Curable compositions and articles

Abstract

This curable composition comprises a compound represented by formula (1) and a heat-conductive filler. [In formula (1), R11 and R12 each independently represent a hydrogen atom or methyl group, and R13 represents a divalent group having a polyoxyalkylene chain.]

Description

[Technical field]

[0001] The present invention relates to curable compositions and articles. [Background technology]

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

[0003] Many liquid materials are known as thermally conductive materials, and are also called heat dissipation grease or thermally conductive grease. For example, Patent Document 1 discloses a thermally conductive grease composition containing a liquid hydrocarbon oil and / or a fluorohydrocarbon oil and a predetermined amount of a thermally conductive inorganic filler. Patent Document 2 discloses a thermally conductive grease containing a specific phenyl ether-based base oil, a specific phenol-based antioxidant, and an inorganic powder filler. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 11-246885 [Patent Document 2] JP 2011-111517 A Summary of the Invention [Problem to be solved by the invention]

[0005] When liquid thermally conductive grease is used, dripping after application or a pump-out phenomenon in which the grease is pushed out from between the components due to deformation of the components to which the thermally conductive grease is applied can occur. Dripping or pump-out generates voids between the grease and the components, reducing the adhesion of the grease to the components and causing an increase in thermal resistance between the heat dissipating grease and the components. Dripping or pump-out can also cause other components to be contaminated by the grease, resulting in poor insulation.

[0006] In order to solve such problems, a thermally conductive material formed in a solid state such as a sheet may be used. By using a solid thermally conductive material, it is possible to suppress dripping or pump-out phenomena. On the other hand, in electronic components having a heat generating member and a heat dissipating member, repeated cooling and heating may cause deformation such as warping of the members. Therefore, a solid thermally conductive material is required to have excellent elongation so that it can follow the deformation of the members.

[0007] In one aspect, the present invention has an object to provide a curable composition that can give a cured product having excellent elongation. [Means for solving the problem]

[0008] As a result of intensive research, the present inventors have found that a cured product of a curable composition containing a specific compound having a polyoxyalkylene chain and two (meth)acryloyl groups has excellent elongation. In addition, they have found that this curable composition can be suitably used as a thermally conductive material by containing a thermally conductive filler, and have completed the present invention. In some aspects, the present invention provides the following [1] to

[11] .

[0009] [1] A curable composition comprising a compound represented by the following formula (1) and a thermally conductive filler: [ka] [In formula (1), R 11 and R 12each independently represents a hydrogen atom or a methyl group; R 13 represents a divalent group having a polyoxyalkylene chain. [2] The curable composition according to [1], wherein the polyoxyalkylene chain contains a structural unit represented by the following formula (2): [ka] [3] The curable composition according to [1], wherein the polyoxyalkylene chain contains a structural unit represented by the following formula (3): [ka] [4] The curable composition according to [1], wherein the polyoxyalkylene chain is a copolymer chain containing a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3): [ka] [ka] [5] The curable composition according to [4], wherein the copolymer chain is a random copolymer chain. [6] The curable composition according to any one of [1] to [5], wherein the compound represented by formula (1) has a weight-average molecular weight of 5,000 or more. [7] The curable composition according to any one of [1] to [6], wherein the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more. [8] The curable composition according to any one of [1] to [7], wherein the compound represented by formula (1) has a viscosity at 25°C of 1000 Pa s or less. [9] The curable composition according to any one of [1] to [8], further comprising an antioxidant.

[10] The curable composition according to [9], wherein the antioxidant is a phenolic antioxidant.

[11] An article comprising: a heat source; and a cured product of the curable composition according to any one of [1] to

[10] , which is provided in thermal contact with the heat source. Effect of the Invention

[0010] According to one aspect of the present invention, there is provided a curable composition capable of giving a cured product having excellent elongation. According to another aspect of the present invention, there is provided a curable composition capable of giving a cured product having excellent elongation and low elasticity. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic cross-sectional view showing one embodiment of an article comprising a cured product of a curable composition. [Diagram 2] FIG. 2 is a schematic cross-sectional view showing another embodiment of an article comprising a cured product of a curable composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings as appropriate. Note that the present invention is not limited to the following embodiment.

[0013] 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".

