11,000 or more, 12,000 or more, 13,000 or more, 14,000 or more, or 15,000 or more, from the viewpoint of providing a cured product with lower elasticity and excellent elongation. The weight average molecular weight of the compound represented by formula (1) is preferably 100,000 or less, 80,000 or less, 60,000 or less, 34,000 or less, 31,000 or less, or 28,000 or less, from the viewpoint of making it easier to adjust the viscosity of the composition.

[0028] The compound represented by formula (1) may be liquid at 25°C. In this case, the viscosity of the compound represented by formula (1) at 25°C is preferably 1000 Pa·s or less, 800 Pa·s or less, 600 Pa·s or less, 500 Pa·s or less, 350 Pa·s or less, 300 Pa·s or less, or 200 Pa·s or less, from the viewpoint of facilitating application of the composition to a coating surface and improving adhesion of the cured product to a coating surface. The viscosity of the compound represented by formula (1) at 25°C may be 0.1 Pa·s or more, 0.2 Pa·s or more, 0.3 Pa·s or more, 1 Pa·s or more, 2 Pa·s or more, or 3 Pa·s or more.

[0029] The compound represented by formula (1) may be solid at 25°C. In this case, from the viewpoint of improving the handleability of the composition, the compound represented by formula (1) is preferably liquid at 50°C. In this case, from the viewpoint of further improving the handleability of the composition, the viscosity of the compound represented by formula (1) at 50°C is preferably 100 Pa·s or less, more preferably 50 Pa·s or less, even more preferably 30 Pa·s or less, and particularly preferably 20 Pa·s or less. The viscosity of the compound represented by formula (1) at 50°C may be 0.1 Pa·s or more, 0.2 Pa·s or more, or 0.3 Pa·s or more.

[0030] In this specification, viscosity refers to a value measured in accordance with JIS Z8803, specifically, a value measured using an E-type viscometer (for example, PE-80L manufactured by Toki Sangyo Co., Ltd.). The viscometer can be calibrated in accordance with JIS Z8809-JS14000. The viscosity of the compound represented by formula (1) can be adjusted by adjusting the weight-average molecular weight of the compound.

[0031] From the viewpoint of providing a cured product with superior elongation, the content of the compound represented by formula (1) is preferably 1 mass % or more, 1.3 mass % or more, 1.5 mass % or more, or 1.7 mass % or more, based on the total amount of the composition, and may be, for example, 5 mass % or less, 4 mass % or less, 3 mass % or less, or 2 mass % or less.

[0032] The polymerizable component may further contain, as a polymerizable compound, a compound represented by formula (2) in addition to the compound represented by formula (1), or may further contain a compound represented by formula (3), or may further contain other polymerizable compounds other than the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3) (details will be described later). From the viewpoint of achieving superior elongation in the cured product, the content of the compound represented by formula (1) is preferably 5 parts by mass or more, 7 parts by mass or more, 10 parts by mass or more, or 12 parts by mass or more, relative to 100 parts by mass of the total of the compound represented by formula (1), the compound represented by formula (2), the compound represented by formula (3), and other polymerizable compounds (hereinafter referred to as the "total content of the polymerizable components"), and may be, for example, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, or 40 parts by mass or less.

[0033] The polymerizable component may further contain a compound represented by the following formula (2): In this case, the heat resistance of the cured product is improved. [ka] In formula (2), R 21 and R 22R each independently represents a hydrogen atom or a monovalent organic group, and may be bonded to each other to form a ring. 23 represents a hydrogen atom or a methyl group.

[0034] In one embodiment, R 21 and R 22 One of R may be a hydrogen atom and the other may be a monovalent organic group, and in another embodiment, R 21 and R 22 and R may both be hydrogen atoms, and in another embodiment, R 21 and R 22 and may be monovalent organic groups which may be bonded to each other to form a ring.

[0035] R 21 and R 22 When R are not bonded to each other to form a ring, the monovalent organic group may be, for example, a monovalent hydrocarbon group or an alkyl group. The number of carbon atoms in the monovalent hydrocarbon group (alkyl group) may be, for example, 1 or more and 6 or less. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. 21 and R 22 Examples of compounds represented by formula (2) in which the groups are not bonded to each other to form a ring include dimethylacrylamide, diethylacrylamide, and diisopropylacrylamide.

[0036] R 21 and R 22 are preferably bonded to each other to form a ring. In this case, the ring may be, for example, a 5-membered ring, a 6-membered ring, or a 7-membered ring, and is preferably a 6-membered ring. The ring is formed by bonding a nitrogen atom and R 21 and R 22 and a group represented by the formula: and may contain, in addition to the nitrogen atom, carbon atoms, hydrogen atoms, oxygen atoms, sulfur atoms, etc., and preferably contains only carbon atoms, hydrogen atoms, and oxygen atoms. That is, R 21 and R 22The group represented by R may be a group containing a carbon atom, a hydrogen atom, an oxygen atom, a sulfur atom, etc., and preferably a group containing only a carbon atom, a hydrogen atom, and an oxygen atom. 21 and R 22 Examples of the compound represented by formula (2) in which are bonded to each other to form a ring include N-(meth)acryloylmorpholine, N-acryloylthiomorpholine, N-acryloyloxazoline, N-acryloylthiazolidine, N-acryloylimidazolidine, N-(meth)acryloylpiperazine, N-vinylpyrrolidone, and N-vinylcaprolactam.

[0037] From the viewpoint of providing a cured product with better heat resistance, the content of the compound represented by formula (2) is preferably 0.1 mass% or more, 0.2 mass% or more, 0.3 mass% or more, 0.5 mass% or more, 0.7 mass% or more, or 1 mass% or more, based on the total amount of the composition, and may be, for example, 2 mass% or less, 1.5 mass% or less, 1.3 mass% or less, or 1 mass% or less.

[0038] From the viewpoint of providing a cured product with better heat resistance, the content of the compound represented by formula (2) is preferably 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass or more, relative to 100 parts by mass of the total content of the polymerizable components, and may be, for example, 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less.

[0039] The polymerizable component may further contain a compound represented by the following formula (3): In this case, the heat resistance of the cured product is improved. [ka] In formula (3), R 31 and R 32 each independently represents a hydrogen atom or a methyl group, R 33 represents a divalent group having a poly(meth)acrylate chain.

[0040] In one embodiment, R 31 and R 32One of R may be a hydrogen atom and the other may be a methyl group, and in another embodiment, R 31 and R 32 and R may both be hydrogen atoms, and in another embodiment, R 31 and R 32 may both be methyl groups.

[0041] The poly(meth)acrylate chain contains a structural unit represented by the following formula (3a): [ka] In formula (3a), R 34 represents a hydrogen atom or a monovalent organic group, and R 35 represents a hydrogen atom or a methyl group.

[0042] R 34 The monovalent organic group represented by the formula (I) may be, for example, a hydrocarbon group, or an organic group having an oxygen atom, a nitrogen atom, or the like. The hydrocarbon group may be linear or may have a ring (e.g., an aromatic ring). The number of carbon atoms in the hydrocarbon group may be, for example, 1 or more and 18 or less. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, a 2-propylheptyl group, a nonyl group, a decyl group, an isodecyl group, a dodecyl group, an octadecyl group, a phenyl group, a toluyl group, and a benzyl group.

