Sets of curable compositions and articles

Abstract

To provide a set of curable compositions that can produce cured products with low elasticity and excellent elongation. [Solution] A curable composition set comprising a first liquid containing an oxidizing agent and a second liquid containing a reducing agent, wherein at least one of the first liquid and the second liquid contains a compound represented by the following formula (1), TIFF2026083015000016.tif32149 [In formula (1), R 11 and R 12 Each of these independently represents a hydrogen atom or a methyl group, R 13 This represents a divalent group having a polyoxyalkylene chain. A curable composition set in which at least one of the first and second liquids contains a thermally conductive filler.

Description

[Technical Field]

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

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

[0003] Many liquid materials are known as thermally conductive materials, and are also called heat dissipation greases or thermally conductive greases. For example, Patent Document 1 discloses a thermally conductive grease composition containing a liquid hydrocarbon oil and / or fluorinated hydrocarbon oil and a predetermined amount of a thermally conductive inorganic filler. Patent Document 2 also 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] Japanese Patent Publication No. 2011-111517 [Overview of the project] [Problems that the invention aims to solve]

[0005] When using liquid thermal conductive grease, dripping after application or a pump-out phenomenon may occur, where the grease is pushed out from between components due to deformation of the component to which the thermal conductive grease is applied. Dripping or pump-out creates voids between the grease and the component, reducing the adhesion of the grease to the component and increasing the thermal resistance between the heat dissipation grease and the component. Dripping or pump-out can also contaminate other components with grease, potentially leading to insulation failure.

[0006] To solve these problems, thermally conductive materials formed in a solid form, such as a sheet, are sometimes used. By using solid thermally conductive materials, dripping or pump-out phenomena can be suppressed. On the other hand, in electronic components equipped with heat-generating and heat-dissipating components, repeated heating and cooling can cause deformation such as warping of the components. Therefore, solid thermally conductive materials are required to be low-elasticity and highly elongated so that they can follow the deformation of the components.

[0007] In one aspect, the present invention aims to provide a set of curable compositions that can produce cured products with low elasticity and excellent elongation. [Means for solving the problem]

[0008] As a result of diligent research, the inventors have found that the cured products of a set of curable compositions containing a specific compound having a polyoxyalkylene chain and two (meth)acryloyl groups exhibit low elasticity and excellent elongation. Furthermore, they have found that this curable composition, by containing a thermally conductive filler, is suitably used as a thermally conductive material, thus completing the present invention. In several aspects, the present invention provides the following [1] to

[11] .

[0009] [1] A curable composition set comprising 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 following formula (1): [ka] [In formula (1), R 11 and R 12 each independently represent a hydrogen atom or a methyl group, and R 13 represents a divalent group having a polyoxyalkylene chain.] A curable composition set in which at least one of the first liquid and the second liquid contains a thermal conductivity filler. [2] The curable composition set according to [1], wherein the polyoxyalkylene chain contains a structural unit represented by the following formula (2). [Chemical formula] [3] The curable composition set according to [1], wherein the polyoxyalkylene chain contains a structural unit represented by the following formula (3). [Chemical formula] [4] The curable composition set 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). [Chemical formula] [Chemical formula] [5] The curable composition set according to [4], wherein the copolymer chain is a random copolymer chain. [6] The curable composition set according to any one of [1] to [5], wherein the weight average molecular weight of the compound represented by formula (1) is 5000 or more. [7] The curable composition set 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 set according to any one of [1] to [7], wherein the viscosity of the compound represented by formula (1) at 25 °C is 1000 Pa·s or less. [9] The curable composition set according to any one of [1] to [8], further containing an antioxidant.