[0014] The weight average molecular weight (Mw) in this specification means a value measured by 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℃

[0015] [Curable composition] The curable composition according to one embodiment contains 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.

[0016] In one embodiment, R 11 and R 12 may be a hydrogen atom and the other a methyl group, and in another embodiment, R 11 and R 12 may both be hydrogen atoms, and in another embodiment, R 11 and R 12 may both be methyl groups.

[0017] In one embodiment, the polyoxyalkylene chain contains a structural unit represented by the following formula (2): This makes it possible to increase the strength of the cured product while suppressing an excessive increase in the viscosity of the curable composition. [ka]

[0018] 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.

[0019] In another embodiment, the polyoxyalkylene chain contains a structural unit represented by the following formula (3): This can facilitate handling of the curable composition. [ka]

[0020] 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.

[0021] In another embodiment, the polyoxyalkylene chain is preferably a copolymer chain containing the structural unit represented by formula (2) and the structural unit represented by formula (3) described above, from the viewpoint of easily achieving both the strength of the cured product of the compound represented by formula (1) and the handleability of the curable 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 handleability of the curable composition.

[0022] In each of the above-mentioned embodiments, the polyoxyalkylene chain may have, in addition to the structural unit represented by formula (2) and the structural unit represented by formula (3), 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.

[0023] R 13may be a divalent group having other organic groups in addition to the polyoxyalkylene chain. The other organic groups may be chain-like groups other than the polyoxyalkylene chain, such as a methylene chain (a chain having -CH2- as a structural unit), a polyester chain (a chain having -COO- in a structural unit), a polyurethane chain (a chain having -OCON- in a structural unit), etc.

[0024] 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 and 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.

[0025] Multiple R's 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 Each of the polyoxyalkylene chains represented by the formula (2) is preferably a copolymer chain containing an oxyethylene group (structural unit represented by the formula (2) above) and an oxypropylene group (structural unit represented by the formula (3) above).

[0026] In each of the above-mentioned 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, so that the elongation of the cured product is more excellent and the strength of the cured product can be increased. 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).

[0027] 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.

[0028] From the viewpoint of a cured product having lower elasticity and excellent elongation, the weight average molecular weight of the compound represented by formula (1) is preferably 5000 or more, 6000 or more, 7000 or more, 8000 or more, 9000 or more, 10000 or more, 11000 or more, 12000 or more, 13000 or more, 14000 or more, or 15000 or more. From the viewpoint of making it easier to adjust the viscosity of the curable composition, the weight average molecular weight of the compound represented by formula (1) is preferably 100000 or less, 80000 or less, 60000 or less, 34000 or less, 31000 or less, or 28000 or less.

[0029] 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 to a coating surface and from the viewpoint of enhancing 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.

[0030] The compound represented by formula (1) may be solid at 25°C. In this case, from the viewpoint of further improving the handleability of the curable composition, the compound represented by formula (1) is preferably liquid at 50°C. In addition, in this case, from the viewpoint of further improving the handleability of the curable 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.

[0031] The viscosity refers to a value measured based on JIS Z 8803, specifically, a value measured using an E-type viscometer (e.g., PE-80L, manufactured by Toki Sangyo Co., Ltd.). The viscometer can be calibrated based on JIS Z 8809-JS14000. The viscosity of the compound represented by formula (1) can be adjusted by adjusting the weight-average molecular weight of the compound.

[0032] The content of the compound represented by formula (1) is preferably 1 mass% or more, more preferably 1.5 mass% or more, and even more preferably 2 mass% or more, based on the total amount of the curable composition, from the viewpoint of a cured product having lower elasticity and excellent elongation. The content of the compound represented by formula (1) may be 20 mass% or less, 17 mass% or less, or 15 mass% or less, based on the total amount of the curable composition.

[0033] The curable composition may contain other polymerizable compounds (details will be described later) other than the compound represented by formula (1). In this case, the content of the compound represented by formula (1) is preferably 10 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, or 35 parts by mass or more relative to 100 parts by mass of the total of the compound represented by formula (1) and the other polymerizable compounds (hereinafter referred to as "total content of polymerizable components"), from the viewpoint of a cured product having lower elasticity and excellent elongation. The content of the compound represented by formula (1) may be 80 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less relative to 100 parts by mass of the total content of polymerizable components.