[0043] Examples of organic groups having an oxygen atom include groups having an alkoxy group, groups having a hydroxyl group, groups having a carboxyl group, and groups having a glycidyl group. Examples of organic groups having an oxygen atom include 2-methoxyethyl, 3-methoxybutyl, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, carboxyl, and glycidyl groups. Examples of organic groups having a nitrogen atom include groups having an amino group and a nitrile group. Examples of organic groups having a nitrogen atom include 2-aminoethyl and nitrile groups. R 24 In one embodiment, the monovalent organic group represented by the formula (I) may be a group having a polar group, or may be a group having a hydroxyl group or a carboxyl group.

[0044] For example, the compound represented by formula (3) may be a compound represented by the following formula (3-2). [ka] In formula (3-2), R 31 and R 32 is R in equation (3). 31 and R 32 are synonymous with R 34 and R 35 is R in equation (3a) 34 and R 35 where a is an integer of 2 or greater.

[0045] The weight-average molecular weight of the compound represented by formula (3) is preferably 3,000 or more, 4,000 or more, 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, 9,000 or more, 10,000 or more, 11,000 or more, 12,000 or more, or 13,000 or more. From the viewpoint of easily adjusting the viscosity of the composition, the weight-average molecular weight of the compound represented by formula (3) is preferably 100,000 or less, 80,000 or less, 60,000 or less, 34,000 or less, 31,000 or less, or 28,000 or less. a in formula (3a) may be an integer such that the weight-average molecular weight of the compound represented by formula (3) falls within the above-mentioned range.

[0046] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the compound represented by formula (3) is preferably 1.4 or less, or 1.2 or less.

[0047] The compound represented by formula (3) may be liquid at 23°C. In this case, the viscosity of the compound represented by formula (3) at 23°C is 1000 Pa·s or less, 800 Pa·s or less, 700 Pa·s or less, 600 Pa·s or less, or 550 Pa·s or less, from the viewpoint of facilitating application of the composition to a coating surface and improving adhesion of the cured product to a coating surface. The viscosity of the compound represented by formula (3) at 25°C may be 5 Pa·s or more, 10 Pa·s or more, 15 Pa·s or more, 20 Pa·s or more, 25 Pa·s or more, 30 Pa·s or more, or 35 Pa·s or more.

[0048] The glass transition temperature (Tg) of the compound represented by formula (3) may be 0° C. or lower, −10° C. or lower, or −30° C. or lower, or may be −60° C. or higher, −50° C. or higher, or −40° C. or higher. The glass transition temperature refers to a value measured by differential scanning calorimetry.

[0049] From the viewpoint of providing a cured product with better heat resistance, the content of the compound represented by formula (3) is preferably 0.1 mass % or more, 0.3 mass % or more, 0.5 mass % or more, or 0.7 mass % or more, based on the total amount of the composition, and may be, for example, 3 mass % or less, 2 mass % or less, or 1 mass % or less.

[0050] From the viewpoint of providing a cured product with better heat resistance, the content of the compound represented by formula (3) is preferably 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, or 7 parts by mass or more, relative to 100 parts by mass of the total content of the polymerizable components, and may be, for example, 40 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less.

[0051] The mass ratio of the content of the compound represented by formula (1) to the content of the compound represented by formula (3) (content (mass) of the compound represented by formula (1) / content (mass) of the compound represented by formula (3)) is preferably 1 or more, 1.2 or more, 1.4 or more, 1.8 or more, or 2.2 or more from the viewpoint of providing a cured product with better elongation, and is preferably 6 or less, 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, 2.8 or less, or 2.4 or less from the viewpoint of providing a cured product with better heat resistance.

[0052] The polymerizable component may further contain a polymerizable compound other than the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3), which is copolymerizable with the compound represented by formula (1) described above, for the purpose of adjusting the physical properties of the composition, etc.

[0053] The other polymerizable compound may be, for example, a compound having one (meth)acryloyl group other than the compound represented by formula (2). The compound may be, for example, an alkyl(meth)acrylate. The other polymerizable compound may be a compound having, in addition to one (meth)acryloyl group, an aromatic hydrocarbon group, a group containing a polyoxyalkylene chain, a group containing a heterocycle, an alkoxy group, a phenoxy group, a group containing a silane group, a group containing a siloxane bond, a halogen atom, a hydroxyl group, a carboxyl group, an amino group, or an epoxy group. In particular, by including an alkyl(meth)acrylate in the composition, the viscosity of the composition can be adjusted. Furthermore, by including a compound having, in addition to a (meth)acryloyl group, a hydroxyl group, a carboxyl group, an amino group, or an epoxy group in the composition, the adhesion of the composition and its cured product to a member can be further improved.

[0054] The alkyl group in the alkyl (meth)acrylate (the alkyl group portion other than the (meth)acryloyl group) may be linear, branched, or alicyclic. The number of carbon atoms in the alkyl group may be, for example, 1 to 30. The number of carbon atoms in the alkyl group may be 1 to 11, 1 to 8, 1 to 6, or 1 to 4, or may be 12 to 30, 12 to 28, 12 to 24, 12 to 22, 12 to 18, or 12 to 14.

[0055] Examples of alkyl (meth)acrylates having a linear alkyl group include alkyl (meth)acrylates having a linear alkyl group having 1 to 11 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, and undecyl (meth)acrylate. Examples thereof include alkyl (meth)acrylates having a linear alkyl group having 12 to 30 carbon atoms, such as sil (meth)acrylate (lauryl (meth)acrylate), tetradecyl (meth)acrylate, hexadecyl (meth)acrylate (cetyl (meth)acrylate), octadecyl (meth)acrylate (stearyl (meth)acrylate), docosyl (meth)acrylate (behenyl (meth)acrylate), tetracosyl (meth)acrylate, hexacosyl (meth)acrylate, and octacosyl (meth)acrylate.

[0056] Examples of alkyl (meth)acrylates having a branched alkyl group include alkyl (meth)acrylates having a branched alkyl group having 1 to 11 carbon atoms, such as s-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, isopentyl (meth)acrylate, isoamyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, and isodecyl (meth)acrylate; Examples of the alkyl (meth)acrylate include alkyl (meth)acrylates having a branched alkyl group having 12 to 30 carbon atoms, such as decyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isoundecyl (meth)acrylate, isododecyl (meth)acrylate, isotridecyl (meth)acrylate, isopentadecyl (meth)acrylate, isohexadecyl (meth)acrylate, isoheptadecyl (meth)acrylate, isostearyl (meth)acrylate, and decyltetradecanyl (meth)acrylate.

[0057] Examples of alkyl(meth)acrylates having an alicyclic alkyl group (cycloalkyl group) include cyclohexyl(meth)acrylate, 3,3,5-trimethylcyclohexyl(meth)acrylate, isobornyl(meth)acrylate, terpene(meth)acrylate, and dicyclopentanyl(meth)acrylate.

[0058] Examples of the compound having a (meth)acryloyl group and an aromatic hydrocarbon group include benzyl (meth)acrylate.

[0059] Examples of compounds having a (meth)acryloyl group and a group containing a polyoxyalkylene chain include polyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, polybutylene glycol (meth)acrylate, and methoxypolybutylene glycol (meth)acrylate.