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

[11] An article comprising a heat source and a cured product of any of the curable composition sets described in [1] to

[10] , provided to be in thermal contact with the heat source. [Effects of the Invention]

[0010] According to one aspect of the present invention, it is possible to provide a set of curable compositions that can produce cured products with low elasticity and excellent elongation. [Brief explanation of the drawing]

[0011] [Figure 1] This is a schematic cross-sectional view showing one embodiment of an article comprising a cured product of a curable composition set. [Figure 2] This is a schematic cross-sectional view showing another embodiment of an article comprising a cured product of a curable composition set. [Modes for carrying out the invention]

[0012] The embodiments of the present invention will be described in detail below with reference to the drawings as appropriate. However, the present invention is not limited to the embodiments described below.

[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] In this specification, the weight-average molecular weight (Mw) refers to the value determined by measuring the following conditions using gel permeation chromatography (GPC) with polystyrene as the standard substance. • Measuring instrument: HLC-8320GPC (product name, manufactured by Tosoh Corporation) • Analytical column: TSKgel SuperMultipore HZ-H (3-column linked) (Product name, manufactured by Tosoh Corporation) • Guard column: TSKguardcolumn SuperMP(HZ)-H (product name, manufactured by Tosoh Corporation) ·Eluent:THF ·Measurement temperature: 25℃

[0015] [Curing Composition Set] A curable composition set according to one embodiment comprises a first liquid containing an oxidizing agent and a second liquid containing a reducing agent. By mixing the first liquid and the second liquid, the oxidizing agent and the reducing agent react to generate free radicals, and polymerization of polymerizable components such as the compound represented by formula (1), described later, proceeds. According to the curable composition set of 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 (hereinafter this cured product is also referred to as the "cured product of the curable composition set") is obtained.

[0016] The oxidizing agent contained in the first solution acts as a polymerization initiator (radical polymerization initiator). The oxidizing agent may be, for example, an organic peroxide or an azo compound. Examples of organic peroxides include hydroperoxides, peroxydicarbonates, peroxyesters, peroxyketals, dialkylperoxides, diacylperoxides, etc. Examples of azo compounds include AIBN (2,2'-azobisisobutyronitrile) and V-65 (azobisdimethylvaleronitrile). The oxidizing agent can be used alone or in combination of two or more types.

[0017] Examples of hydroperoxides include diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide.

[0018] 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.

[0019] Examples of 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 Examples include t-2-ethylhexanate, t-hexylperoxy-2-ethylhexanate, t-butylperoxy-2-ethylhexanate, t-butylperoxyisobutyrate, 1,1-bis(t-butylperoxy)cyclohexane, t-butylperoxy-3,5,5-trimethylhexanate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluylperoxy)hexane, t-hexylperoxybenzoate, and t-butylperoxyacetate.

[0020] 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.

[0021] 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.

[0022] Examples of diacyl peroxides include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoyl peroxytoluene, and benzoyl peroxide.

[0023] The oxidizing agent is preferably a peroxide, more preferably a hydroperoxide, even more preferably 1,1,3,3-tetramethylbutyl hydroperoxide or cumene hydroperoxide, and particularly preferably 1,1,3,3-tetramethylbutyl hydroperoxide, from the viewpoint of storage stability.

[0024] The oxidizing agent content may be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more, and may be 10% by mass or less, 5% by mass or less, or 3% by mass or less, based on the total amount of the first and second liquids.

[0025] The reducing agent contained in the second solution may be, for example, a tertiary amine, a thiourea derivative, or a transition metal salt. Examples of tertiary amines include triethylamine, tripropylamine, tributylamine, and N,N-dimethylparatoluidine. Examples of thiourea derivatives include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylenethiourea. Examples of transition metal salts include cobalt naphthenate, copper naphthenate, and vanadylacetylacetonate. The reducing agent can be used individually or in combination of two or more types.

[0026] From the viewpoint of excellent curing speed, the reducing agent is preferably a thiourea derivative or a transition metal salt. The thiourea derivative may be, for example, ethylene thiourea. From the same viewpoint, the transition metal salt is preferably vanadyl acetylacetonate.

[0027] The content of the reducing agent may be 0.05% by mass or more, 0.1% by mass or more, or 0.3% by mass or more, and may be 5% by mass or less, 3% by mass or less, or 1% by mass or less based on the total amount of the first liquid and the second liquid.