[0034] The curable composition contains a thermally conductive filler. This improves the thermal conductivity of the curable composition and its cured product, making the curable composition suitable for use as a thermally conductive material, heat dissipation material, etc. A thermally conductive filler is a filler with a thermal conductivity of 10 W / m·K or more.

[0035] The thermally conductive filler may be insulating or conductive, and is preferably an insulating filler. Materials constituting the insulating thermally conductive filler include aluminum oxide, 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 the conductive thermally conductive filler include aluminum, silver, copper, etc. The shape of the thermally conductive filler may be spherical or polyhedral.

[0036] From the viewpoint of enabling a thin application of the cured product of the curable 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 measuring device (e.g., SALD-2300 (manufactured by Shimadzu Corporation)).

[0037] From the viewpoint of increasing the thermal conductivity of the curable composition, the content of the thermally conductive filler is preferably 60 mass % or more, more preferably 70 mass % or more, and even more preferably 80 mass % or more, and may be 97 mass % or less, 95 mass % or less, or 93 mass % or less, based on the total amount of the curable composition.

[0038] From the viewpoint of enhancing the thermal conductivity of the curable composition, the content of the thermally conductive filler is preferably 70 vol. % or more, more preferably 75 vol. % or more, and even more preferably 80 vol. % or more, and may be 90 vol. % or less, 88 vol. % or less, or 85 vol. % or less, based on the total volume of the curable composition.

[0039] The curable composition may further contain another polymerizable compound copolymerizable with the compound represented by the above formula (1) for the purpose of adjusting the physical properties of the curable composition or the like.

[0040] The other polymerizable compound may be, for example, a compound having one (meth)acryloyl group. 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, the viscosity of the curable composition can be adjusted by the curable composition containing an alkyl (meth)acrylate. In addition, the curable composition contains a compound having, in addition to a (meth)acryloyl group, a hydroxyl group, a carboxyl group, an amino group, or an epoxy group, and the adhesion of the curable composition and its cured product to a member can be further improved.

[0041] 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.

[0042] Examples of the alkyl (meth)acrylate 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 of such alkyl (meth)acrylates 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.

[0043] 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 isoundecyl (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.

[0044] 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.

[0045] An example of the compound having a (meth)acryloyl group and an aromatic hydrocarbon group is benzyl (meth)acrylate.

[0046] 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.

[0047] An example of a compound having a (meth)acryloyl group and a group containing a heterocycle is tetrahydrofurfuryl (meth)acrylate.

[0048] An example of a compound having a (meth)acryloyl group and an alkoxy group is 2-methoxyethyl acrylate.

[0049] An example of a compound having a (meth)acryloyl group and a phenoxy group is phenoxyethyl (meth)acrylate.

[0050] 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.

[0051] Examples of the compound having a (meth)acryloyl group and a group containing a siloxane bond include silicone (meth)acrylate.

[0052] 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 fluorine atoms 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.

[0053] 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.

[0054] 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.).

[0055] Examples of the compound 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.

[0056] 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.

[0057] The content of the other polymerizable compounds is preferably 1 mass % or more, more preferably 3 mass % or more, and even more preferably 5 mass % or more, based on the total amount of the curable composition, from the viewpoint of making it easier to adjust the viscosity of the curable composition or from the viewpoint of further increasing the adhesion of the curable composition, and may be 20 mass % or less, 15 mass % or less, or 10 mass % or less.

[0058] From the viewpoint of making it easier to adjust the viscosity of the curable composition or from the viewpoint of further increasing the adhesion of the curable composition, the content of the other polymerizable compounds is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and even more preferably 50 parts by mass or more, relative to 100 parts by mass in total of the content of the polymerizable components, and may be 90 parts by mass or less, 80 parts by mass or less, or 70 parts by mass or less.

[0059] The curable 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.

[0060] When the curable composition contains a thermal polymerization initiator, a cured product of the curable composition can be obtained by applying heat to the curable composition. In this case, the curable composition may be a curable composition that is cured by heating at preferably 105°C or higher, more preferably 110°C or higher, and even more preferably 115°C or higher, and may be a curable 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 curable composition may be appropriately selected according to the composition of the curable composition so that the curable composition is suitably cured.

[0061] 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. The thermal polymerization initiator may be used alone or in combination of two or more of these.

