Methods for producing cured product and semiconductor, and composition

Abstract

This method for producing a cured product of a composition includes heating a composition, which contains a curable component and a thermally conductive filler, at a temperature T1. The temperature T1 and a peak top temperature Tp on a DSC curve for the composition, which is determined by carrying out differential scanning calorimetric measurements from 25°C to 200°C at a temperature increase rate of 10ºC / min, satisfy the relationship of formula (A).　Formula (A): 10ºC≤T1-Tp≤40ºC

Description

Method for producing cured product and semiconductor device, and composition

[0001] The present disclosure relates to a method for producing a cured product and a semiconductor device, and a composition.

[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 for efficiently dissipating the generated heat is required. Thermal interface materials (TIMs), also known as heat dissipation materials, are materials 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 a cooling component or the like via the TIM, making it easier for the heat to be dissipated from the heat dissipation component.

[0003] The use of a composition containing a curable component and a thermally conductive filler as a thermally conductive material has been investigated. For example, Patent Document 1 discloses a thermally conductive silicone composition containing a silicone component and a polyhedral filler.

[0004] International Publication No. 2021 / 044867

[0005] One aspect of the present disclosure aims to provide a method for producing a cured product with excellent thermal conductivity and a semiconductor device with excellent heat dissipation efficiency using a composition containing a curable component and a thermally conductive filler, and a composition capable of forming a cured product with excellent thermal conductivity and a semiconductor device with excellent heat dissipation efficiency.

[0006] The present inventors have discovered that a method comprising heating a composition containing a curable component and a thermally conductive filler, in which the difference between the temperature T1 at which the composition is heated and the peak-top temperature Tp of the DSC curve of the composition is within a specific numerical range, can produce a cured product with excellent thermal conductivity and a semiconductor device with excellent heat dissipation efficiency. In some aspects, the present disclosure provides the following [1] to

[19] . [1] A method for producing a cured product of a composition containing a curable component and a thermally conductive filler, comprising heating the composition at a temperature T1, wherein the temperature T1 and the peak-top temperature Tp of the DSC curve of the composition obtained by differential scanning calorimetry in which the composition is heated from 25°C to 200°C at a heating rate of 10°C / min satisfy the relationship represented by the following formula (A): 10°C≦T1−Tp≦40°C (A) [2] A method for manufacturing a semiconductor device, comprising heating a composition containing a curable component and a thermally conductive filler, the composition being disposed between an electronic component and a heat dissipation member, at temperature T1, wherein the temperature T1 and the peak-top temperature Tp of a DSC curve of the composition obtained by differential scanning calorimetry in which the composition is heated from 25°C to 200°C at a heating rate of 10°C / min satisfy the following formula (A): 10°C≦T1−Tp≦40°C (A) [3] The manufacturing method according to [1] or [2], wherein the curable component contains a compound having an ethylenically unsaturated group. [4] The manufacturing method according to [3], wherein the compound having an ethylenically unsaturated group contains a compound having two or more ethylenically unsaturated groups. [5] The manufacturing method according to [3] or [4], wherein the compound having an ethylenically unsaturated group is a compound having a (meth)acryloyl group. [6] The manufacturing method according to [4] or [5], wherein the compound having two or more ethylenically unsaturated groups further has a poly(meth)acrylate chain. [7] The manufacturing method according to any one of [1] to [6], wherein the thermally conductive filler is a metal filler. [8] The manufacturing method according to [7], wherein the metal filler is a silver filler.

[0007] [9] A composition comprising a curable component and a thermally conductive filler, the composition being used by being heated at a temperature T1, wherein the temperature T1 and a peak-top temperature Tp of a DSC curve of the composition obtained by differential scanning calorimetry in which the composition is heated from 25°C to 200°C at a heating rate of 10°C / min satisfy the following formula (A): 10°C≦T1−Tp≦40°C (A)

[10] The composition according to [9], the composition being used by being heated at the temperature T1 in a state where the composition is disposed between an electronic component and a heat dissipation member.

[11] The composition according to [9] or

[10] , the curable component comprising a compound having an ethylenically unsaturated group.

[12] The composition according to

[11] , the compound having an ethylenically unsaturated group comprising a compound having two or more ethylenically unsaturated groups.

[13] The composition according to

[11] or

[12] , the compound having an ethylenically unsaturated group is a compound having a (meth)acryloyl group.

[14] The composition according to

[12] or

[13] , wherein the compound having two or more ethylenically unsaturated groups further has a poly(meth)acrylate chain.

[15] The composition according to any one of [9] to

[14] , wherein the thermally conductive filler is a metal filler.

[16] The composition according to

[15] , wherein the metal filler is a silver filler.

[17] A cured product of the composition according to any one of [9] to

[16] .

[18] A heat dissipation material comprising the cured product according to

[17] .

[19] A semiconductor device comprising the heat dissipation material according to

[18] .

[0008] One aspect of the present disclosure provides a method for producing a cured product with excellent thermal conductivity and a semiconductor device with excellent heat dissipation efficiency using a composition containing a curable component and a thermally conductive filler, and a composition capable of forming a cured product with excellent thermal conductivity and a semiconductor device with excellent heat dissipation efficiency.

[0009] 1A and 1B are schematic cross-sectional views showing an embodiment of a method for manufacturing a semiconductor device, and 1C are schematic cross-sectional views showing another embodiment of a method for manufacturing a semiconductor device.

[0010] Hereinafter, embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

[0011] 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".

[0012] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and ratio of weight average molecular weight to number average molecular weight (Mw / Mn) refer to values ​​measured by gel permeation chromatography (GPC) under the following conditions and determined using polystyrene as a standard substance: Measuring instrument: HLC-8320GPC (product name, manufactured by Tosoh Corporation); Analytical column: TSKgel SuperMultipore HZ-H (three 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°C.

[0013] One embodiment of the present disclosure is a method for producing a cured product of a composition, the method comprising heating a composition containing a curable component and a thermally conductive filler at a temperature T1, wherein the temperature T1 and the peak-top temperature Tp of the DSC curve of the composition obtained by differential scanning calorimetry in which the composition is heated from 25°C to 200°C at a heating rate of 10°C / min satisfy the relationship represented by the following formula (A): 10°C≦T1−Tp≦40°C (A)

[0014] In the above-described production method, the difference between T1 and Tp is within a specific numerical range, so that the resulting cured product has excellent thermal conductivity.

[0015] The composition includes a curable component. The curable component refers to a component that can undergo a polymerization reaction, crosslinking, or the like by heating or the like to form a cured product. Examples of the curable component include resins that have curability, such as epoxy resins, phenolic resins, silicone resins, melamine resins, urea resins, acrylic resins, and unsaturated polyester resins.

[0016] The curable component may include a compound having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, a (meth)acryloyl group, and a maleimide group. The ethylenically unsaturated group may be, for example, a (meth)acryloyl group. Examples of the compound having an ethylenically unsaturated group include a compound having two or more ethylenically unsaturated groups and a compound having one ethylenically unsaturated group.

[0017] The compound having two or more ethylenically unsaturated groups may have two or three or more ethylenically unsaturated groups. The compound having two or more ethylenically unsaturated groups may be, for example, a compound having two or more (meth)acryloyl groups. The compound may have only one of an acryloyl group and a methacryloyl group, or may have both.