[0028] In the curable composition set, at least one of the first liquid and the second liquid contains a compound represented by the following formula (1).

Chemical formula

[0029] In one embodiment, one of R 11 and R 12 may be a hydrogen atom and the other may be a methyl group. In another embodiment, both of R 11 and R 12 may be hydrogen atoms. In another embodiment, both of R 11 and R 12 may be methyl groups.

[0030] In one embodiment, the polyoxyalkylene chain contains a structural unit represented by the following formula (2). Thereby, while suppressing an excessive increase in the viscosity of the curable composition (referring to one or both of the first liquid and the second liquid. The same applies hereinafter), the strength of the cured product can be increased.

Chemical formula

[0031] In this case, R 13The group may be a divalent group having a polyoxyethylene chain, and the compound represented by formula (1) is preferably a compound represented by the following formulas (1-2) (polyethylene glycol di(meth)acrylate). [ka] In formula (1-2), R 11 and R 12 R in equation (1) 11 and R 12 These are synonymous, and m is an integer greater than or equal to 2.

[0032] In another embodiment, the polyoxyalkylene chain includes a structural unit represented by the following formula (3). This facilitates the handling of the curable composition. [ka]

[0033] In this case, R 13 The group may be a divalent group having a polyoxypropylene chain, and the compound represented by formula (1) is preferably a compound represented by the following formulas (1-3) (polypropylene glycol di(meth)acrylate). [ka] In formula (1-3), R 11 and R 12 R in equation (1) 11 and R 12 These are equivalent to the above, and n is an integer greater than or equal to 2.

[0034] In another embodiment, the polyoxyalkylene chain is preferably a copolymer chain containing the structural units represented by formula (2) and 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 handling of the curable composition. The copolymer chain may be an alternating copolymer chain, a block copolymer chain, or a random copolymer chain. The copolymer chain is preferably a random copolymer chain from the viewpoint of further lowering the crystallinity of the compound represented by formula (1) and further facilitating the handling of the curable composition.

[0035] In each of the embodiments described above, the polyoxyalkylene chain may have, in addition to the structural units represented by formula (2) and formula (3), oxyalkylene groups having 4 to 5 carbon atoms, such as oxytetramethylene groups, oxybutylene groups, and oxypentylene groups, as structural units.

[0036] R 13 In addition to the polyoxyalkylene chain described above, the group may be a divalent group further having other organic groups. The other organic groups may be chain-like groups other than the polyoxyalkylene chain, such as a methylene chain (a chain with -CH2- as a structural unit), a polyester chain (a chain containing -COO- as a structural unit), a polyurethane chain (a chain containing -OCON- as a structural unit), etc.

[0037] For example, the compound represented by formula (1) may also be a compound represented by the following formulas (1-4). [ka] In formula (1-4), R 11 and R 12 R in equation (1) 11 and R 12 These are synonymous, and R 14 and R 15 Each of these is an alkylene group having 2 to 5 carbon atoms, and k1, k2, and k3 are each independent integers of 2 or more. k2 may be an integer less than or equal to 16, for example.

[0038] Multiple Rs exist 14 and R 15 Each of them may be identical to the others, or they may be different to each other. There are multiple R's. 14 and R 15 Each preferably contains an ethylene group and a propylene group. That is, (R 14 O) k1 Polyoxyalkylene chains represented by (R 15 O) k3 The polyoxyalkylene chains represented by are preferably copolymer chains containing an oxyethylene group (structural unit represented by formula (2) above) and an oxypropylene group (structural unit represented by formula (3) above).

[0039] In each of the embodiments described above, 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, which further improves the elongation of the cured product and increases the strength of the cured product. 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), respectively.

[0040] 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.

[0041] 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 the cured product having lower elasticity and superior elongation. 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, from the viewpoint of making it easier to adjust the viscosity of the curable composition.