[0062] When the curable composition contains a photopolymerization initiator, for example, the curable composition can be irradiated with light (e.g., light having at least a part of the wavelength of 200 to 400 nm (ultraviolet light)) to obtain a cured product of the curable composition. The light irradiation conditions may be appropriately set depending on the type of the photopolymerization initiator.

[0063] 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, an acylphosphine oxide-based photopolymerization initiator, or the like.

[0064] 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., BASF's "Irgacure 651"), anisole methyl ether, etc. Acetophenone-based photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone (e.g., BASF's "Irgacure 184"), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (e.g., BASF's "Irgacure 2959"), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (e.g., BASF's "Irgacure 1173"), methoxyacetophenone, etc.

[0065] Examples of the α-ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropan-1-one, etc. Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride, etc. Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime, etc.

[0066] Benzoin-based photopolymerization initiators include benzoin, etc. Benzil-based photopolymerization initiators include benzil, etc. Benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinyl benzophenone, α-hydroxycyclohexyl phenyl ketone, etc. Ketal-based photopolymerization initiators include benzil dimethyl ketal, etc. Thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, etc.

[0067] 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. ethylphosphine oxide, bis(2,6-dimethoxybenzoyl)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.

[0068] The above-mentioned photopolymerization initiators may be used alone or in combination of two or more.

[0069] The content of the polymerization initiator is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and even more preferably 0.05 parts by mass or more, based on 100 parts by mass of the total content of the polymerizable components, from the viewpoint of favorable progress of polymerization. The content of the polymerization initiator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, based on 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 curable composition is in a suitable range and suppressing decomposition products.

[0070] The curable composition may further contain a plasticizer. By containing a plasticizer in the curable composition, the adhesion of the curable 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 resin, and terpene resin, and polyalkylene glycol.

[0071] 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.

[0072] The curable composition may further contain an antioxidant from the viewpoint of improving the thermal reliability of the cured product of the curable 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.

[0073] The phenol-based 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 a t-butyl group is bonded to one or both of the ortho positions relative to a hydroxyl group in a phenol ring. The phenol-based 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.

[0074] 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 curable composition.

[0075] The curable composition may further contain other additives as necessary. Examples of other additives include surface treatment agents (e.g., silane coupling agents), dispersants, curing accelerators, colorants, crystal nucleating agents, heat stabilizers, foaming agents, flame retardants, vibration dampers, dehydrating agents, and flame retardant assistants (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 curable composition.

[0076] The curable composition is preferably liquid at 25°C. This allows it to be suitably applied to the surface of an object such as a heat source member or a cooling member, and also increases adhesion to the applied surface. The curable composition may be solid at 25°C, and in this case, it is preferable that it becomes liquid by heating (for example, at 50°C or higher). The curable composition may be applied in a liquid state and then cured, which can prevent the curable composition from causing dripping and pump-out phenomena.

[0077] [Curable composition set] According to one embodiment of the present invention, a multi-liquid type curable composition set can be provided. The curable composition set according to one embodiment is a curable composition set including 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 a compound represented by the above formula (1). At least one of the first liquid and the second liquid contains the above thermally conductive filler. By mixing the first liquid and the second liquid, the oxidizing agent and the reducing agent react to generate free radicals, and polymerization of the polymerizable component such as the compound represented by formula (1) proceeds. According to the curable 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 can be obtained immediately. That is, according to the curable composition set, a cured product of the curable composition can be obtained at a high speed.

[0078] In the curable 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.

[0079] The content of the compound represented by formula (1) based on the total amount of liquid constituting the curable composition set (for example, the total amount of the first liquid and the second liquid in the case of a two-liquid type curable composition set) may be the same as the content range of the compound represented by formula (1) based on the total amount of the curable composition described above. The same applies to the content of the thermally conductive filler contained in the curable composition set.

[0080] The oxidizing agent contained in the first liquid serves 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, a diacyl peroxide, or the like. 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 kinds.

[0081] Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

[0082] 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.

[0083] 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. t-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, and t-butylperoxyacetate.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] From the viewpoint of storage stability, the oxidizing agent is preferably a peroxide, more preferably a hydroperoxide, and further preferably cumene hydroperoxide.

[0088] The content of the oxidizing agent may be 0.1 mass % or more, 0.5 mass % or more, or 1 mass % or more, and may be 10 mass % or less, 5 mass % or less, or 3 mass % or less, based on the total amount of the liquid constituting the curable composition set.