[0018] The compound having two or more ethylenically unsaturated groups may further have a polymer chain. The compound having two or more ethylenically unsaturated groups may be, for example, a compound having ethylenically unsaturated groups at both ends of the polymer chain, or may be a compound having (meth)acryloyl groups at both ends of the polymer chain. The two (meth)acryloyl groups present at both ends may each independently be an acryloyl group or a methacryloyl group.

[0019] The polymer chain may be, for example, a poly(meth)acrylate chain, and the compound having two or more ethylenically unsaturated groups may be, for example, a (meth)acrylic polymer having (meth)acryloyl groups at both ends of the poly(meth)acrylate chain.

[0020] The poly(meth)acrylate chain contains a (meth)acrylic acid ester ((meth)acrylate) as a monomer unit. The (meth)acrylate as a monomer unit may have, for example, a hydrocarbon group, an organic group having an oxygen atom, an organic group having a nitrogen atom, or the like. The poly(meth)acrylate chain may have a side chain bonded to the (meth)acrylate as a monomer unit, and the structure of the side chain is not particularly limited.

[0021] In a (meth)acrylate having a hydrocarbon group, the hydrocarbon group may be linear or may have a ring (e.g., an aromatic ring). Examples of the hydrocarbon group include an alkyl group, an aryl group (e.g., a phenyl group, a toluyl group), and an aralkyl group (e.g., a benzyl group). The number of carbon atoms in the hydrocarbon group may be, for example, 1 or more and 18 or less. The (meth)acrylate having a hydrocarbon group may be an alkyl(meth)acrylate, an aryl(meth)acrylate, an aralkyl(meth)acrylate, or the like. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, and octadecyl (meth)acrylate. Examples of aryl (meth)acrylates include phenyl (meth)acrylate. Examples of aralkyl (meth)acrylates include benzyl (meth)acrylate.

[0022] In a (meth)acrylate having an organic group having an oxygen atom, the organic group having an oxygen atom may be, for example, a group having an alkoxy group, a group having a hydroxy group, a group having a carboxy group, a group having a glycidyl group, etc. Examples of a (meth)acrylate having an organic group having an oxygen atom include 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, carboxy (meth)acrylate, and glycidyl (meth)acrylate.

[0023] In the (meth)acrylate having an organic group having a nitrogen atom, the organic group having a nitrogen atom may be, for example, a group having an amino group, a group having a nitrile group, etc. Examples of the (meth)acrylate having an organic group having a nitrogen atom include 2-aminoethyl (meth)acrylate and nitrile (meth)acrylate.

[0024] From the viewpoint of providing a cured product with lower elasticity and excellent elongation, the Mw of the compound having two or more ethylenically unsaturated groups (a compound having ethylenically unsaturated groups at both ends of the polymer chain) 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, 13,000 or more, 15,000 or more, 19,000 or more, 21,000 or more, 23,000 or more, or 25,000 or more. From the viewpoint of making it easier to adjust the viscosity of the composition, the Mw of the compound having two or more ethylenically unsaturated groups (a compound having ethylenically unsaturated groups at both ends of the polymer chain) is preferably 150,000 or less, 120,000 or less, 100,000 or less, 80,000 or less, 60,000 or less, or 40,000 or less.

[0025] The compound having two or more ethylenically unsaturated groups may be liquid at 23°C. The viscosity of the compound having two or more ethylenically unsaturated groups at 23°C may be 1000 Pa·s or less, 900 Pa·s or less, or 800 Pa·s or less, from the viewpoint of making the composition easier to apply to a surface to be coated and further enhancing the adhesion of the cured product to a surface to be coated. The viscosity of the compound having two or more ethylenically unsaturated groups at 23°C may be 1 Pa·s or more, 50 Pa·s or more, 100 Pa·s or more, 200 Pa·s or more, 300 Pa·s or more, 400 Pa·s or more, or 500 Pa·s or more, from the viewpoint of making the composition easier to apply to a surface to be coated and providing a cured product with better elongation.

[0026] In this specification, viscosity refers to a value measured in accordance with JIS Z8803, and specifically refers to a value measured using an E-type viscometer (for example, TV100-E manufactured by Toki Sangyo Co., Ltd.). The viscometer can be calibrated in accordance with JIS Z8809-JS14000.

[0027] The compound having two or more ethylenically unsaturated groups may have a glass transition temperature (Tg). From the viewpoint of providing a cured product with lower elasticity and excellent elongation, the glass transition temperature (Tg) of the compound having two or more ethylenically unsaturated groups may be 0°C or lower, -10°C or lower, -20°C or lower, -30°C or lower, or -40°C or lower. The Tg of the compound having two or more ethylenically unsaturated groups may be -70°C or higher, -60°C or higher, or -55°C or higher. In this specification, Tg means a value measured by differential scanning calorimetry.

[0028] From the viewpoint of providing a cured product with better heat resistance, the content of the compound having two or more ethylenically unsaturated groups may be 0.5 mass% or more, 1 mass% or more, or 3 mass% or more, and may be 15 mass% or less, 10 mass% or less, or 8 mass% or less, based on the total mass of the composition.

[0029] From the viewpoint of providing a cured product with better heat resistance, the content of the compound having two or more ethylenically unsaturated groups is preferably 10 parts by mass or more, 20 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 amount of the curable components, and may be, for example, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less.

[0030] The compound having one ethylenically unsaturated group may be copolymerizable with the compound having two or more ethylenically unsaturated groups. The compound having one ethylenically unsaturated group may be, for example, a compound having one (meth)acryloyl group. By including a compound having one (meth)acryloyl group in the composition, the physical properties of the cured product, such as thermal conductivity, can be more easily adjusted. The compound having one (meth)acryloyl group may be a compound having, in addition to one (meth)acryloyl group, a hydrocarbon group, a group containing a polyoxyalkylene chain, a group containing a heterocycle, an alkoxy group, a phenoxy group, a group containing a siloxane bond, a halogeno group, a hydroxy group, a carboxy group, an amino group, or an epoxy group. The hydrocarbon group may be linear or branched, and may have a ring (aromatic or non-aromatic ring). The hydrocarbon group may be a chain or cyclic aliphatic hydrocarbon group, or may be an aromatic hydrocarbon group. An example of a chain aliphatic hydrocarbon group is an alkyl group. Examples of cyclic aliphatic hydrocarbon groups include cycloalkyl groups, and examples of aromatic hydrocarbon groups include phenyl groups.

[0031] The compound having a (meth)acryloyl group and an alkyl group may be an alkyl(meth)acrylate. The alkyl group in the alkyl(meth)acrylate (the alkyl group portion other than the (meth)acryloyl group) may be linear or branched. The number of carbon atoms in the alkyl group may be 1 or more, 3 or more, 5 or more, or 6 or more, and may be 30 or less, 25 or less, 20 or less, 15 or less, or 13 or less. The number of carbon atoms in the alkyl group may be, for example, 1 to 30, 3 to 20, or 5 to 15.

[0032] Examples of alkyl(meth)acrylates having a linear alkyl group include alkyl(meth)acrylates having a linear alkyl group with 1 to 6 carbon atoms, such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, and n-hexyl(meth)acrylate; and alkyl(meth)acrylates having a linear alkyl group with 7 to 11 carbon atoms, such as n-heptyl(meth)acrylate, octyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, and undecyl(meth)acrylate. and alkyl(meth)acrylates having a linear alkyl group having 12 to 30 carbon atoms, such as dodecyl(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.