[0042] 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 the coating surface and improving the adhesion of the cured product to the 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.

[0043] The compound represented by formula (1) may be solid at 25°C. In this case, from the viewpoint of further improving the handling of the curable composition, the compound represented by formula (1) is preferably liquid at 50°C. In this case, from the viewpoint of further improving the handling 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.

[0044] Viscosity refers to the value measured according to JIS Z 8803, specifically the value measured using an E-type viscometer (for example, PE-80L manufactured by Toki Sangyo Co., Ltd.). The viscometer can be calibrated according to 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.

[0045] The content of the compound represented by formula (1) is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more, based on the total amount of the first and second liquids, from the viewpoint of the cured product having lower elasticity and superior elongation. The content of the compound represented by formula (1) may be 20% by mass or less, 17% by mass or less, or 15% by mass or less, based on the total amount of the first and second liquids.

[0046] The curable composition may contain other polymerizable compounds (details of which 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, per 100 parts by mass of the total of the compound represented by formula (1) and other polymerizable compounds (hereinafter referred to as "total content of polymerizable components"). 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, per 100 parts by mass of the total content of polymerizable components.

[0047] In a curable composition set, at least one of the first and second liquids 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 refers to a filler with a thermal conductivity of 10 W / m·K or higher. It is preferable that both the first and second liquids contain a thermally conductive filler.

[0048] The thermally conductive filler may be insulating or conductive, and is preferably insulating. Examples of materials constituting an 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, and zinc oxide. Examples of materials constituting a conductive thermally conductive filler include aluminum, silver, and copper. The shape of the thermally conductive filler may be spherical or polyhedral.

[0049] 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, from the viewpoint of being able to thinly arrange the cured product of the curable composition set, 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 refers to the particle size (D50) at which the volume cumulative particle size distribution is 50%, and is measured using a laser diffraction particle size distribution analyzer (for example, SALD-2300 (manufactured by Shimadzu Corporation)).

[0050] From the viewpoint of enhancing the thermal conductivity of the curable composition, the content of the thermally conductive filler is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and may be 97% by mass or less, 95% by mass or less, or 93% by mass or less, based on the total amount of the first liquid and the second liquid.

[0051] From the viewpoint of enhancing the thermal conductivity of the curable composition, the content of the thermally conductive filler is preferably 70% by volume or more, more preferably 75% by volume or more, even more preferably 80% by volume or more, and may be 90% by volume or less, 88% by volume or less, or 85% by volume or less, based on the total volume of the curable composition.

[0052] The curable composition may further contain other polymerizable compounds copolymerizable with the compound represented by formula (1) described above, for the purpose of adjusting the physical properties of the curable composition.

[0053] Other polymerizable compounds may be, for example, compounds having one (meth)acryloyl group. Such compounds may be, for example, alkyl (meth)acrylates. Other polymerizable compounds may also be compounds having, in addition to one (meth)acryloyl group, an aromatic hydrocarbon group, a group containing a polyoxyalkylene chain, a group containing a heterocyclic group, 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 including alkyl (meth)acrylates in the curable composition. Furthermore, the adhesion of the curable composition and its cured product to the member can be further improved by including compounds having a hydroxyl group, a carboxyl group, an amino group, or an epoxy group in addition to the (meth)acryloyl group in the curable composition.

[0054] The alkyl group (the alkyl group portion other than the (meth)acryloyl group) in alkyl (meth)acrylate 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, and may also be 12 to 30, 12 to 28, 12 to 24, 12 to 22, 12 to 18, or 12 to 14.

[0055] Examples of alkyl(meth)acrylates having a linear alkyl group include 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, or undecyl(meth)acrylate, which are alkyl(meth)acrylates having a linear alkyl group with 1 to 11 carbon atoms. Examples of alkyl(meth)acrylates having a linear alkyl group with 12 to 30 carbon atoms include syl(meth)acrylate (lauryl(meth)acrylate), tetradecyl(meth)acrylate, hexadecyl(meth)acrylate (cetyl(meth)acrylate), octadecyl(meth)acrylate (stearyl(meth)acrylate), docosyl(meth)acrylate (behenyl(meth)acrylate), tetracosyl(meth)acrylate, hexacosyl(meth)acrylate, and octacosyl(meth)acrylate.