[0089] 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 the tertiary amine include triethylamine, tripropylamine, tributylamine, and N,N-dimethyl-p-toluidine. Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylenethiourea. Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, and vanadyl acetylacetonate. The reducing agent may be used alone or in combination of two or more.

[0090] 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.

[0091] The content of the reducing agent may be 0.05 mass % or more, 0.1 mass % or more, or 0.3 mass % or more, and may be 5 mass % or less, 3 mass % or less, or 1 mass % or less, based on the total amount of the liquid constituting the curable composition set.

[0092] The curable composition set may further contain other polymerizable compounds and additives that can be used in the curable composition described above. 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 different from the first liquid and the second liquid. The content of these components based on the total amount of the liquids constituting the curable composition set may be the same as the content range of these components based on the total amount of the curable composition described above.

[0093] [Cured materials and thermally conductive materials] The cured product of the above-mentioned curable composition or the cured product of the mixture of the curable composition set has thermal conductivity and excellent elongation (sometimes also has low elasticity), and is therefore suitable for use as a thermally conductive material (also called a heat dissipation material) in electronic components such as power modules, CPUs, ECUs, batteries, LED lighting, LED backlights, etc. That is, one embodiment of the present invention provides a thermally conductive material containing the compound represented by the above-mentioned formula (1) and a thermally conductive filler.

[0094] [Goods] Next, an article including the cured product of the above-mentioned curable composition will be described using an electronic component as an example. Fig. 1 is a schematic cross-sectional view showing one embodiment of an electronic component including the cured product of the curable composition. 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 part.

[0095] The electronic component 1A includes a cured product 11 of the above-described curable composition provided between a semiconductor chip 21 and a heat sink 22. The cured product 11 may be a cured product of a mixture of the above-described curable composition set.

[0096] 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. Then, the heat is dissipated from the heat sink 22 to the outside.

[0097] By using the above-mentioned curable composition, the cured product 11 has excellent elongation (and low elasticity in some cases). Therefore, it has high ability to follow deformation of the electronic component 1A caused by heat or the like. Therefore, heat generated from the semiconductor chip 21 can be effectively conducted to the heat sink 22. In addition, since the cured product 11 is a cured product of the above-mentioned curable composition, it also has excellent strength (for example, breaking strength).

[0098] The cured product 11 can also be obtained by disposing a liquid curable composition 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, the adhesion of the cured product 11 (to the surfaces of the semiconductor chip 21 and the heat sink 22) can be made excellent. The curing means and curing conditions of the curable composition may be adjusted depending on the composition of the curable composition or the type of polymerization initiator.

[0099] 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 it is sufficient that the cured material 11 is in thermal contact with the heat source, and in another embodiment, it may be arranged so as to be in contact with the heat source (semiconductor chip) via another member.

[0100] Fig. 2 is a schematic cross-sectional view showing another embodiment of an electronic component including a cured product of a curable composition. The electronic component 1B shown in Fig. 1 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 product 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 product 11 is provided between the heat spreader 25 and the heat sink 22.

[0101] The substrate 23, the underfill 24, and the heat spreader 25 may be made of materials commonly used in the art. 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.

[0102] The first cured product 11 and the second cured product 11 are cured products of the above-mentioned curable compositions or cured products of the 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.

[0103] The first cured product 11 and the second cured product 11 have thermal conductivity, and therefore act 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. Also, the second cured product 11 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.

[0104] The first cured product 11 and the second cured product 11 also have excellent elongation (and low elasticity in some cases) by using the above-mentioned curable composition. Therefore, the first cured product 11 and the second cured product 11 have high conformability to deformation of the electronic component 1B caused by heat. 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. In addition, the first cured product 11 and the second cured product 11 are cured products of the above-mentioned curable composition, and therefore have excellent strength (for example, breaking strength).