[0033] Examples of alkyl(meth)acrylates having a branched alkyl group include alkyl(meth)acrylates having a branched alkyl group with 1 to 6 carbon atoms, such as s-butyl(meth)acrylate, t-butyl(meth)acrylate, isobutyl(meth)acrylate, isopentyl(meth)acrylate, and isoamyl(meth)acrylate; and alkyl(meth)acrylates having a branched alkyl group with 7 to 11 carbon atoms, such as isooctyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isononyl(meth)acrylate, and isodecyl(meth)acrylate. (meth)acrylate, and alkyl (meth)acrylates having a branched alkyl group having 12 to 30 carbon atoms, such as isomyristyl (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.

[0034] Examples of the compound having a (meth)acryloyl group and a cyclic aliphatic hydrocarbon group (such as a cycloalkyl group) include cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, terpene (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate.

[0035] Examples of the compound having a (meth)acryloyl group and an aromatic hydrocarbon group include benzyl (meth)acrylate.

[0036] 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.

[0037] Examples of compounds having a (meth)acryloyl group and a group containing a heterocycle include N-acryloylmorpholine (ACMO) and tetrahydrofurfuryl (meth)acrylate.

[0038] An example of a compound having a (meth)acryloyl group and an alkoxy group is 2-methoxyethyl acrylate.

[0039] An example of a compound having a (meth)acryloyl group and a phenoxy group is phenoxyethyl (meth)acrylate.

[0040] Examples of compounds having a (meth)acryloyl group and a group containing a siloxane bond include silicone (meth)acrylates.

[0041] Examples of the compound having a (meth)acryloyl group and a halogeno group include trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 1,1,1,3,3,3-hexafluoro-2-propyl (meth)acrylate, perfluoroethylmethyl (meth)acrylate, perfluoropropylmethyl (meth)acrylate, perfluorobutylmethyl (meth)acrylate, perfluoropentylmethyl (meth)acrylate, perfluorohexylmethyl (meth)acrylate, perfluoroheptylmethyl (meth)acrylate, perfluorooctylmethyl (meth)acrylate, perfluorononylmethyl (meth)acrylate, perfluorodecylmethyl (meth)acrylate, perfluoroundecylmethyl (meth)acrylate, perfluorododecylmethyl (meth)acrylate, perfluoro Examples of (meth)acrylates having a fluoro group include orotridecylmethyl (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.

[0042] Examples of the compound having a (meth)acryloyl group and a hydroxy 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.

[0043] Examples of the compound having a (meth)acryloyl group and a carboxy 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.).

[0044] 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.

[0045] 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.

[0046] The compound having one (meth)acryloyl group may be a (meth)acrylic polymer having one (meth)acryloyl group at one end of a poly(meth)acrylate chain, such as "MM110C" manufactured by Kaneka Corporation.

[0047] The composition may contain one or more of the above compounds having one ethylenically unsaturated group.

[0048] The content of the compound having one ethylenically unsaturated group may be 1 mass% or more, 2 mass% or more, 3 mass% or more, 4 mass% or more, or 5 mass% or more, and may be 15 mass% or less, 13 mass% or less, 11 mass% or less, or 9 mass% or less, based on the total mass of the composition.

[0049] The content of the compound having one ethylenically unsaturated group may be 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, or 45 parts by mass or more, and may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less, relative to 100 parts by mass of the total amount of the curable components.

[0050] The composition may contain a curing agent. The curing agent may be a thermal curing agent. The thermal curing agent may be a compound that generates radicals by heat. By adding the curing agent and adjusting the type and amount thereof, the peak top temperature Tp of the DSC curve of the composition can be adjusted.

[0051] Examples of compounds that generate radicals when heated include azo compounds and organic peroxides. Examples of azo compounds include azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, and azodibenzoyl. Examples of organic peroxides include benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, di-t-butylperoxyhexahydroterephthalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, 1,1-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, and t-butylperoxybenzoate. As the curing agent, these may be used alone or in combination of two or more. From the viewpoint of providing a cured product with even better thermal conductivity, the curing agent may be a compound having a peroxy ester structure, such as 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexyl monocarbonate, or t-butylperoxybenzoate.

[0052] The one-minute half-life temperature of the curing agent may be 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, 150°C or higher, 155°C or higher, or 160°C or higher. The one-minute half-life temperature of the curing agent may be 200°C or lower, 195°C or lower, 190°C or lower, 185°C or lower, 180°C or lower, 175°C or lower, 170°C or lower, or 165°C or lower. The one-minute half-life temperature of the curing agent means a set temperature at which it takes one minute for the curing agent in benzene to decompose and the concentration to be reduced to half when the sample is dissolved in benzene to a concentration of 0.10 mol / L, sealed in a nitrogen-purged glass tube, and placed at a certain set temperature.

[0053] The one-hour half-life temperature of the curing agent may be 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, 95°C or higher, 100°C or higher, 105°C or higher, 110°C or higher, or 115°C or higher. The one-hour half-life temperature of the curing agent may be 150°C or lower, 140°C or lower, 130°C or lower, 125°C or lower, or 120°C or lower. The one-hour half-life temperature of the curing agent means a set temperature at which it takes one hour for the curing agent in benzene to decompose and the concentration to be reduced by half when a sample obtained by dissolving the curing agent in benzene to a concentration of 0.10 mol / L is sealed in a nitrogen-purged glass tube and placed at a certain set temperature.

[0054] The content of the curing agent may be 0.01 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, or 0.5 parts by mass or more, relative to 100 parts by mass of the total amount of the curable components, from the viewpoint of allowing the molecular weight of the polymer in the cured product of the composition to fall within a suitable range, and from the viewpoint of suppressing decomposition products, the content of the curing agent 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 amount of the polymerizable components.

[0055] The composition includes a thermally conductive filler. The thermally conductive filler refers to a filler having a thermal conductivity of 5 W / (m·K) or more. From the viewpoint of achieving superior thermal conductivity in a cured product, the thermal conductivity of the thermally conductive filler may be 10 W / (m·K) or more, 20 W / (m·K) or more, 30 W / (m·K) or more, 40 W / (m·K) or more, 50 W / (m·K) or more, 100 W / (m·K) or more, 150 W / (m·K) or more, 200 W / (m·K) or more, 250 W / (m·K) or more, 300 W / (m·K) or more, 350 W / (m·K) or more, or 400 W / (m·K) or more.

[0056] The thermally conductive filler may be a metal filler or a non-metal filler. The metal constituting the metal filler may be, for example, silver, gold, copper, aluminum, etc. From the viewpoint of providing a cured product with superior thermal conductivity, the metal filler is preferably a silver filler. The metal content in the metal filler may be 90 mass% or more, 95 mass% or more, 98 mass% or more, or 99 mass% or more based on the total mass of the metal filler. The metal filler may be a filler consisting essentially of metal (a filler in which substantially 100 mass% of the filler is metal, or a filler consisting only of metal and unavoidable impurities).

[0057] Examples of constituent materials of the non-metallic filler include aluminum oxide, aluminum hydroxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, silicon carbide, aluminum fluoride, calcium fluoride, and zinc oxide.

[0058] The thermally conductive filler may have a flaky, spherical, polyhedral, blocky, dendritic, plate-like, or other shape. From the viewpoint of achieving superior thermal conductivity in the cured product, the thermally conductive filler preferably has a flaky shape. Two or more types of thermally conductive fillers may be used as the thermally conductive filler. For example, two or more types of thermally conductive fillers having different shapes may be used.