[0060] Examples of compounds having a (meth)acryloyl group and a group containing a heterocycle include tetrahydrofurfuryl (meth)acrylate.

[0061] Examples of the compound having a (meth)acryloyl group and an alkoxy group include 2-methoxyethyl acrylate.

[0062] Examples of the compound having a (meth)acryloyl group and a phenoxy group include phenoxyethyl (meth)acrylate.

[0063] Examples of compounds having a (meth)acryloyl group and a group containing a silane group include 3-acryloxypropyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, and 10-acryloyloxydecyltriethoxysilane.

[0064] Examples of the compound having a (meth)acryloyl group and a group containing a siloxane bond include silicone (meth)acrylate.

[0065] Examples of the compound having a (meth)acryloyl group and a halogen atom include trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 1,1,1,3,3,3-hexafluoro-2-propyl (meth)acrylate, perfluoroethyl methyl (meth)acrylate, perfluoropropyl methyl (meth)acrylate, perfluorobutyl methyl (meth)acrylate, perfluoropentyl methyl (meth)acrylate, perfluorohexyl methyl (meth)acrylate, perfluoroheptyl methyl (meth)acrylate, perfluorooctyl methyl (meth)acrylate, perfluorononyl methyl (meth)acrylate, perfluorodecyl methyl (meth)acrylate, perfluoroundecyl methyl (meth)acrylate, perfluorododecyl methyl (meth)acrylate, and perfluoro Examples of (meth)acrylates having a fluorine atom include tridecylmethyl (meth)acrylate, perfluorotetradecylmethyl (meth)acrylate, 2-(trifluoromethyl)ethyl (meth)acrylate, 2-(perfluoroethyl)ethyl (meth)acrylate, 2-(perfluoropropyl)ethyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluoropentyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluoroheptyl)ethyl (meth)acrylate, 2-(perfluorooctyl)ethyl (meth)acrylate, 2-(perfluorononyl)ethyl (meth)acrylate, 2-(perfluorotridecyl)ethyl (meth)acrylate, and 2-(perfluorotetradecyl)ethyl (meth)acrylate.

[0066] Examples of the compound having a (meth)acryloyl group and a hydroxyl group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate; and hydroxyalkyl cycloalkane (meth)acrylates such as (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.

[0067] Examples of the compound having a (meth)acryloyl group and a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, monohydroxyethyl phthalate acrylate (e.g., "Aronix M5400" manufactured by Toagosei Co., Ltd.), and 2-acryloyloxyethyl succinate (e.g., "NK Ester A-SA" manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0068] Examples of compounds having a (meth)acryloyl group and an amino group include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate.

[0069] Examples of the compound having a (meth)acryloyl group and an epoxy group include glycidyl (meth)acrylate, α-ethyl glycidyl (meth)acrylate, α-n-propyl glycidyl (meth)acrylate, α-n-butyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, α-ethyl-6,7-epoxyheptyl (meth)acrylate, 3-methyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, 5-methyl-5,6-epoxyhexyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and α-ethyl-β-methylglycidyl (meth)acrylate.

[0070] From the viewpoint of making it easier to adjust the viscosity of the composition or from the viewpoint of further increasing the adhesiveness of the composition, the content of the other polymerizable compounds is preferably 1 mass % or more, 2 mass % or more, 3 mass % or more, 4 mass % or more, or 5 mass % or more, based on the total amount of the composition, and may be, for example, 10 mass % or less, 8 mass % or less, or 6 mass % or less.

[0071] From the viewpoint of making it easier to adjust the viscosity of the composition or further increasing the adhesion of the composition, the content of the other polymerizable compounds is preferably 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 55 parts by mass or more, or 60 parts by mass or more, relative to 100 parts by mass of the total content of the polymerizable components, and may be, for example, 90 parts by mass or less, 80 parts by mass or less, or 70 parts by mass or less.

[0072] The composition may further contain a polymerization initiator. The polymerization initiator may be, for example, a thermal polymerization initiator that generates radicals by heat, a photopolymerization initiator that generates radicals by light, etc. The polymerization initiator is preferably a thermal polymerization initiator.

[0073] When the composition contains a thermal polymerization initiator, a cured product of the composition can be obtained by applying heat to the composition. In this case, the composition may be a composition that is cured by heating preferably at 105°C or higher, more preferably 110°C or higher, and even more preferably 115°C or higher, and may be a composition that is cured by heating at, for example, 200°C or lower, 190°C or lower, or 180°C or lower. The heating time when heating the composition may be appropriately selected depending on the composition of the composition so that the composition is suitably cured.

[0074] Examples of the thermal polymerization initiator include azo compounds such as azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, and azodibenzoyl, and organic peroxides such as benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, 1,1-t-butylperoxy-3,3,5-trimethylcyclohexane, and t-butylperoxyisopropyl carbonate. These thermal polymerization initiators may be used alone or in combination of two or more.

[0075] When the composition contains a photopolymerization initiator, a cured product of the composition can be obtained, for example, by irradiating the composition with light (e.g., light including at least a part of the wavelength of 200 to 400 nm (ultraviolet light)). The conditions for light irradiation may be appropriately set depending on the type of photopolymerization initiator.

[0076] The photopolymerization initiator may be, for example, a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an α-ketol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator, a photoactive oxime-based photopolymerization initiator, a benzoin-based photopolymerization initiator, a benzyl-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, a ketal-based photopolymerization initiator, a thioxanthone-based photopolymerization initiator, or an acylphosphine oxide-based photopolymerization initiator.

[0077] Examples of benzoin ether-based photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one (e.g., "Irgacure 651" manufactured by BASF), anisole methyl ether, etc. Examples of acetophenone-based photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone (e.g., "Irgacure 184" manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (e.g., "Irgacure 2959" manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (e.g., "Irgacure 1173" manufactured by BASF), and methoxyacetophenone.

[0078] Examples of α-ketol photopolymerization initiators include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropan-1-one. Examples of aromatic sulfonyl chloride photopolymerization initiators include 2-naphthalenesulfonyl chloride. Examples of photoactive oxime photopolymerization initiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.

[0079] Examples of benzoin-based photopolymerization initiators include benzoin. Examples of benzyl-based photopolymerization initiators include benzil. Examples of benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexyl phenyl ketone. Examples of ketal-based photopolymerization initiators include benzil dimethyl ketal. Examples of thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.

[0080] Examples of acylphosphine photopolymerization initiators include bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylpropan-1-yl)phosphine oxide, and bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide. cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylpropan-1-yl)phosphine Oxide, bis(2,6-dibutoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethytoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tri(2-methylbenzoyl)phosphine oxide, etc.

[0081] The above-mentioned photopolymerization initiators may be used alone or in combination of two or more.

[0082] The content of the polymerization initiator is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and particularly preferably 0.5 parts by mass or more, relative to 100 parts by mass of the total content of the polymerizable components, from the viewpoint of allowing the polymerization to proceed smoothly. The content of the polymerization initiator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, relative to 100 parts by mass of the total content of the polymerizable components, from the viewpoint of ensuring that the molecular weight of the polymer in the cured product of the composition falls within a suitable range and suppressing decomposition products.