[0056] Examples of alkyl(meth)acrylates having branched alkyl groups include 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, isodecyl(meth)acrylate, and other alkyl(meth)acrylates having branched alkyl groups with 1 to 11 carbon atoms, as well as isomiristyl Examples of alkyl(meth)acrylates having branched alkyl groups with 12 to 30 carbon atoms include 12-30 carbon atoms, such as 14-(meth)acrylate, 2-propylheptyl(meth)acrylate, isoundecyl(meth)acrylate, isododecyl(meth)acrylate, isotridecyl(meth)acrylate, isopentadecyl(meth)acrylate, isohexadecyl(meth)acrylate, isoheptadecyl(meth)acrylate, isostearyl(meth)acrylate, and decyltetradecanyl(meth)acrylate.

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

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

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

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

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

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

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

[0064] Examples of compounds having a (meth)acryloyl group and a group containing a siloxane bond include silicone (meth)acrylates.

[0065] Compounds 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, 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 include (meth)acrylates containing a fluorine atom, such as tridecylmethyl (meth)acrylate, perfluorotetradecylmethyl (meth)acrylate, 2-(trifluoromethyl)ethyl (meth)acrylate, 2-(perfluoroethyl)ethyl (meth)acrylate, 2-(perfluoropropyl)ethyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluoropentyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluoroheptyl)ethyl (meth)acrylate, 2-(perfluorooctyl)ethyl (meth)acrylate, 2-(perfluorononyl)ethyl (meth)acrylate, 2-(perfluorotridecyl)ethyl (meth)acrylate, and 2-(perfluorotetradecyl)ethyl (meth)acrylate.

[0066] Examples of compounds 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 hydroxyalkylcycloalkane (meth)acrylates such as (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.

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

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

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

[0070] The content of other polymerizable compounds is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on the total amount of the first and second liquids, and may be 20% by mass or less, 15% by mass or less, or 10% by mass or less, from the viewpoint of making it easier to adjust the viscosity of the curable composition or from the viewpoint of further improving the adhesion of the curable composition.

[0071] The content of 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, based on 100 parts by mass of the total content of polymerizable components, and may be 90 parts by mass or less, 80 parts by mass or less, or 70 parts by mass or less, from the viewpoint of making it easier to adjust the viscosity of the curable composition or from the viewpoint of further improving the adhesion of the curable composition.

[0072] The curable composition may further contain a plasticizer. The inclusion of a plasticizer in the curable composition can further enhance the adhesion of the curable composition and the elongation of the cured product. Examples of plasticizers include tackifiers such as butadiene rubber, isoprene rubber, silicone rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene propylene rubber, urethane rubber, acrylic resin, rosin-based resin, terpene-based resin, or polyalkylene glycol.

[0073] The plasticizer content 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, based on 100 parts by mass of the total content of polymerizable components.

[0074] The curable composition may further contain an antioxidant from the viewpoint of improving the thermal reliability of the cured product of the curable composition set. The antioxidant may be, for example, a phenolic antioxidant, a benzophenone antioxidant, a benzoate antioxidant, a hindered amine antioxidant, a benzotriazole antioxidant, etc., and is preferably a phenolic antioxidant.

[0075] Phenolic antioxidants, for example, have 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 the hydroxyl group in the phenol ring. Phenolic antioxidants have one or more such hindered phenol rings, preferably two or more, more preferably three or more, and even more preferably four or more.

[0076] The antioxidant content may be 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, based on the total amount of the first and second liquids, and may be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less.