[0059] From the viewpoint of providing a cured product with superior thermal conductivity, the average particle size of the thermally conductive filler is preferably 1.0 μm or more, 3.0 μm or more, or 5.0 μm or more, and 16.0 μm or less, 14.0 μm or less, 12.0 μm or less, or 10.0 μm or less. The average particle size of the thermally conductive filler can be measured using a laser diffraction particle size distribution measuring device (laser diffraction method).

[0060] The BET specific surface area of ​​the thermally conductive filler is 0.08 m ２ / g or more, or 0.1m ２ / g or more, and ２ / g or less, 0.8m ２ / g or less, or 0.5m ２ / g or less.

[0061] The content of the thermally conductive filler may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 83% by mass or more, based on the total mass of the composition, from the viewpoint of providing a cured product with superior thermal conductivity. The content of the thermally conductive filler may be 98% by mass or less, 95% by mass or less, 90% by mass or less, or 87% by mass or less, based on the total mass of the composition, from the viewpoint of further improving the adhesiveness of the cured product.

[0062] The content of the thermally conductive filler may be 10% by volume or more, 20% by volume or more, 30% by volume or more, or 33% by volume or more, based on the total volume of the composition, from the viewpoint of providing a cured product with superior thermal conductivity. The content of the thermally conductive filler may be 90% by volume or less, 70% by volume or less, 50% by volume or less, or 40% by volume or less, based on the total volume of the composition, from the viewpoint of further improving the adhesiveness of the cured product.

[0063] The composition may contain a polymer in addition to the compound having an ethylenically unsaturated group described above. Examples of such polymers include polymers containing a compound having one (meth)acryloyl group as a monomer unit. Examples of compounds having one (meth)acryloyl group include compounds having, in addition to one (meth)acryloyl group, a hydrocarbon group, a group containing a polyoxyalkylene chain, a group containing a heterocycle, an alkoxy group, a phenoxy group, a group containing a siloxane bond, a halogeno group, a hydroxy group, a carboxy group, an amino group, or an epoxy group. Details of these compounds may be as described above for the compound having one (meth)acryloyl group as a compound having one ethylenically unsaturated group.

[0064] A polymer containing a compound having one (meth)acryloyl group as a monomer unit may contain, for example, an alkyl(meth)acrylate as a monomer unit. In the alkyl(meth)acrylate, the number of carbon atoms in the alkyl group may be 1 or more, 2 or more, or 3 or more, and may be 18 or less, 15 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 5 or less. The alkyl group may be linear or branched.

[0065] In the polymer containing a compound having one (meth)acryloyl group as a monomer unit, the alkyl (meth)acrylate as a monomer unit preferably includes at least one selected from the group consisting of ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and isodecyl (meth)acrylate. In the polymer containing a compound having one (meth)acryloyl group as a monomer unit, the alkyl (meth)acrylate as a monomer unit particularly preferably includes butyl acrylate.

[0066] The Tg of the alkyl(meth)acrylate homopolymer may be 100° C. or less, 50° C. or less, 30° C. or less, 10° C. or less, 0° C. or less, −10° C. or less, −20° C. or less, −30° C. or less, or −40° C. or less. The Tg of the alkyl(meth)acrylate homopolymer may be, for example, −100° C. or more, or −80° C. or more. When a polymer containing a compound having one (meth)acryloyl group as a monomer unit contains two or more alkyl(meth)acrylates, the Tg of the alkyl(meth)acrylate homopolymer means a value calculated based on the FOX formula.

[0067] The content of alkyl (meth)acrylate in a polymer containing a compound having one (meth)acryloyl group as a monomer unit may be 30% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 85% by mass or more, and may be 98% by mass or less, 95% by mass or less, 90% by mass or less, or 88% by mass or less, based on the total mass of the monomer units contained in the polymer.

[0068] A polymer containing a compound having one (meth)acryloyl group as a monomer unit may contain a hydroxyalkyl (meth)acrylate as a monomer unit. In the hydroxyalkyl (meth)acrylate, the number of carbon atoms in the hydroxyalkyl group may be 1 or more or 2 or more, and may be 18 or less, 15 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 5 or less. In the hydroxyalkyl group, the hydroxy group may be bonded to a primary carbon of the alkyl group or may be bonded to a secondary carbon of the alkyl group.

[0069] In the polymer containing a compound having one (meth)acryloyl group as a monomer unit, the hydroxyalkyl (meth)acrylate as a monomer unit preferably includes at least one selected from the group consisting of hydroxybutyl acrylate, hydroxypropyl acrylate, and hydroxyethyl acrylate. In the polymer containing a compound having one (meth)acryloyl group as a monomer unit, the hydroxyalkyl (meth)acrylate as a monomer unit particularly preferably includes hydroxyethyl acrylate.

[0070] The content of hydroxyalkyl (meth)acrylate in a polymer containing a compound having one (meth)acryloyl group as a monomer unit may be 1 mass% or more, 5 mass% or more, 7 mass% or more, or 10 mass% or more, and may be 40 mass% or less, 30 mass% or less, 20 mass% or less, or 17 mass% or less, based on the total mass of monomer units contained in the polymer.

[0071] The polymer containing a compound having one (meth)acryloyl group as a monomer unit may be a homopolymer or a copolymer. The copolymer may be a random copolymer, an alternating copolymer, a graft copolymer, or a block copolymer. The polymer containing a compound having one (meth)acryloyl group as a monomer unit may be, for example, a copolymer containing an alkyl (meth)acrylate and a hydroxyalkyl (meth)acrylate as monomer units, or may be a random copolymer containing an alkyl (meth)acrylate and a hydroxyalkyl (meth)acrylate as monomer units.

[0072] The mass ratio of alkyl (meth)acrylate to hydroxyalkyl (meth)acrylate as monomer units in a polymer containing a compound having one (meth)acryloyl group as a monomer unit (alkyl (meth)acrylate / hydroxyalkyl (meth)acrylate) may be 50 / 50 or more, 60 / 40 or more, 70 / 30 or more, 80 / 20 or more, or 85 / 15 or more, and may be 99 / 1 or less, 98 / 2 or less, 97 / 3 or less, or 95 / 5 or less.

[0073] A polymer containing a compound having one (meth)acryloyl group as a monomer unit may or may not contain other monomer units as monomer units other than alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate. The content of other monomer units in a polymer containing a compound having one (meth)acryloyl group as a monomer unit may be 0.1% by mass or more, and may be 20% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less, based on the total mass of the monomer units contained in the polymer.

[0074] The Mw of a polymer containing a compound having one (meth)acryloyl group as a monomer unit may be 100,000 or more, 150,000 or more, 200,000 or more, or 250,000 or more, and may be 1,000,000 or less, 800,000 or less, 600,000 or less, 500,000 or less, or 400,000 or less.

[0075] The Mw / Mn of a polymer containing a compound having one (meth)acryloyl group as a monomer unit may be 1.0 or more, or 1.1 or more, and may be 2.5 or less, 2.2 or less, 2.0 or less, or 1.8 or less.

[0076] The content of the polymer containing a compound having one (meth)acryloyl group as a monomer unit may be 0.5 mass% or more, 0.8 mass% or more, 1.0 mass% or more, or 1.3 mass% or more, based on the total mass of the composition, and may be 20 mass% or less, 10 mass% or less, 7 mass% or less, or 5 mass% or less.