[0105] The first cured product 11 and the second cured product 11 can also be obtained by disposing a liquid curable composition 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, in the electronic component 1B, it is possible to suppress the occurrence of voids due to the dripping and pump-out phenomenon of the curable composition, and as a result, it is possible to make the 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) excellent. EXAMPLES

[0106] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0107] In the examples, the following components were used: (A-1) A compound represented by the following formula (1-5) synthesized by the procedure shown below (weight average molecular weight: 8000, a mixture in which m in formula (1-5) is an integer of approximately 180 ± 3, viscosity at 50°C: 10 Pa s (solid at 25°C)) [ka] (A-2) A compound represented by formula (1-6) synthesized by the procedure shown below (weight average molecular weight: 9400, a mixture in which m1+m2 in formula (1-6) is approximately 160±5 (m1 and m2 are each an integer of 2 or more), and n is an integer of approximately 38±5, viscosity at 50°C: 8 Pa s (solid at 25°C)) [ka] (A-3) A compound represented by formula (1-7) synthesized by the procedure shown below (weight average molecular weight: 15,000, a mixture in which m1+m2 in formula (1-7) is approximately 252±5, and n1+n2 is approximately 63±5 integers (wherein m1, m2, n1, and n2 are each independently integers of 2 or greater, m1+n1≧100, m2+n2≧100), viscosity at 25°C: 50 Pa s) [ka] In formula (1-7), -r- is a symbol representing random copolymerization. (A-4) A compound represented by formula (1-8) synthesized by the procedure shown below (weight average molecular weight: 16,000, a mixture in which m in formula (1-8) is approximately 246±5 and n is an integer of approximately 105±5, viscosity at 25°C: 55 Pa s) [ka] In formula (1-8), -r- is a symbol representing random copolymerization. (a) Bifunctional acrylate having no polyoxyalkylene chain (acrylic diacrylate, manufactured by Kaneka Corporation)

[0108] (B-1) 2-Ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) (B-2) 2-Acryloyloxyethyl succinate ("NK Ester A-SA" manufactured by Shin-Nakamura Kogyo Co., Ltd.) (B-3) 4-Hydroxybutyl acrylate (Osaka Organic Chemical Industry Co., Ltd.) (B-4) Isodecyl acrylate ("FA111A" manufactured by Hitachi Chemical Co., Ltd.)

[0109] (C-1) Plasticizer ("Tackifier KE359" manufactured by Arakawa Chemical Industries, Ltd.) (C-2) Plasticizer (glycol having a polyoxyalkylene chain, "Newpol 75H-90000" manufactured by Sanyo Chemical Industries, Ltd.) (C-3) Plasticizer ("Tackifier KE311" manufactured by Arakawa Chemical Industries, Ltd.) (C-4) Plasticizer (Arakawa Chemical Industries, Ltd. "Tackifier PE590")

[0110] (D-1) Phenol-based antioxidant (ADEKA Corporation "ADEKA STAB AO-80") (D-2) Phenol-based antioxidant (ADEKA Corporation "ADEKA STAB AO-60") (E) Thermal polymerization initiator (di-t-butyl peroxide)

[0111] (F-1) Alumina filler (Sumitomo Chemical Co., Ltd. "Advanced Alumina AA-18") (F-2) Alumina filler (Sumitomo Chemical Co., Ltd. "Advanced Alumina AA-3") (F-3) Alumina filler (Sumitomo Chemical Co., Ltd. "Advanced Alumina AA-04") (F-4) Alumina filler ("Alumina Beads CB-A30S" manufactured by Showa Denko Co., Ltd.) (F-5) Aluminum filler ("Toyal Tech Filler TFH-A10P" manufactured by Toyo Aluminum Co., Ltd.) (F-6) Aluminum filler ("Toyal Tech Filler TFH-A05P" manufactured by Toyo Aluminum Co., Ltd.) (G) Silane coupling agent ("KBM-5803" manufactured by Shin-Etsu Chemical Co., Ltd.) (H) Dispersant (BYK-Chemie "DISPERBYK-111")

[0112] [Synthesis of compound represented by formula (1-5)] A 500mL flask consisting of a stirrer, a thermometer, a nitrogen gas inlet tube, an exhaust tube and a heating jacket was used as a reactor, and 120g of polyethylene glycol #6000 and 300g of toluene were added to the reactor, and the mixture was stirred at 45°C and 250 revolutions per minute, and nitrogen was passed at 100mL / min, and stirred for 30 minutes. The temperature was then lowered to 25°C, and after the temperature drop was completed, 2.9g of acryloyl chloride was dropped into the reactor and stirred for 30 minutes. Then, 3.8g of triethylamine was dropped and stirred for 2 hours. The temperature was then raised to 45°C, and the mixture was reacted for 2 hours. The reaction liquid was filtered, and the filtrate was desolvated to obtain a compound represented by formula (1-5).