[0077] The curable composition may further contain other additives as needed. Examples of other additives include surface treatment agents (e.g., silane coupling agents), dispersants, curing accelerators, colorants, nucleating agents, heat stabilizers, foaming agents, flame retardants, vibration dampers, dehydrating agents, and flame retardant aids (e.g., metal oxides). The content of other additives may be 0.1% by mass or more and 30% by mass or less, based on the total amount of the first and second liquids.

[0078] The first and second liquids may be liquid at 25°C. This allows for suitable application to the surface of objects such as heat source components and cooling components, and also improves adhesion to the application surface.

[0079] In the cured product composition set, it is preferable that each component other than the oxidizing agent and reducing agent is included in both the first and second liquids. That is, in one embodiment, it is preferable that the first liquid contains an oxidizing agent, a compound represented by formula (1), and a thermally conductive filler (and other components used as needed), and the second liquid contains a reducing agent, a compound represented by formula (1), and a thermally conductive filler (and other components used as needed).

[0080] [Cured products and thermally conductive materials] The cured product of the above-described curable composition set has thermal conductivity, low elasticity, and excellent elongation, making it suitable for use as a thermal conductive material (also called a heat dissipation material) in electronic components such as power modules, CPUs, and ECUs, batteries, LED lighting, and LED backlights. That is, one embodiment of the present invention provides a thermal conductive material containing the compound represented by formula (1) described above and a thermal conductive filler.

[0081] [Goods] Next, we will explain articles that include the cured product of the curable composition set described above, using an electronic component as an example. Figure 1 is a schematic cross-sectional view showing one embodiment of an electronic component that includes the cured product of the curable composition set. The electronic component 1A shown in Figure 1 includes a semiconductor chip 21 as a heat source and a heat sink 22 as a heat dissipation part.

[0082] The electronic component 1A includes a cured product 11 of the curable composition set described above, which is placed between the semiconductor chip 21 and the heat sink 22. Since the cured product 11 is thermally conductive, it acts as a thermally conductive material (thermal interface material) in the electronic component 1A, conducting heat from the semiconductor chip 21 to the heat sink 22. Then, the heat is dissipated from the heat sink 22 to the outside.

[0083] The cured product 11, by using the curable composition set described above, has low elasticity and excellent elongation. Therefore, it has high adaptability to deformation of the electronic component 1A caused by heat, etc. Consequently, heat generated from the semiconductor chip 21 can be effectively conducted to the heat sink 22. Furthermore, since the cured product 11 is a cured product of the curable composition set described above, it also has excellent strength (e.g., fracture strength).

[0084] The cured product 11 is obtained by placing the first liquid and the second liquid between the semiconductor chip 21 and the heat sink 22. Therefore, the generation of voids due to liquid dripping and pump-out phenomena can be suppressed, and as a result, the adhesion of the cured product 11 (adhesion to the surfaces of the semiconductor chip 21 and the heat sink 22) can be made excellent.

[0085] In the electronic component 1A described in Figure 1, the cured material 11 is arranged to be in direct contact with the semiconductor chip 21 and the heat sink 22. However, the cured material 11 only needs to be in thermal contact with the heat source, and in another embodiment, it may be arranged to be in contact with the heat source (semiconductor chip) via another component.

[0086] Figure 2 is a schematic cross-sectional view showing another embodiment of an electronic component comprising a cured product of a curable composition set. The electronic component 1B shown in Figure 1 is a processor comprising a semiconductor chip 21 as a heat source, a heat sink 22 as a heat dissipation part, and a heat spreader 25 provided between the semiconductor chip 21 and the heat sink 22, all arranged on one surface of a substrate 23 via an underfill 24. 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.

[0087] The substrate 23, underfill 24, and 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 epoxy resin, and the heat spreader 25 may be a metal plate.

[0088] The first cured product 11 and the second cured product 11 are cured products of the curable composition set described above. The first cured product 11 is in direct contact with the semiconductor chip 21, which is the heat source, while the second cured product 11 is in thermal contact with the semiconductor chip 21, which is the heat source, via the first cured product 11 and the heat spreader 25.