[0077] The content of the polymer containing a compound having one (meth)acryloyl group as a monomer unit may be 1 part by mass or more, 3 parts by mass or more, 7 parts by mass or more, or 10 parts by mass or more, and may be 30 parts by mass or less, 25 parts by mass or less, or 20 parts by mass or less, relative to 100 parts by mass of the total amount of the curable components.

[0078] The composition may further contain a thiol compound. When the composition contains a thiol compound, the heat resistance and elongation at break of the cured product can be further improved, and the tensile modulus of elasticity can be reduced. Furthermore, when the composition contains a silane compound together with the thiol compound, the adhesiveness of the cured product can be further improved. The thiol compound is a compound having one or more thiol groups. The thiol compound is preferably a polyfunctional thiol compound having two or more thiol groups. The number of thiol groups in the thiol compound may be 5 or less, or 4 or less.

[0079] The thiol group of the thiol compound may be a primary thiol group or a secondary thiol group. The primary thiol group is a thiol group bonded to a carbon atom bonded to one carbon atom and two hydrogen atoms, and the secondary thiol group is a thiol group bonded to a carbon atom bonded to two carbon atoms and one hydrogen atom. The thiol compound preferably has one or more secondary thiol groups, and more preferably has two or more secondary thiol groups.

[0080] The polyfunctional thiol compound may be, for example, a compound represented by the following formula (1), (2), or (3).

[0081] In formula (1), X １ , X ２ , X ３ and X ４ each independently represents a monovalent group having a thiol group or a hydrogen atom, and X １ , X ２ , X ３ and X ４ In formula (2), two or more of X are monovalent groups having a thiol group. ５ , X ６ and X ７ each independently represents a monovalent group having a thiol group or a hydrogen atom, and X ５ , X ６ and X ７ In formula (3), at least two of X are monovalent groups having a thiol group. ８ and X ９each independently represents a monovalent group having a thiol group, and R １ represents an alkylene group. １ may be an alkylene group having 2 to 10 carbon atoms. The monovalent group having a thiol group may be a group having a secondary thiol group represented by the following formula (11), or may be a group having a primary thiol group represented by the following formula (12) or (13). In formula (11), R ２ represents an alkylene group. ３ represents an alkylene group. ４ represents an alkylene group. ２ may be an alkylene group having 1 to 8 carbon atoms. ３ and R ４ may each independently be an alkylene group having 2 to 10 carbon atoms.

[0082] Examples of polyfunctional thiol compounds having a secondary thiol group include pentaerythritol tetrakis(3-mercaptobutyrate) represented by the following formula (1a) (e.g., Karenz MT PE1 manufactured by Resonac Corporation), 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinane-2,4,6-trione represented by the following formula (2a) (e.g., Karenz MT NR1 manufactured by Resonac Corporation), and 1,4-bis(3-mercaptobutyryloxy)butane represented by the following formula (3a) (e.g., Karenz MT BD1 manufactured by Resonac Corporation).

[0083] Other examples of polyfunctional thiol compounds having a secondary thiol group include ethylene glycol bis(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), pentaerythritol tri(3-mercaptobutyrate), trimethylolethane(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), and dipentaerythritol hexakis(3-mercaptobutyrate).

[0084] Other examples of polyfunctional thiol compounds having a primary thiol group include pentaerythritol trippropanethiol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 4,4'-thiobisbenzenethiol, 4,4'-biphenyldithiol, 1,5-dimercaptonaphthalene, 4,5 -bis(mercaptomethyl)-ortho-xylene, 1,3,5-benzenetrithiol, 1,4-butanediol bis(thioglycolate), dithioethythritol, 3,6-dioxa-1,8-octanedithiol, 3,7-dithia-1,9-nonanedithiol, bis(2-mercaptoethyl)sulfide, ethylene glycol bis(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(mercaptoacetate), butane Diol bis(3-mercaptopropionate), butanediol bis(3-mercaptoisobutyrate), pentaerythritol tri(mercaptoacetate), pentaerythritol tri(3-mercaptopropionate), pentaerythritol tri(3-mercaptoisobutyrate), pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptoisobutyrate), trimethylolethane(mercaptoacetate) ester), trimethylolethane (3-mercaptopropionate), trimethylolethane (3-mercaptoisobutyrate), trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptoisobutyrate), dipentaerythritol hexakis(mercaptoacetate), dipentaerythritol hexakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptoisobutyrate), 1,4-bis(3-mercaptopropyloxy)butane, tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, and tetraethylene glycol bis(3-mercaptopropionate).

[0085] The composition may contain one or more of the above thiol compounds.

[0086] The content of the thiol compound may be 0.01% by mass or more, or 0.02% by mass or more, and may be 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.3% by mass or less, or 0.1% by mass or less, based on the total mass of the composition.

[0087] The composition may further contain a silane compound. By containing the silane compound in the composition, the viscosity of the composition, as well as the thermal conductivity, elongation at break, and tensile modulus of the cured product can be further adjusted. The silane compound may be a silane coupling agent.

[0088] The silane compound may have an alkoxy group bonded to a silicon atom. The alkoxy group may be a methoxy group or an ethoxy group. The number of alkoxy groups bonded to a silicon atom may be 1 or more, 2 or more, or 3 or more, and may be 4 or less.

[0089] The silane compound may have a phenyl group, an epoxy group, a (meth)acryloyl group, an amino group, a ureido group, a mercapto group, an isocyanate group, etc. The silane compound preferably has an alkoxy group bonded to a silicon atom and at least one group selected from the group consisting of a phenyl group, an epoxy group, a (meth)acryloyl group, and an amino group, and more preferably has an alkoxy group bonded to a silicon atom and an epoxy group.

[0090] Examples of silane compounds having an alkoxy group and a phenyl group bonded to a silicon atom include phenyltrimethoxysilane and phenyltriethoxysilane. Examples of silane compounds having an alkoxy group and an epoxy group bonded to a silicon atom include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane.

[0091] Examples of silane compounds having an alkoxy group and a (meth)acryloyl group bonded to a silicon atom include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, and 3-(meth)acryloxypropylmethyldiethoxysilane.

[0092] In a silane compound having an alkoxy group and an amino group bonded to a silicon atom, the amino group is a primary amino group (—NH ２ ) or a secondary amino group (—NH—). Examples of silane compounds having an alkoxy group and an amino group bonded to a silicon atom include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.

[0093] The content of the silane compound may be 0.01% by mass or more, 0.02% by mass or more, or 0.05% by mass or more, and may be 5% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0.5% by mass or less, based on the total mass of the composition.

[0094] The composition may further contain an antioxidant from the viewpoint of improving the thermal reliability of the cured product. 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.

[0095] 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 on the phenol ring. The phenolic antioxidant may have one or more such hindered phenol rings, preferably two or more, more preferably three or more, and even more preferably four or more.

[0096] 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 5 mass % or less, 3 mass % or less, 1 mass % or less, or 0.7 mass % or less, based on the total mass of the composition.

[0097] The composition may contain a non-thermally conductive filler. The non-thermally conductive filler refers to a filler having a thermal conductivity of less than 5 W / (m·K). The non-thermally conductive filler may be composed of an organic material such as an acrylic resin, a styrene resin, a urethane resin, a polyimide resin, or an epoxy resin, or may be composed of an inorganic material such as silica (silicon dioxide) or glass. The non-thermally conductive filler may function as a gap filler (spacer). The average particle size of the non-thermally conductive filler may be, for example, 10 μm or more, or 20 μm or more, and may be 100 μm or less. The average particle size of the non-thermally conductive filler can be measured by laser diffraction.