[0083] In one embodiment, the composition contains a thermally conductive filler. The thermally conductive filler is a filler having a thermal conductivity of 10 W / m·K or more. The thermally conductive filler may be insulating or conductive, and is preferably an insulating filler. Materials constituting insulating thermally conductive fillers include aluminum oxide (alumina), aluminum hydroxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, silicon carbide, silicon dioxide, aluminum fluoride, calcium fluoride, zinc oxide, etc. Materials constituting conductive thermally conductive fillers include aluminum, silver, copper, etc. The thermally conductive filler preferably contains aluminum oxide (alumina). The thermally conductive filler may be spherical or polyhedral in shape.

[0084] From the viewpoint of enabling a thin application of the cured product of the composition, the average particle size of the thermally conductive filler is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less, and may be 0.05 μm or more, 0.1 μm or more, or 0.3 μm or more. The average particle size of the thermally conductive filler means the particle size (D50) at which the volume cumulative particle size distribution is 50%, and is measured using a laser diffraction particle size distribution analyzer (e.g., SALD-2300 (manufactured by Shimadzu Corporation)).

[0085] From the viewpoint of increasing the thermal conductivity of the composition, the content of the thermally conductive filler is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total amount of the composition, and may be 97% by mass or less, 95% by mass or less, or 93% by mass or less.

[0086] From the viewpoint of increasing the thermal conductivity of the composition, the content of the thermally conductive filler is preferably 65% ​​by volume or more, more preferably 70% by volume or more, and even more preferably 75% by volume or more, based on the total volume of the composition, and may be 90% by volume or less, 88% by volume or less, or 85% by volume or less.

[0087] In the composition according to this embodiment, a coupling agent is chemically adsorbed to the surface of the thermally conductive filler. In other words, the composition according to this embodiment contains a coupling agent chemically adsorbed to the surface of the thermally conductive filler. The chemical adsorption of the coupling agent to the surface of the thermally conductive filler can be confirmed by IR measurement (diffuse reflectance method) of the thermally conductive filler. Specifically, a solvent (e.g., methyl ethyl ketone) is first added to the composition to dissolve components other than the thermally conductive filler, such as polymerizable components. The thermally conductive filler is then recovered by filtration and vacuum dried. The drying temperature is below 100°C to prevent unreacted coupling agent that is not chemically adsorbed to the surface of the thermally conductive filler from reacting. Next, the dried thermally conductive filler is added to excess methyl ethyl ketone (at least 40 times the mass of the thermally conductive filler contained in the composition), stirred, and allowed to stand at room temperature (20-30°C) for at least 12 hours to allow the thermally conductive filler to settle. The supernatant liquid (at least 90% by mass of the added methyl ethyl ketone) is then removed. This removes any coupling agent that is not chemically adsorbed to the surface of the thermally conductive filler. The thermally conductive filler is then dried in an oven at 100°C, after which IR measurement (diffuse reflectance method) of the thermally conductive filler is performed. If the coupling agent is chemically adsorbed to the surface of the thermally conductive filler, the IR measurement will be 2800 to 3000 cm -1 Peaks of methoxy groups, methyl groups, and methylene chains derived from the coupling agent are observed in this range.

[0088] The coupling agent may be, for example, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like. The coupling agent is preferably a silane coupling agent. The silane coupling agent may be a compound having an alkoxysilyl group such as a dialkoxysilyl group or a trialkoxysilyl group. The silane coupling agent may have, for example, an organic functional group such as a vinyl group, a (meth)acryloyl group, an epoxy group, an amino group, a mercapto group, or an imidazole group; an alkyl group having 1 to 10 carbon atoms, or the like. The silane coupling agent preferably has a (meth)acryloyl group. The above-mentioned coupling agents may be used alone or in combination of two or more.

[0089] The content of the coupling agent is preferably 0.01 parts by mass or more, 0.02 parts by mass or more, or 0.025 parts by mass or more per 100 parts by mass of the thermally conductive filler, from the viewpoint of further reducing the viscosity of the composition and further increasing the breaking strength of the cured product. The content of the coupling agent is preferably 2 parts by mass or less, 1.5 parts by mass or less, or 1 part by mass or less, based on the total amount of the composition. If the content of the coupling agent is too high, the coupling agent is likely to self-condense, which may result in an excessive increase in the breaking strength of the cured product, an increase in the tensile modulus, and a decrease in the breaking elongation.

[0090] The composition may further contain a plasticizer. By containing the plasticizer in the composition, the adhesiveness of the composition and the elongation of the cured product can be further improved. Examples of the plasticizer include tackifiers such as butadiene rubber, isoprene rubber, silicone rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, urethane rubber, acrylic resin, rosin-based resin, and terpene-based resin, and polyalkylene glycol.

[0091] The content of the plasticizer may be 0.1 parts by mass or more, 1 part by mass or more, or 3 parts by mass or more, and may be 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, or 10 parts by mass or less, relative to 100 parts by mass of the total content of the polymerizable components.

[0092] The composition may further contain an antioxidant from the viewpoint of improving the thermal reliability of a cured product of the composition. The antioxidant may be, for example, a phenol-based antioxidant, a benzophenone-based antioxidant, a benzoate-based antioxidant, a hindered amine-based antioxidant, a benzotriazole-based antioxidant, or the like, and is preferably a phenol-based antioxidant.

[0093] The phenolic antioxidant has, for example, a hindered phenol structure (hindered phenol ring). The hindered phenol structure (hindered phenol ring) may be, for example, a structure in which t-butyl groups are bonded to one or both of the ortho positions relative to the hydroxyl group in the phenol ring. The phenolic antioxidant has one or more such hindered phenol rings, preferably two or more, more preferably three or more, and even more preferably four or more.

[0094] The content of the antioxidant may be 0.1 mass% or more, 0.2 mass% or more, or 0.3 mass% or more, and may be 10 mass% or less, 9 mass% or less, 8 mass% or less, or 7 mass% or less, based on the total amount of the composition.

[0095] The composition may further contain other additives as needed. Examples of other additives include surface treatment agents (excluding coupling agents chemically adsorbed to the surface of the thermally conductive filler), dispersants, curing accelerators, colorants, crystal nucleating agents, heat stabilizers, foaming agents, flame retardants, vibration dampers, dehydrating agents, and flame retardant aids (e.g., metal oxides). The content of other additives may be 0.1% by mass or more and 30% by mass or less based on the total amount of the composition.

[0096] From the viewpoint of further improving the heat resistance of the cured product, it is preferable that the amount of iron contained in the composition is small. Iron can be mixed, for example, when a coupling agent is chemically adsorbed to the surface of the thermally conductive filler. The amount of iron contained in the composition is preferably 80 ppm by mass or less, 50 ppm by mass or less, or 30 ppm by mass or less, based on the total amount of nonvolatile content in the composition excluding the thermally conductive filler and the coupling agent chemically adsorbed to the surface of the thermally conductive filler. When the polymerizable component does not contain the compound represented by formula (2) or the compound represented by formula (3), the amount of iron contained in the composition is preferably 35 ppm by mass or less, 30 ppm by mass or less, or 25 ppm by mass or less, based on the total amount of nonvolatile content in the composition excluding the thermally conductive filler and the coupling agent chemically adsorbed to the surface of the thermally conductive filler. Note that "nonvolatile content" refers to components other than volatile substances such as solvents, and refers to components that remain without volatilizing when the composition is dried.