[0089] Since the first cured material 11 and the second cured material 11 are thermally conductive, they act as thermally conductive materials (thermal interface materials) in the electronic component 1B. Specifically, the first cured material 11 promotes heat conduction from the semiconductor chip 21 to the heat spreader 25. The second cured material 11 also promotes heat conduction from the heat spreader 25 to the heat sink 22. Then, heat is dissipated from the heat sink 22 to the outside.

[0090] The first cured product 11 and the second cured product 11 also exhibit low elasticity and excellent elongation by using the above-described curable composition set. 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. Consequently, heat generated from the semiconductor chip 21 can be more effectively conducted to the heat spreader 25, and furthermore, that heat can be more effectively conducted to the heat sink 22. In addition, since the first cured product 11 and the second cured product 11 are cured products of the above-described curable composition set, they also have excellent strength (e.g., fracture strength).

[0091] The first cured product 11 and the second cured product 11 are obtained by placing the first liquid and the second liquid between the semiconductor chip 21 and the heat spreader 25, or between the heat spreader 25 and the heat sink 22. Therefore, even in the electronic component 1B, the dripping of the curable composition and the generation of voids due to the pump-out phenomenon can be suppressed, and as a result, 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) can be made excellent. [Examples]

[0092] 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.

[0093] In the examples, the following components were used as common components for the first and second solutions. (A-1) A mixture of compounds represented by formula (1-7) synthesized by the procedure shown below (weight-average molecular weight: 15000, where m1+m2 in formula (1-7) is approximately 252±5 and n1+n2 is approximately 63±5 integers (where m1, m2, n1, and n2 are each independently integers of 2 or more, m1+n1≧100, m2+n2≧100), viscosity at 25℃: 50 Pa·s) [ka] In equations (1-7), -r- is a sign representing random copolymerization. (A-2) Compounds represented by formula (1-8) synthesized by the procedure shown below (weight-average molecular weight: 16000, a mixture in which m in formula (1-8) is approximately 246±5 and n is approximately an integer of 105±5, viscosity at 25℃: 55 Pa·s) [ka] In equations (1-8), -r- is a sign representing random copolymerization.

[0094] (B-1) 4-Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (B-2) Isodecyl acrylate (Hitachi Chemical Co., Ltd. "FA111A")

[0095] (C) Plasticizer (Arakawa Chemical Industries, Ltd. "Tackifire KE359") (D) Phenolic antioxidant (ADEKA Corporation's "ADEKA Stab AO-80")

[0096] (E-1) Alumina filler (Sumitomo Chemical Co., Ltd. "Advanced Alumina AA-18") (E-2) Alumina filler (Sumitomo Chemical Co., Ltd. "Advanced Alumina AA-3") (E-3) Alumina filler (Sumitomo Chemical Co., Ltd. "Advanced Alumina AA-04") (F) Silane coupling agent (KBM-5803, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0097] [Synthesis of compounds represented by formulas (1-7)] A 500 mL flask, consisting of a stirrer, thermometer, nitrogen gas inlet tube, outlet tube, and heating jacket, was used as the reactor. 225 g of glycol having polyoxyalkylene chains (Sanyo Chemical Industries, Ltd. "Newpol 75H-90000") and 300 g of toluene were added to the reactor and stirred at 45°C and a stirring speed of 250 revolutions / minute. Nitrogen was supplied at 100 mL / min and stirred for 30 minutes. The mixture was then cooled to 25°C, and after cooling was complete, 2.9 g of acryloyl chloride was added dropwise to the reactor and stirred for 30 minutes. Then, 3.8 g of triethylamine was added dropwise and stirred for 2 hours. The temperature was then raised to 45°C and the reaction was carried out for 2 hours. The reaction mixture was filtered, and the filtrate was desoluble to obtain the compound represented by formula (1-7).