[0098] The content of the non-thermally conductive filler may be 0.05% by mass or more, 0.1% by mass or more, or 0.15% by mass or more, and may be 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.5% by mass or less, or 0.3% by mass or less, based on the total mass of the composition.

[0099] The composition may further contain other additives as necessary. Examples of the other additives include thixotropic agents, surface treatment agents (excluding the above-mentioned silane compounds), 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 the other additives may be 0.1% by mass or more and 1% by mass or less, based on the total mass of the composition.

[0100] The composition is preferably liquid at 25°C. This allows it to be suitably applied to the surface of an adherend, such as a heat source component such as an electronic component or a heat dissipation component, and further enhances adhesion to the coated surface. The composition may be solid at 25°C, and in this case, it is preferable that it becomes liquid upon heating (for example, at 50°C or higher).

[0101] The composition may have a peak top temperature Tp of 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, 115°C or higher, 120°C or higher, 125°C or higher, or 130°C or higher in a DSC curve obtained by differential scanning calorimetry in which the composition is heated from 25°C to 200°C at a heating rate of 10°C / min.

[0102] The composition may have an onset temperature To of a DSC curve obtained by differential scanning calorimetry in which the composition is heated from 25°C to 200°C at a heating rate of 10°C / min. The onset temperature To of the DSC curve may be 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 105°C or higher, 110°C or higher, 115°C or higher, or 120°C or higher, and may be 160°C or lower, 150°C or lower, 140°C or lower, 135°C or lower, 130°C or lower, or 125°C or lower.

[0103] In this specification, the peak-top temperature and onset temperature of a DSC curve obtained by differential scanning calorimetry in which a composition is heated from 25°C to 200°C at a heating rate of 10°C / min are determined from a DSC curve in which heat flow is plotted on the vertical axis and temperature on the horizontal axis, obtained by measuring a composition weighed out so that the total amount of components in the composition excluding the thermally conductive filler is 0.8 to 1.2 mg and performing DSC measurement under conditions of a heating rate of 10°C / min and a measurement temperature range of 25°C to 200°C. The peak-top temperature Tp is the temperature at the apex of the exothermic peak detected in the DSC curve. Furthermore, the onset temperature To is the temperature at the intersection of a straight line extending the baseline on the low-temperature side of the exothermic peak detected in the DSC curve toward the high-temperature side and a tangent drawn to the curve on the low-temperature side of the exothermic peak at the point where the gradient is maximum.

[0104] In a production method according to one embodiment, as shown in formula (A), the difference (T1-Tp) between temperature T1 and temperature Tp is 10° C. or more and 40° C. or less. In a production method according to one embodiment, the difference may be 11° C.≦T1-Tp, 12° C.≦T1-Tp, or 13° C.≦T1-Tp, or may be T1-Tp≦35° C., T1-Tp≦30° C., T1-Tp≦25° C., or T1-Tp≦24° C.

[0105] Furthermore, the difference between temperature T1 and temperature To (T1-To) may be 0°C or higher, 5°C or higher, 10°C or higher, 15°C or higher, 20°C or higher, 23°C or higher, 25°C or higher, or 30°C or higher, or may be 80°C or lower, 60°C or lower, 50°C or lower, 45°C or lower, or 40°C or lower.

[0106] From the viewpoint of providing a cured product with superior thermal conductivity, the temperature T1 may be 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 105°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 135°C or higher, 140°C or higher, 150°C or higher, 155°C or higher, or 160°C or higher, and may be, for example, 225°C or lower, 220°C or lower, 210°C or lower, 200°C or lower, 195°C or lower, 190°C or lower, 185°C or lower, or 180°C or lower. The temperature T1 may be, for example, 160°C.

[0107] The heating time when heating at temperature T1 may be 1 minute or more, 3 minutes or more, 5 minutes or more, or 7 minutes or more, and may be 3 hours or less, 2 hours or less, 1 hour or less, 40 minutes or less, 30 minutes or less, or 20 minutes or less. The heating time when heating at temperature T1 may be, for example, 10 minutes.

[0108] When heating at temperature T1, pressure may be applied together with heating, or may not be applied. The pressure may be, for example, 0 MPa or more, 0.001 MPa or more, 0.005 MPa or more, or 0.01 MPa or more, and may be 0.5 MPa or less, 0.2 MPa or less, or 0.1 MPa or less.

[0109] A production method according to an embodiment may further include heating the composition at temperature T2 after heating at temperature T1. Temperature T2 may be higher or lower than temperature T1. By making temperature T2 higher than temperature T1, curing of the composition can be facilitated. Even when a production method according to an embodiment further includes heating the composition at temperature T2 after heating at temperature T1, keeping the difference between temperature T1 and temperature Tp within the above-mentioned range contributes to improving the thermal conductivity of the cured product.

[0110] The difference between temperature T2 and temperature T1 (T2-T1) may be 0°C or more, 10°C or more, or 15°C or more, and may be 140°C or less, 130°C or less, 120°C or less, 110°C or less, 100°C or less, 90°C or less, 80°C or less, 70°C or less, 60°C or less, 50°C or less, 40°C or less, 30°C or less, or 25°C or less.

[0111] From the viewpoint of providing a cured product with superior thermal conductivity, the temperature T2 may be 120°C or higher, 140°C or higher, 150°C or higher, 160°C or higher, 170°C or higher, or 175°C or higher, and may be, for example, 250°C or lower, 230°C or lower, 210°C or lower, 200°C or lower, 190°C or lower, or 185°C or lower. The temperature T2 may be, for example, 180°C.

[0112] The heating time when heating at temperature T2 may be 10 minutes or more, 30 minutes or more, or 40 minutes or more, and may be 5 hours or less, 3 hours or less, 2 hours or less, or 1 hour or less. The heating time when heating at temperature T2 may be, for example, 60 minutes.

[0113] A cured product of the composition can be obtained by the manufacturing method described above. One embodiment of the present disclosure can also be understood as a composition that includes a curable component and a thermally conductive filler, and is used by being heated at a temperature T1, wherein the temperature T1 and the peak top temperature Tp of the DSC curve of the composition obtained by differential scanning calorimetry in which the composition is heated from 25°C to 200°C at a heating rate of 10°C / min satisfy the relationship represented by the following formula (A). The specific embodiments described above can be applied as specific embodiments of the composition without any particular restrictions: 10°C≦T1−Tp≦40°C (A)

[0114] Furthermore, according to the above-described production method, a cured product with excellent thermal conductivity can be obtained. The cured product of the obtained composition has excellent thermal conductivity and is therefore suitable for applications such as heat dissipation materials, pressure sensitive adhesives, die attach materials, structural adhesives, battery binders, stress relief agents, sealants, coating agents, and paints, and is particularly suitable for use as a heat dissipation material. One embodiment of the present disclosure is a heat dissipation material including a cured product of the above-described composition. More specifically, the cured product can be particularly suitable for use in heat dissipation applications for semiconductor packages used in personal computers, servers, base stations, and the like. The above-described composition may be used to form a semiconductor device, or may be used to form a heat dissipation material in a semiconductor device.