[0097] The amount of iron contained in the composition is measured by ICP-OES using, for example, an Agilent 5100 (Agilent Technologies, Inc.). Specifically, a methanol / hydrochloric acid mixed solution is prepared with a mixture ratio of methanol / hydrochloric acid / pure water = 50 / 29.7 / 20.3 (mass%). Next, 5 g of the composition and 5 g of the methanol / hydrochloric acid mixed solution are weighed into a screw tube and a magnetic stirrer is placed in the tube. The mixture is then heated and stirred in a water bath at 50°C for 1 hour to dissolve the iron contained in the composition. Approximately 3 ml of the supernatant liquid is then withdrawn with a syringe and filtered through a 0.2 μm filter. The iron content in the filtrate is then quantified by ICP-OES. The amount of iron contained in the cured product of the composition can also be measured using the same method as above. In the case of the cured product, the cured product can be ground into powder and then dissolved in a methanol / hydrochloric acid mixed solution.

[0098] [Method of producing the composition] The composition can be produced by a method for producing a composition, which includes, for example, a step of treating a thermally conductive filler with a coupling agent (filler treatment step), and a step of mixing the treated thermally conductive filler obtained by the filler treatment step with a polymerizable component containing the compound represented by formula (1) (mixing step). Another embodiment of the present invention is a method for producing such a composition.

[0099] In the filler treatment process, a coupling agent is chemically adsorbed onto the surface of the thermally conductive filler. Specifically, for example, first, a liquid (hydrolysis treatment liquid) is prepared by hydrolyzing the coupling agent, and the hydrolysis treatment liquid is added to the thermally conductive filler and stirred. After that, the thermally conductive filler is dried, and if necessary, pulverized and classified to obtain the treated thermally conductive filler. When two or more types of thermally conductive fillers are used together, the thermally conductive fillers are uniformly mixed before adding the hydrolysis treatment liquid. This process allows the coupling agent to be chemically adsorbed onto the surface of the thermally conductive filler.

[0100] As mentioned above, iron may be mixed in when the coupling agent is chemically adsorbed onto the surface of the thermally conductive filler, so it is preferable to adjust (reduce) the amount of iron contained in the composition in the filler treatment step. Specific examples of such measures include using a mixer capable of stirring at a low rotation speed (e.g., 150 rpm to 500 rpm) such as a planetary mixer, minimizing the mixing time (e.g., the mixing time after adding the hydrolysis treatment solution), and minimizing the amount of the hydrolysis treatment solution to reduce the amount of iron mixed in due to wear of the equipment; and coating equipment such as mixers and grinders with resin or the like to make it less likely for iron to be mixed in even if the equipment is worn.

[0101] The stirring time in the filler treatment step is preferably as short as possible within the range that allows uniform stirring. In particular, after adding the hydrolysis treatment liquid to the thermally conductive filler, the thermally conductive filler tends to adhere to the substrate, and the amount of iron mixed in due to wear of the substrate increases, so it is preferable to shorten the stirring time. The stirring time when mixing two or more types of thermally conductive fillers is preferably 7.5 to 20 minutes, more preferably 7.5 to 12.5 minutes. Furthermore, the stirring time after adding the hydrolysis treatment liquid to the thermally conductive filler is preferably 7.5 to 12.5 minutes.

[0102] The amount of hydrolysis solution used in the filler treatment step is preferably adjusted by balancing these two factors: if it is too small relative to the amount of thermally conductive filler, the hydrolysis solution will not spread evenly over the entire thermally conductive filler, and if it is too large relative to the amount of thermally conductive filler, lumps will easily form and the amount of iron mixed in due to wear of the equipment will increase. The amount of hydrolysis solution is preferably 0.4 to 0.8 parts by mass relative to 100 parts by mass of thermally conductive filler.

[0103] In the mixing step, the amount of the thermally conductive filler added after the treatment is adjusted so that the content of the thermally conductive filler in the composition is the same as the content range based on the total amount or volume of the composition described above. Also, the content of the compound represented by formula (1) in the polymerizable component may be the same as the content range of the compound represented by formula (1) based on the total content of the polymerizable components described above.

[0104] The polymerizable component may contain, in addition to the compound represented by formula (1), the compound represented by formula (2) described above, the compound represented by formula (3) described above, or the other polymerizable compounds described above. The contents of these components based on the total content of the polymerizable components may be as described above.

[0105] The mixing step may be a step of mixing the treated thermally conductive filler with a polymerizable component containing the compound represented by formula (1) and one or more additives selected from the group consisting of the above-mentioned polymerization initiator, plasticizer, antioxidant, and other additives. The amount of these components added may be the same as the content of these components based on the total amount of the composition described above, or may be the same as the content of these components based on the total content of the polymerizable components in the composition.

[0106] [Composition set] The above-described composition may be in the form of a multi-liquid composition (composition set). A composition set according to one embodiment includes a first liquid containing an oxidizing agent and a second liquid containing a reducing agent. At least one of the first liquid and the second liquid contains the compound represented by formula (1) described above. Furthermore, at least one of the first liquid and the second liquid contains the thermally conductive filler described above. As described above, a coupling agent is chemically adsorbed to the surface of the thermally conductive filler. By mixing the first liquid and the second liquid, the oxidizing agent and the reducing agent react to generate free radicals, which then cause polymerization of the polymerizable component containing the compound represented by formula (1). According to the composition set according to this embodiment, by mixing the first liquid and the second liquid, a cured product of the mixture of the first liquid and the second liquid is immediately obtained. In other words, according to the composition set, a cured product of the composition can be obtained at a rapid rate.

[0107] In the composition set, preferably, the first liquid contains an oxidizing agent, a compound represented by formula (1), and a thermally conductive filler, and the second liquid contains a reducing agent, a compound represented by formula (1), and a thermally conductive filler.

[0108] The content of the compound represented by formula (1) based on the total amount of the liquids constituting the composition set (for example, in the case of a two-part composition set, the total amount of the first and second liquids) may be the same as the range of the content of the compound represented by formula (1) based on the total amount of the compositions described above. The content of the thermally conductive filler contained in the composition set may be the same as the range of the content of the thermally conductive filler based on the total amount or volume of the compositions described above.

[0109] The oxidizing agent contained in the first liquid functions as a polymerization initiator (radical polymerization initiator). The oxidizing agent may be, for example, an organic peroxide or an azo compound. The organic peroxide may be, for example, a hydroperoxide, a peroxydicarbonate, a peroxyester, a peroxyketal, a dialkyl peroxide, or a diacyl peroxide. The azo compound may be, for example, AIBN (2,2'-azobisisobutyronitrile), V-65 (azobisdimethylvaleronitrile), or the like. The oxidizing agent may be used alone or in combination of two or more.

[0110] Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

[0111] Examples of peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, di(2-ethylhexylperoxy)dicarbonate, dimethoxybutyl peroxydicarbonate, and di(3-methyl-3-methoxybutylperoxy)dicarbonate.

[0112] Peroxyesters include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, and 1-cyclohexyl-1-methylethyl peroxy. 2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, 1,1-bis(t-butylperoxy)cyclohexane, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-hexylperoxybenzoate, t-butylperoxyacetate, and the like.

[0113] Examples of peroxyketals include 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, and 2,2-bis(t-butylperoxy)decane.