[0098] [Synthesis of compounds represented by formulas (1-8)] The compound represented by formula (1-8) was obtained by the same method as in the synthesis method of the compound represented by formula (1-7), except that the glycol having a polyoxyalkylene chain ("Newpol 75H-90000" manufactured by Sanyo Chemical Industries, Ltd.) was replaced with 240 g of polyoxyethylene polyoxypropylene glycol (molecular weight 16000).

[0099] [Preparation of a set of curable compositions] The common components and an oxidizing agent (oxidizing agent 1: cumene hydroperoxide (containing approximately 20% aromatic hydrocarbons) (Tokyo Chemical Industries, Ltd.), or oxidizing agent 2: 1,1,3,3-tetramethylbutyl hydroperoxide (Trigonox TMBH-L, manufactured by Kayaku Nurion Co., Ltd.)) were mixed in the amounts (parts by mass) shown in Table 1 to obtain the first solution. The common components and a reducing agent (ethylenethiourea) were also mixed in the amounts (parts by mass) shown in Table 1 to obtain the second solution. Note that the amounts of the common components shown in Table 1 are the amounts used in the first and second solutions, respectively.

[0100] [Evaluation of curing time] The curing time was evaluated using a rheometer (Anton Paar). The first and second liquids were mixed at the mixing mass ratio shown in Table 1 to obtain a mixture of the first and second liquids (curable composition). Approximately 1.5 g of the curable composition was weighed onto the rheometer's disposable sample dish (Anton Paar), and the distance between the disposable dish and the disposable plate D-PP25 (Anton Paar) was adjusted so that the thickness of the curable composition was 0.5 mm. After removing the excess curable composition from the disposable dish, the disposable plate was vibrated at 1 Hz with a strain of 2%, and the measurement was started with the sample kept at a constant temperature of 25°C. The time from the start of measurement until the storage modulus value rose was defined as the curing time.

[0101] [Measurement of thermal conductivity] The first and second liquids were mixed in the mass ratio shown in Table 1 to obtain a mixture of the first and second liquids (curable composition). Next, the curable composition was filled into a 10cm × 10cm × 0.2mm mold (made of SUS plate), and after covering it with a SUS plate, it was heated at 50°C for 30 minutes to cure, thereby obtaining a cured product of the curable composition set with a thickness of 0.2mm (cured product of the mixture of the first and second liquids). The obtained cured product was cut into 10mm × 10mm × 0.2mm squares, blackened with graphite spray, and then the thermal diffusivity was measured at 25°C using the xenon flash method (NETZSCH-Geratebau GmbH, Selb / Bayern "LFA447 nanoflash"). The thermal conductivity in the thickness direction of the cured material was determined from 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 (TA Instruments "DSC250"). 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))

[0102] [Measurement of tensile modulus, elongation at break, and breaking strength] The tensile modulus, elongation at break, and breaking strength of the cured material obtained above were measured at 25°C using a tensile testing machine ("Autograph EZ-TEST EZ-S" manufactured by Shimadzu Corporation). For the measurements, a cured material with dimensions of 0.2 mm (thickness) × 5 mm (width) × 30 mm (length) was measured in accordance with JIS K7161 under conditions of a chuck distance of 20 mm and a tensile speed of 5 mm / min.

[0103] Table 1 shows the measurement results for each physical property of the cured products from Examples 1 to 9.

[0104] [Table 1]

[0105] As can be seen from Table 1, by including the compound represented by formula (1) in the curable composition set, a cured product with low elasticity and excellent elongation (low tensile modulus and high elongation at break) was obtained. [Explanation of symbols]

[0106] 1A, 1B... Electronic components, 11... Cured product of a curable composition set, 21... Semiconductor chip (heat source), 22... Heat sink, 23... Substrate, 24... Underfill, 25... Heat spreader.

Claims

[Claim 1] A curable composition set comprising 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 following formula (1): 【Chemistry 1】 [In formula (1), R １１ and R １２ Each of these independently represents a hydrogen atom or a methyl group, R １３ This represents a divalent group having a polyoxyalkylene chain. A curable composition set in which at least one of the first liquid and the second liquid contains a thermally conductive filler.

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