[0115] One embodiment of the present disclosure is a method for manufacturing a semiconductor device, which includes heating a composition that includes a curable component and a thermally conductive filler and is disposed between an electronic component and a heat dissipation member at a temperature T1, wherein the temperature T1 and a peak-top temperature Tp of a DSC curve of the composition obtained by differential scanning calorimetry in which the composition is heated from 25°C to 200°C at a heating rate of 10°C / min satisfy the relationship represented by the following formula (A): 10°C≦T1−Tp≦40°C (A)

[0116] A method for manufacturing a semiconductor device will be described below based on a specific example. Fig. 1 is a schematic cross-sectional view showing an example of a method for manufacturing a semiconductor device. The example of the method for manufacturing a semiconductor device includes heating composition 3 at a temperature T1 in a composite 10 including a semiconductor chip 1 as an electronic component, a heat sink 2 as a heat dissipation member, and composition 3 disposed between the semiconductor chip 1 and the heat sink 2. Composition 3 includes a curable component and a thermally conductive filler.

[0117] The specific embodiments of the composition described above can be applied without any particular limitation to specific embodiments of the composition 3. The composite 10 shown in Fig. 1 can be produced, for example, by placing (e.g., applying) the composition 3 on either the semiconductor chip 1 or the heat sink 2, and then placing the other of the semiconductor chip 1 and the heat sink 2 on the composition 3.

[0118] In the composite 10 shown in Figure 1, the composition 3 is disposed so as to be in direct contact with the semiconductor chip 1 and the heat sink 2, but the composition need only be disposed so that its cured product is in thermal contact with the electronic component that serves as the heat source. For example, the composition may be disposed so as to be in contact with the electronic component (semiconductor chip) via another component. Furthermore, the composition does not necessarily need to be disposed so as to be in direct contact with a heat dissipation component such as a heat sink, but may be disposed so as to be in thermal contact with the heat dissipation component.

[0119] 2 is a schematic cross-sectional view showing another example of a method for manufacturing a semiconductor device. This example of the method for manufacturing a semiconductor device includes a composite 20 including a semiconductor chip 1 as an electronic component arranged on one surface of a substrate 4 via an underfill 5, a heat sink 2 as a heat dissipation member, a heat spreader 6 arranged between the semiconductor chip 1 and the heat sink 2, a first composition 3 arranged between the semiconductor chip 1 and the heat spreader 6, and a second composition 3 arranged between the heat spreader 6 and the heat sink 2, and the composite 20 includes the first composition 3 and the second composition 3 arranged at a temperature T1.

[0120] The substrate 4, the underfill 5, and the heat spreader 6 may be made of materials commonly used in the art. For example, the substrate 4 may be a laminate substrate, the underfill 5 may be made of a resin such as an epoxy resin, and the heat spreader 6 may be a metal plate.

[0121] The specific embodiments of the compositions described above can be applied without particular limitation as specific embodiments of the first composition 3 and the second composition 3. The composite 20 shown in Fig. 2 can be produced by disposing (e.g., applying) the first composition 3 on a semiconductor chip 1, disposing a heat spreader 6 on the first composition 3, disposing (e.g., applying) the second composition 3 on the heat spreader, and disposing a heat sink 2 on the second composition 3.

[0122] In these methods for manufacturing a semiconductor device, the difference between temperatures T1 and Tp (T1-Tp), the temperature T1, and the heating time when heating at temperature T1 may be as described above for the difference between temperatures T1 and Tp (T1-Tp), the temperature T1, and the heating time when heating at temperature T1, respectively, in the methods for manufacturing a cured product of the composition. In addition, in these methods for manufacturing a semiconductor device, pressure may be applied when heating at temperature T1, and the applied pressure may be as described above for the applied pressure in the methods for manufacturing a cured product of the composition.

[0123] The above-described method for manufacturing a semiconductor device may further include heating the composition (composition 3, or first composition 3 and second composition 3) at temperature T2 after heating at temperature T1. Temperature T2 and the heating time when heating at temperature T2 may be as described above for temperature T2 and the heating time when heating at temperature T2 in the method for manufacturing a cured product of the composition, respectively.

[0124] As described above, by heating composition 3, the first composition 3, and the second composition 3 at temperature T1, and if necessary, further heating at temperature T2, the curing of composition 3, the first composition 3, and the second composition 3 can be promoted.

[0125] 1 , a semiconductor device can be obtained that includes a semiconductor chip 1, a heat sink 2, and a cured product of the composition 3 provided between the semiconductor chip 1 and the heat sink 2. Because the cured product of the composition 3 has excellent thermal conductivity, in the obtained semiconductor device, the cured product of the composition 3 acts as a thermally conductive material (thermal interface material), conducting heat from the semiconductor chip 1 to the heat sink 2. The heat is then dissipated from the heat sink 2 to the outside.

[0126] Furthermore, by progressing the curing of the first composition 3 and the second composition 3 shown in Figure 2, a semiconductor device (processor) can be obtained that includes a semiconductor chip 1 arranged on one surface of a substrate 4 via an underfill 5, a heat sink 2, a heat spreader 6 arranged between the semiconductor chip 1 and the heat sink 2, a cured product of the first composition 3 arranged between the semiconductor chip 1 and the heat spreader 6, and a cured product of the second composition 3 arranged between the heat spreader 6 and the heat sink 2.

[0127] In this semiconductor device (processor), the cured product of the first composition 3 is in direct contact with the semiconductor chip 1, which is an electronic component, while the cured product of the second composition 3 is in thermal contact with the semiconductor chip 1, which is an electronic component, via the cured product of the first composition 3 and the heat spreader 6.

[0128] Because the cured product of the first composition 3 and the cured product of the second composition 3 have excellent thermal conductivity, in the obtained semiconductor device, the cured product of the first composition 3 and the cured product of the second composition 3 function as a thermally conductive material (thermal interface material). That is, the cured product of the first composition 3 promotes thermal conduction from the semiconductor chip 1 to the heat spreader 6. Furthermore, the cured product of the second composition 3 promotes thermal conduction from the heat spreader 6 to the heat sink 2. Heat is then dissipated from the heat sink 2 to the outside.

[0129] In the examples shown in Figures 1 and 2, a semiconductor chip is used as the electronic component and a heat sink is used as the heat dissipation member, but the electronic component and heat dissipation member are not limited to these, and any electronic component that serves as a heat source and any heat dissipation member that is commonly used in the technical field can be used without any particular restrictions.

[0130] The semiconductor device manufacturing method described above can provide a semiconductor device with excellent heat dissipation efficiency. The composition described above is suitable for use in the semiconductor device manufacturing method described above, and may be used by being placed between an electronic component and a heat dissipation member and heated at the temperature T1. The specific embodiments of the electronic component and the heat dissipation member can be the same as those described above, without any particular limitations.

[0131] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0132] [Preparation of Compositions] Compositions a, b, c, and d were obtained by mixing the components in the blending ratios shown in Table 1. Details of each component are as follows: In compositions a, b, c, and d, the content of the thermally conductive filler based on the total volume of each composition was 36.0% by volume.

[0133] (Curable Components) A-1: ​​(meth)acrylic polymer having (meth)acryloyl groups at both ends of the poly(meth)acrylate chain ("RC310C" manufactured by Kaneka Corporation, Mw: 30,000, viscosity at 23°C: 760 Pa·s, Tg: -44°C) B-1: isodecyl acrylate ("FA-111A" manufactured by Resonac Corporation) B-2: 2-ethylhexyl acrylate ("AEH" manufactured by Nippon Shokubai Co., Ltd.) B-3: 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Ltd.) B-4: N-acryloylmorpholine ("ACMO" manufactured by KJ Chemicals Co., Ltd.) B-5: 2-acryloyloxyethyl succinate ("NK Ester A-SA" manufactured by Shin-Nakamura Kogyo Co., Ltd.)