[0114] Examples of dialkyl peroxides include α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and t-butylcumyl peroxide.

[0115] Examples of diacyl peroxides include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoylperoxytoluene, and benzoyl peroxide.

[0116] From the viewpoint of storage stability, the oxidizing agent is preferably a peroxide, more preferably a hydroperoxide, and even more preferably cumene hydroperoxide.

[0117] The content of the oxidizing agent may be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more, and may be 10% by mass or less, 5% by mass or less, or 3% by mass or less, based on the total amount of the liquid constituting the composition set.

[0118] The reducing agent contained in the second liquid may be, for example, a tertiary amine, a thiourea derivative, a transition metal salt, etc. Examples of tertiary amines include triethylamine, tripropylamine, tributylamine, and N,N-dimethyl-p-toluidine. Examples of thiourea derivatives include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylenethiourea. Examples of transition metal salts include cobalt naphthenate, copper naphthenate, and vanadyl acetylacetonate. One reducing agent may be used alone, or two or more may be used in combination.

[0119] The reducing agent is preferably a thiourea derivative or a transition metal salt from the viewpoint of excellent curing speed. The thiourea derivative may be, for example, ethylenethiourea. From the same viewpoint, the transition metal salt is preferably vanadyl acetylacetonate.

[0120] The content of the reducing agent may be 0.05% by mass or more, 0.1% by mass or more, or 0.3% by mass or more, and may be 5% by mass or less, 3% by mass or less, or 1% by mass or less, based on the total amount of the liquid constituting the composition set.

[0121] The composition set may further contain the compound represented by formula (2), the compound represented by formula (3), other polymerizable compounds, and additives that can be used in the above-mentioned compositions. These components may be contained in one or both of the first liquid and the second liquid, or may be contained in a third liquid that is different from the first liquid and the second liquid. The content of these components based on the total amount of the liquids constituting the composition set may be the same as the content range of these components based on the total amount of the above-mentioned compositions.

[0122] From the viewpoint of further improving the heat resistance of the cured product, it is preferable that the amount of iron contained in the composition set is small. The amount of iron contained in the composition set may be the same as the range of the iron content based on the total content of the polymerizable components in the composition described above.

[0123] The above-described compositions and composition sets have low viscosity, and their cured products have thermal conductivity and high breaking strength. Therefore, they are suitable for use as thermally conductive materials (also known as heat dissipation materials) in electronic components such as power modules, CPUs, and ECUs, batteries, LED lighting, and LED backlights. Similarly, cured products of the above-described compositions and cured products of the mixtures of the composition sets have thermal conductivity and high breaking strength, making them suitable for the above-described applications. When the composition and composition set contain a compound represented by formula (2) and / or a compound represented by formula (3), their cured products have high heat resistance and are therefore particularly suitable for the above-described applications. Furthermore, when the iron content of the composition and composition set is low, their cured products have high heat resistance and are therefore particularly suitable for the above-described applications.

[0124] [Goods] Next, an article including a cured product of the above-described composition or composition set (hereinafter simply referred to as "cured product") will be described. The article according to one embodiment includes a heat source and a cured product in thermal contact with the heat source. Below, an electronic component will be described as a more specific example of the article. FIG. 1 is a schematic cross-sectional view showing one embodiment of an electronic component including the cured product. The electronic component 1A shown in FIG. 1 includes a semiconductor chip 21 as a heat source and a heat sink 22 as a heat dissipation section.

[0125] Electronic component 1A includes cured product 11 provided between semiconductor chip 21 and heat sink 22. Cured product 11 is a cured product of the above-described composition or a cured product of a mixture of the composition set.

[0126] Since the cured product 11 has thermal conductivity, the cured product 11 acts as a thermally conductive material (thermal interface material) in the electronic component 1A, and conducts heat from the semiconductor chip 21 to the heat sink 22. The heat is then dissipated from the heat sink 22 to the outside.

[0127] The cured product 11 has excellent heat resistance, and is therefore less susceptible to deterioration due to heat. Therefore, the heat generated from the semiconductor chip 21 can be effectively conducted to the heat sink 22.

[0128] The cured product 11 can also be obtained by placing a liquid composition (composition set) between the semiconductor chip 21 and the heat sink 22 and then curing it. This makes it possible to suppress the occurrence of voids due to dripping and pump-out phenomena, and as a result, it is possible to improve the adhesion of the cured product 11 (adhesion to the surfaces of the semiconductor chip 21 and the heat sink 22). The curing means and curing conditions for the composition can be adjusted depending on the composition of the composition or the type of polymerization initiator.

[0129] In the electronic component 1A described in FIG. 1, the cured material 11 is arranged so as to be in direct contact with the semiconductor chip 21 and the heat sink 22, but the cured material 11 only needs to be in thermal contact with the heat source, and in another embodiment, the cured material 11 may be arranged so as to be in contact with the heat source (semiconductor chip) via another member.

[0130] Fig. 2 is a schematic cross-sectional view showing another embodiment of an electronic component including a cured material. Electronic component 1B shown in Fig. 2 is a processor including a semiconductor chip 21 as a heat source arranged on one surface of a substrate 23 via an underfill 24, a heat sink 22 as a heat dissipation section, and a heat spreader 25 provided between the semiconductor chip 21 and the heat sink 22. A first cured material 11 is provided between the semiconductor chip 21 and the heat spreader 25 so as to be in contact with the semiconductor chip 21. A second cured material 11 is provided between the heat spreader 25 and the heat sink 22.

[0131] The substrate 23, underfill 24, and heat spreader 25 may be made of materials commonly used in the relevant technical field. For example, the substrate 23 may be a laminate substrate, the underfill 24 may be made of a resin such as an epoxy resin, and the heat spreader 25 may be a metal plate.

[0132] The first cured product 11 and the second cured product 11 are cured products of the above-mentioned curable compositions or cured products of a mixture of the above-mentioned curable composition set. The first cured product 11 is in direct contact with the semiconductor chip 21, which is a heat source, while the second cured product 11 is in thermal contact with the semiconductor chip 21, which is a heat source, via the first cured product 11 and the heat spreader 25.

[0133] The first cured product 11 and the second cured product 11 have thermal conductivity and therefore function as a thermally conductive material (thermal interface material) in the electronic component 1B. That is, the first cured product 11 promotes thermal conduction from the semiconductor chip 21 to the heat spreader 25. The second cured product 11 also promotes thermal conduction from the heat spreader 25 to the heat sink 22. Then, the heat is dissipated from the heat sink 22 to the outside.

[0134] The first cured product 11 and the second cured product 11 also have excellent heat resistance, which reduces thermal degradation of the first cured product 11 and the second cured product 11. Therefore, the heat generated from the semiconductor chip 21 can be more effectively conducted to the heat spreader 25, and further, the heat can be more effectively conducted to the heat sink 22.

[0135] The first cured product 11 and the second cured product 11 can also be obtained by disposing a liquid composition (composition set) between the semiconductor chip 21 and the heat spreader 25, or between the heat spreader 25 and the heat sink 22, and then curing the composition. Therefore, even in the electronic component 1B, it is possible to suppress the occurrence of voids due to dripping and pump-out of the composition (composition set), and as a result, it is possible to achieve excellent adhesion of the first cured product 11 and the second cured product 11 (adhesion to the surfaces of the semiconductor chip 21, the heat spreader 25, and / or the heat sink 22). [Example]

[0136] The present invention will be specifically described below based on examples, but the present invention is not limited to the following examples.