[0113] [Synthesis of compounds represented by formulas (1-6) to (1-8)] In the synthesis method of the compound represented by formula (1-5), except that polyethylene glycol #6000 was changed to polyoxyethylene polyoxypropylene glycol (141 g of "Newpol PE78" manufactured by Sanyo Chemical Industries, Ltd.), a compound represented by formula (1-6) was obtained by the same method. In addition, in the synthesis method of the compound represented by formula (1-5), except that polyethylene glycol #6000 was changed to a glycol having a polyoxyalkylene chain (225 g of "Newpol 75H-90000" manufactured by Sanyo Chemical Industries, Ltd.), a compound represented by formula (1-7) was obtained by the same method. In addition, in the synthesis method of the compound represented by formula (1-5), except that polyethylene glycol #6000 was changed to 240 g of polyoxyethylene polyoxypropylene glycol (molecular weight 16000), a compound represented by formula (1-8) was obtained by the same method.

[0114] [Preparation of Curable Composition and Cured Product] Curable compositions were obtained by mixing the components in the compounding ratios shown in Table 1. Next, the curable compositions were filled into a 10 cm x 10 cm x 0.2 mm mold (made of SUS plate), covered with a SUS plate, and then heated at 135°C for 15 minutes to be cured, thereby obtaining cured products of the curable compositions according to Examples 1 to 19 and Comparative Example 1, each having a thickness of 0.2 mm.

[0115] [Measurement of thermal conductivity] The prepared cured product was cut into a square of 10 mm × 10 mm × 0.2 mm, blackened with graphite spray, and then the thermal diffusivity was measured at 25 ° C. by the xenon flash method ("LFA447 nanoflash" manufactured by NETZSCH-Geratebau GmbH, Selb / Bayern). The thermal conductivity in the thickness direction of the cured product was calculated based on the product of this value, the density measured by the Archimedes method, and the specific heat at 25 ° C. measured by a differential scanning calorimeter ("DSC250" manufactured by TA Instruments) according to the following formula. Thermal conductivity λ(W / (m·K))=α×ρ×Cp α: Thermal diffusivity (m 2 / s) ρ: Density (kg / cm 3 ) Cp: ​​Specific heat (capacity) (kJ / (kg K))

[0116] [Measurement of breaking elongation, tensile modulus, and breaking strength] The cured product was measured for breaking elongation, tensile modulus, and breaking strength 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 (film thickness) x 5 mm (width) x 30 mm (length) at a chuck distance of 20 mm and a pulling speed of 5 mm / min, based on JIS K7161.

[0117] For the cured products of Examples 1 to 19 and Comparative Example 1, the physical properties were measured and the results are shown in Table 1.

[0118] [Table 1]

[0119] [Table 2] [Explanation of symbols]

[0120] Reference Signs List 1A, 1B...electronic components, 11...cured product of curable composition, 21...semiconductor chip (heat source), 22...heat sink, 23...substrate, 24...underfill, 25...heat spreader.

Claims

1. A curable composition 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. The polyoxyalkylene chain is a copolymer chain containing a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3), 【Chemistry 2】 【Chemistry 3】 a content of the compound represented by formula (1) being 1 mass% or more and 20 mass% or less, and a content of the thermally conductive filler being 60 mass% or more and 97 mass% or less, based on the total amount of the curable composition.

2. The curable composition according to claim 1 , wherein the copolymer chain is a random copolymer chain.

3. The curable composition according to claim 1 or 2, wherein the compound represented by formula (1) has a weight average molecular weight of 5,000 or more.

4. The curable composition according to any one of claims 1 to 3, wherein the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more.

5. The curable composition according to any one of claims 1 to 4, wherein the compound represented by formula (1) has a viscosity at 25°C of 1000 Pa·s or less.

6. The curable composition according to any one of claims 1 to 5, further comprising an antioxidant.

7. The curable composition of claim 6 , wherein the antioxidant is a phenolic antioxidant.

8. A heat source; An article comprising: a cured product of the curable composition according to any one of claims 1 to 7, the cured product being in thermal contact with the heat source.

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