[0134] (Curing Agents) C-1: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (manufactured by NOF Corporation, "Perocta O", 1-minute half-life temperature: 124.3°C, 1-hour half-life temperature: 84.4°C) C-2: t-butylperoxy-2-ethylhexanoate (manufactured by NOF Corporation, "Perbutyl O", 1-minute half-life temperature: 134.0°C, 1-hour half-life temperature: 92.1°C) C-3: t-butylperoxy-2-ethylhexyl monocarbonate (manufactured by NOF Corporation, "Perbutyl E", 1-minute half-life temperature: 161.4°C, 1-hour half-life temperature: 119.3°C) C-4: t-butyl peroxybenzoate (NOF Corporation, "Perbutyl Z", 1-minute half-life temperature: 166.8°C, 1-hour half-life temperature: 124.7°C)

[0135] (Thermal conductive filler) D-1: flaky silver filler ("Silcoat AgC-2262" manufactured by Fukuda Metal Industries Co., Ltd., average particle size: 5.3 μm, BET specific surface area: 0.1 to 0.4 m ２ / g)

[0136] (Others) E-1: Random copolymer containing butyl acrylate (Tg of homopolymer: -55°C) and hydroxyethyl acrylate as monomer units (manufactured by Resonac Corporation, butyl acrylate:hydroxyethyl acrylate (mass ratio) = 88:12, Mw = 330,000, Mw / Mn = 1.5) F-1: 1,4-bis(3-mercaptobutyryloxy)butane (manufactured by Resonac Corporation, "Karenz MT BD1") G-1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403") H-1: Phenolic antioxidant (manufactured by BASF Japan Ltd., "Irganox 1010") I-1: Gap filler (manufactured by Hayakawa Rubber Co., Ltd., "SD-BD", average particle size: 50 μm)

[0137] [DSC Measurement] DSC measurement was performed on each of the prepared compositions according to the following procedure. An amount (6 to 8 mg) of the composition was weighed out so that the total amount of components in the composition excluding the silver filler was approximately 1 mg. DSC measurement was performed using a TA Instruments Discovery DSC250s under the following conditions: a heating rate of 10°C / min, and a measurement temperature range of 25°C to 200°C. This resulted in a DSC curve with heat flow on the vertical axis and temperature on the horizontal axis. For each composition, a single exothermic peak was detected in the resulting DSC curve, which was thought to be due to the curing reaction of the composition. The temperature at the apex of this exothermic peak was determined as the peak-top temperature Tp. The onset temperature To was determined as the temperature at the intersection of a straight line extending the low-temperature baseline toward the high-temperature side and a tangent drawn to the curve on the low-temperature side of the exothermic peak at the point where the gradient was greatest. The results are shown in Table 1.

[0138]

[0139] [Sample Preparation] Samples for the Examples and Comparative Examples were prepared using the compositions shown in Tables 2 to 4, following the procedure described below. Two copper plates (27 mm x 27 mm x 1 mm thick) with nickel plating on their surfaces were prepared. Approximately 50 mg of the composition shown in Tables 2 to 4 was applied to the surface of one of the copper plates, and the other copper plate was placed on top of the applied composition. The resulting composite was heated for 10 minutes at a temperature T1 shown in Tables 2 to 4 while applying a pressure of approximately 0.3 MPa under atmospheric pressure. It was then heated for 60 minutes at 180°C (temperature T2) under atmospheric pressure. This resulted in a sample in which the cured composition was placed between two copper plates. Tables 2 to 4 also show the peak-top temperature Tp of the DSC curve for each composition, determined by the DSC measurement described above.

[0140] [Measurement of Thermal Conductivity] The thermal diffusivity of the obtained sample was measured at 25°C using a 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 using a differential scanning calorimeter ("DSC250" manufactured by TA Instruments) according to the following formula. The results are shown in Tables 2 to 4. 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))

[0141]

[0142]

[0143]

[0144] REFERENCE SIGNS LIST 1...semiconductor chip, 2...heat sink, 3...composition, 4...substrate, 5...underfill, 6...heat spreader, 10, 20...composite

Claims

1. A method for producing a cured product of a composition comprising a curable component and a thermally conductive filler, comprising heating the composition at a temperature T1, wherein the temperature T1 and the peak-top temperature Tp of the DSC curve of the composition obtained by differential scanning calorimetry in which the composition is heated from 25°C to 200°C at a heating rate of 10°C / min satisfy the following formula (A): 10°C≦T1-Tp≦40°C (A) 2. A method for manufacturing a semiconductor device, comprising heating a composition that contains a curable component and a thermally conductive filler and is disposed between an electronic component and a heat dissipation member at a temperature T1, wherein the temperature T1 and the peak-top temperature Tp of the DSC curve of the composition obtained by differential scanning calorimetry in which the composition is heated from 25°C to 200°C at a heating rate of 10°C / min satisfy the following formula (A): 10°C≦T1-Tp≦40°C (A) 3. The manufacturing method according to claim 1 or 2, wherein the curable component comprises a compound having an ethylenically unsaturated group.

4. The method according to claim 3, wherein the compound having an ethylenically unsaturated group includes a compound having two or more ethylenically unsaturated groups.

5. The method according to claim 3 or 4, wherein the compound having an ethylenically unsaturated group is a compound having a (meth)acryloyl group.

6. The method according to claim 4 or 5, wherein the compound having two or more ethylenically unsaturated groups further has a poly(meth)acrylate chain.

7. The manufacturing method according to any one of claims 1 to 6, wherein the thermally conductive filler is a metal filler.

8. The manufacturing method according to claim 7, wherein the metal filler is a silver filler.

9. The manufacturing method according to claim 1 or 2, wherein the curable component comprises a compound having an ethylenically unsaturated group, and the thermally conductive filler is a metal filler.

10. A composition comprising a curable component and a thermally conductive filler, which is used by being heated at a temperature T1, wherein the temperature T1 and the peak top temperature Tp of the DSC curve of the composition obtained by differential scanning calorimetry in which the composition is heated from 25°C to 200°C at a heating rate of 10°C / min satisfy the relationship of the following formula (A): 10°C≦T1-Tp≦40°C (A) 11. The composition according to claim 10, which is used by being heated to said temperature T1 while being disposed between an electronic component and a heat dissipation member.

12. The composition of claim 10 or 11, wherein the hardenable component comprises a compound having an ethylenically unsaturated group.

13. The composition according to claim 12, wherein the compound having an ethylenically unsaturated group includes a compound having two or more ethylenically unsaturated groups.

14. The composition according to claim 12 or 13, wherein the compound having an ethylenically unsaturated group is a compound having a (meth)acryloyl group.

15. The composition according to claim 13 or 14, wherein the compound having two or more ethylenically unsaturated groups further has a poly(meth)acrylate chain.

16. The composition of any one of claims 10 to 15, wherein the thermally conductive filler is a metal filler.

17. The composition of claim 16, wherein the metal filler is a silver filler.

18. A cured product of the composition according to any one of claims 10 to 17.

19. A heat dissipating material comprising the cured product according to claim 18.

20. A semiconductor device comprising the heat dissipation material according to claim 19.

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