[0137] The following components were used in the examples and comparative examples. <Polymerizable component> (A-1) A compound represented by the following formula (1-5), synthesized by the procedure shown below (weight average molecular weight: 16,000, a mixture in which m in formula (1-5) is approximately 246±5 and n is an integer of approximately 105±5, viscosity at 25°C: 55 Pa s). [ka] In formula (1-5), -r- is a symbol representing random copolymerization.

[0138] (A-2) N-acryloylmorpholine represented by the following formula (2-2) ("ACMO" manufactured by KJ Chemicals Co., Ltd.) [ka]

[0139] (A-3) A compound represented by the following formula (3-3) ("RC200C" manufactured by Kaneka Corporation, weight average molecular weight: 18,000, R in formula (3-3) 31 and R 32 is a hydrogen atom or a methyl group, and R 34 is a compound having a polar group, viscosity at 23°C: 530 Pa·s, Tg: -39°C) [ka] (A-4) Isodecyl acrylate ("FA111A" manufactured by Hitachi Chemical Co., Ltd.) (A-5) 4-Hydroxybutyl acrylate (Osaka Organic Chemical Industry Co., Ltd.) (A-6) 2-Acryloyloxyethyl succinate ("NK Ester A-SA" manufactured by Shin-Nakamura Kogyo Co., Ltd.)

[0140] <Thermal conductive filler> The thermally conductive filler used was a mixture of the following (b-1) to (b-4) in a mass ratio of (b-1):(b-2):(b-3):(b-4) = 33:33:24:10 (referred to as thermally conductive filler (b)). (b-1) Alumina filler ("Alumina Beads CB-A30S" manufactured by Showa Denko K.K.) (b-2) Alumina filler (Sumitomo Chemical Co., Ltd. "Advanced Alumina AA-18") (b-3) Alumina filler (Sumitomo Chemical Co., Ltd. "Advanced Alumina AA-3") (b-4) Alumina filler (Sumitomo Chemical Co., Ltd. "Advanced Alumina AA-04")

[0141] <Coupling agent> (C-1) A silane coupling agent represented by the following formula (4-1) ("KBM-5803" manufactured by Shin-Etsu Chemical Co., Ltd.) [ka] (C-2) A silane coupling agent represented by the following formula (4-2) ("KBM3103C" manufactured by Shin-Etsu Chemical Co., Ltd.) [ka]

[0142] <Other ingredients> (D-1) Plasticizer ("Tackifier KE311" manufactured by Arakawa Chemical Industries, Ltd.) (D-2) Plasticizer (Arakawa Chemical Industries, Ltd. "Tackifier PE590") (E) Phenolic antioxidant (BASF Japan Ltd. "Irganox 1010") (F) Thermal polymerization initiator (di-t-butyl peroxide)

[0143] [Synthesis of Compound Represented by Formula (1-5)] A 500 mL flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, outlet tube, and heating jacket was used as a reactor. 240 g of polyoxyethylene polyoxypropylene glycol (molecular weight 16,000) and 300 g of toluene were added to the reactor, and the mixture was stirred at 45°C and 250 rpm. Nitrogen was introduced at 100 mL / min and stirred for 30 minutes. The temperature was then lowered to 25°C. After the temperature drop was complete, 2.9 g of acryloyl chloride was added dropwise to the reactor and stirred for 30 minutes. 3.8 g of triethylamine was then added dropwise and stirred for 2 hours. The temperature was then raised to 45°C and the mixture was allowed to react for 2 hours. The reaction mixture was filtered, and the filtrate was desolvated to obtain a compound represented by formula (1-5).

[0144] [Preparation of Composition and Cured Product] <Comparative Examples 1 and 2> The thermally conductive filler (b) and the amount of coupling agent shown in Table 1 (parts by mass relative to 100 parts by mass of the thermally conductive filler) (total of 79% by volume (92.35% by mass)) were mixed with the components (total of 7.65% by mass) in the formulation shown in Table 1 to obtain compositions of Comparative Examples 1 and 2. Next, each composition was filled into a 10 cm × 10 cm × 0.2 mm mold (made of SUS plate), and after covering with a SUS plate, it was heated at 135°C for 15 minutes to cure, thereby obtaining a cured composition having a thickness of 0.2 mm.

[0145] <Examples 1 to 15> First, the thermally conductive filler (b) was surface-treated using the above-mentioned thermally conductive filler (b) and the type and amount (parts by mass per 100 parts by mass of the thermally conductive filler) of coupling agent shown in Tables 1 and 2. That is, in the examples, the coupling agent was not blended into the composition together with the polymerizable component, etc., but rather the coupling agent was chemically adsorbed onto the surface of the thermally conductive filler (b) before preparing the composition. Note that the "amount of coupling agent" and "amount of hydrolysis treatment solution" in Tables 1 and 2 represent the amount (parts by mass) per 100 parts by mass of the thermally conductive filler. Specifically, the thermally conductive filler (b) was placed in a 10-liter planetary mixer (with stainless steel inner walls and stirring blades) and stirred at 200 to 500 rpm for 10 minutes. Then, the hydrolysis solution of the coupling agent prepared by the method described below was added in the amount shown in Tables 1 and 2 (parts by mass per 100 parts by mass of the thermally conductive filler). The mixture was stirred at 200 to 500 rpm for the time shown in Tables 1 and 2 (the stirring time after adding the hydrolysis solution). The mixture was then transferred to a tray and dried in an oven at 120°C for 8 hours. The mixture was then crushed (see the "with or without crushing step" column in Tables 1 and 2) and classified to obtain a surface-treated thermally conductive filler (referred to as "thermally conductive filler (B)"). Note that the amount of iron contained in the resulting composition (based on the total nonvolatile content of the composition, excluding the thermally conductive filler and the coupling agent chemically adsorbed on the surface of the thermally conductive filler) varied depending on the amount of hydrolysis solution, the stirring time after adding the hydrolysis solution, and whether or not a crushing step was performed. A 0.1 mol / L mixture of aqueous acetic acid, methanol, and coupling agent (C-1) was mixed in a beaker in a mass ratio of 38 / 56 / 6 and stirred at 50°C for 1 hour. After cooling the resulting mixture, methanol was added in an amount to provide the hydrolysis treatment solution shown in Tables 1 and 2, and if coupling agent (C-2) was used, coupling agent (C-2) was also added. The mixture was stirred and mixed at 25°C for 10 minutes to prepare a hydrolysis treatment solution. The hydrolysis treatment solution of the coupling agent was added to the thermally conductive filler (b) within 30 minutes of preparation.

[0146] Next, 79% by volume (92.35% by mass) of the obtained thermally conductive filler (B) was mixed with each component (total 7.65% by mass) in the blending ratios shown in Tables 1 and 2 to obtain the compositions of Examples 1 to 15. Each of the obtained compositions was filled into a 10 cm × 10 cm × 0.2 mm mold (made of SUS plate), and after covering with a SUS plate, heated at 135°C for 15 minutes to cure, thereby obtaining a cured composition having a thickness of 0.2 mm.

[0147] [viscosity] The viscosity of each composition at 25° C. was measured using an E-type viscometer (PE-80L, manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS Z8803. Prior to the measurement, the viscometer was calibrated in accordance with JIS Z8809-JS14000.

[0148] [Measurement of breaking strength, tensile modulus and breaking elongation] The breaking strength, tensile modulus, and breaking elongation of the cured product were measured at 25°C using a tensile tester (Shimadzu Corporation, "Autograph EZ-TEST EZ-S") The measurements were performed on a cured product measuring 0.2 mm (thickness) × 5 mm (width) × 30 mm (length) at a chuck distance of 20 mm and a pulling speed of 5 mm / min, in accordance with JIS K7161.

[0149] [Heat resistance evaluation] The cured product obtained above was cut into 3 cm x 3 cm pieces, and the weight (initial weight) was measured. The cut pieces were then placed in a thermostatic bath at 175°C, removed after 177 hours, and re-measured (weight after 177 hours). The weight loss was calculated using the following formula: Weight loss (%) = (weight after 177 hours / initial weight) x 100

[0150] Tables 1 and 2 show the measurement results of the physical properties of the compositions of Comparative Examples 1 and 2 and Examples 1 to 15.

[0151] [Table 1]

[0152] [Table 2] [Explanation of symbols]

[0153] 1A, 1B...electronic component, 11...cured product of composition, 21...semiconductor chip (heat source), 22...heat sink, 23...substrate, 24...underfill, 25...heat spreader.

Claims

1. The composition contains a polymerizable component containing a compound represented by the following formula (1) and a thermally conductive filler, 【Chemistry 1】 [In formula (1), R １１ and R １２ each independently represents a hydrogen atom or a methyl group, R １３ represents a divalent group having a polyoxyalkylene chain. A composition in which a coupling agent is chemically adsorbed on the surface of the thermally conductive filler, the coupling agent includes a silane coupling agent having a (meth)acryloyl group, A composition wherein the polyoxyalkylene chain comprises an oxypropylene group.

2. A composition comprising a polymerizable component containing a compound represented by the following formula (1) and a thermally conductive filler: 【Chemistry 2】 [In formula (1), R 11 and R 12 each independently represent a hydrogen atom or a methyl group, and R 13 represents a divalent group having a polyoxyalkylene chain.] A composition in which a coupling agent is chemically adsorbed on the surface of the thermally conductive filler, the coupling agent includes a silane coupling agent having a (meth)acryloyl group, The composition, wherein the polymerizable component further contains a compound represented by the following formula (2): 【Transformation 3】 [In formula (2), R 21 and R 22 each independently represent a hydrogen atom or a monovalent organic group, and may be bonded to each other to form a ring. R 23 represents a hydrogen atom or a methyl group.]

3. A composition comprising a polymerizable component containing a compound represented by the following formula (1) and a thermally conductive filler: 【Chemistry 4】 [In formula (1), R 11 and R 12 each independently represent a hydrogen atom or a methyl group, and R 13 represents a divalent group having a polyoxyalkylene chain.] A composition in which a coupling agent is chemically adsorbed on the surface of the thermally conductive filler, the coupling agent includes a silane coupling agent having a (meth)acryloyl group, The composition, wherein the polymerizable component further contains a compound represented by the following formula (3): 【Transformation 5】 [In formula (3), R 31 and R 32 each independently represent a hydrogen atom or a methyl group, and R 33 represents a divalent group having a poly(meth)acrylate chain.]

4. 4. The composition of claim 2 or 3, wherein the polyoxyalkylene chain comprises an oxyethylene group.

5. 4. The composition of claim 2 or 3, wherein the polyoxyalkylene chain comprises an oxypropylene group.

6. The composition according to any one of claims 1 to 3, wherein the polyoxyalkylene chain is a copolymer chain containing an oxyethylene group and an oxypropylene group.

7. The composition according to claim 6 , wherein the copolymer chain is a random copolymer chain.

8. The composition according to claim 1 or 3, wherein the polymerizable component further contains a compound represented by the following formula (2): 【Transformation 6】 [In formula (2), R ２１ and R ２２ R each independently represents a hydrogen atom or a monovalent organic group, and may be bonded to each other to form a ring. ２３ represents a hydrogen atom or a methyl group.

9. The composition according to claim 1 or 2, wherein the polymerizable component further contains a compound represented by the following formula (3): 【Transformation 7】 [In formula (3), R ３１ and R ３２ each independently represents a hydrogen atom or a methyl group, R ３３ represents a divalent group having a poly(meth)acrylate chain.

10. The composition of any one of claims 1 to 9, wherein the thermally conductive filler comprises aluminum oxide.

11. The composition according to any one of claims 1 to 10, wherein the compound represented by formula (1) has a weight average molecular weight of 5,000 or more.

12. The composition according to any one of claims 1 to 11, wherein the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more.

13. The composition according to any one of claims 1 to 12, wherein the compound represented by formula (1) has a viscosity at 25°C of 1000 Pa·s or less.

14. The composition according to any one of claims 1 to 13, wherein the amount of iron contained in the composition is 80 ppm by mass or less based on the total amount of nonvolatile matters in the composition excluding the thermally conductive filler and the coupling agent.

15. treating the thermally conductive filler with a coupling agent; and mixing the treated thermally conductive filler with a polymerizable component containing a compound represented by the following formula (1): 【Transformation 8】 [In formula (1), R １１ and R １２ each independently represents a hydrogen atom or a methyl group, R １３ represents a divalent group having a polyoxyalkylene chain. the coupling agent includes a silane coupling agent having a (meth)acryloyl group, The method for producing a composition, wherein the polyoxyalkylene chain comprises an oxypropylene group.

16. A cured product of the composition according to any one of claims 1 to 14.

17. A heat source and and the cured product of claim 16 in thermal contact with the heat source.

18. A method of manufacturing a thermally conductive composite, comprising: treating a thermally conductive filler with a coupling agent; and mixing the treated thermally conductive filler with a polymerizable component containing a compound represented by the following formula (1): 【Chemistry 9】 [In formula (1), R 11 and R 12 each independently represent a hydrogen atom or a methyl group, and R 13 represents a divalent group having a polyoxyalkylene chain.] the coupling agent includes a silane coupling agent having a (meth)acryloyl group, The method for producing a composition, wherein the polymerizable component further contains a compound represented by the following formula (2): 【Chemistry 10】 [In formula (2), R 21 and R 22 each independently represent a hydrogen atom or a monovalent organic group, and may be bonded to each other to form a ring. R 23 represents a hydrogen atom or a methyl group.]

19. A method of manufacturing a thermally conductive composite material, comprising: treating a thermally conductive filler with a coupling agent; and mixing the treated thermally conductive filler with a polymerizable component containing a compound represented by the following formula (1): 【Chemistry 11】 [In formula (1), R 11 and R 12 each independently represent a hydrogen atom or a methyl group, and R 13 represents a divalent group having a polyoxyalkylene chain.] the coupling agent includes a silane coupling agent having a (meth)acryloyl group, The method for producing a composition, wherein the polymerizable component further contains a compound represented by the following formula (3): 【Chemistry 12】 [In formula (3), R 31 and R 32 each independently represent a hydrogen atom or a methyl group, and R 33 represents a divalent group having a poly(meth)acrylate chain.]

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