Two-pack curable composition

Abstract

To provide a two-pack curable composition which has good initial moldability (pot life) and has good curability (monomer conversion rate) even at room temperature.SOLUTION: The two-pack curable composition contains: a liquid A containing (i) a radically polymerizable monomer and (ii) at least one compound selected from heterocyclic ring-containing compounds, amino group-substituted aromatic ring-containing compounds, formyl group-substituted aromatic ring-containing compounds, compounds having an alkanolamine skeleton, thiourea structure-containing compounds, and metal salts of carboxylic acids; and a liquid B containing (iii) a peroxide represented by R1-C(=O)-O-O-C(=O)-R2 (where R1 and R2 each independently represent a C1-20 organic group). At least one of the liquid A and the liquid B contains (iv) at least one polymer selected from the group consisting of (meth)acrylic polymers, polyester-based polymers, polyurethane-based polymers, and silicone polymers.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a two-component curable composition, and more particularly to a two-component curable composition that is preferably used, for example, to form a heat dissipating material. [Background technology]

[0002] As the performance of electronic devices such as automobile batteries, computers, and mobile phones improves, the amount of heat generated also increases, resulting in a rise in demand for heat dissipation agents.

[0003] For example, Patent Document 1 discloses a curable composition containing a compound (A) having one (meth)acrylate group in one molecule, a compound (B) having two or more (meth)acrylate groups in one molecule, a polymerization initiator (C), a dispersant (D), and a thermally conductive filler (E) containing zinc oxide. Patent Document 1 discloses that the composition provides a curable composition or a cured product thereof that is excellent in flexibility, shape stability, and thermal conductivity, and that is excellent in suppressing changes in thermal conductivity in high-temperature environments. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 149193 Summary of the Invention [Problem to be solved by the invention]

[0005] As described above, various curable compositions are known, but in recent years, in order to simplify the manufacturing process of heat dissipators and to prevent thermal damage to each component, there has been a growing need for room-temperature curable adhesives that do not require heating on the manufacturing line, instead of heat-curable adhesives. However, when used in applications such as dissipating heat generated from a heat dissipator by being interposed between a heat dissipator such as an automobile battery and a heat sink, a heat dissipation fin, a resin film, or a metal plate, the adhesive must exhibit sufficient curability at room temperature, etc., but such compositions have a high initial curability, which poses a problem in that it is not possible to ensure sufficient time for molding.

[0006] Therefore, an object of the present disclosure is to provide a two-component curable composition that has good initial moldability (pot life) and good curability (also referred to as monomer conversion rate) even at room temperature. [Means for solving the problem]

[0007] The present inventors have conducted various studies to achieve the above object and have arrived at the present invention. That is, one of the curable compositions of the present disclosure includes: (i) a radically polymerizable monomer; (ii) a liquid A containing at least one compound selected from a heterocycle-containing compound, an amino group-substituted aromatic ring-containing compound, a formyl group-substituted aromatic ring-containing compound, a compound having an alkanolamine skeleton, a thiourea structure-containing compound, and a metal salt of a carboxylic acid; and (iii) a liquid R 1 -C(=O)-OOC(=O)-R 2 Peroxides represented by (where R 1 , R 2 and Liquid B containing (iv) at least one of Liquid A and Liquid B containing (each independently represents an organic group having 1 to 20 carbon atoms), and at least one of Liquid A and Liquid B containing (iv) at least one polymer selected from the group consisting of (meth)acrylic polymers, polyester polymers, polyurethane polymers, and silicone polymers. [Effects of the Invention]

[0008] The two-part curable composition of the present disclosure has good initial moldability (pot life) and good curability (monomer conversion) even at room temperature. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present disclosure will be described in detail below. In addition, a combination of two or more of the individual preferred embodiments of the present disclosure described below is also a preferred embodiment of the present disclosure.

[0010] [Two-component curable composition of the present disclosure] The two-component curable composition of the present disclosure contains separate components A and B. The two-component curable composition of the present disclosure may also contain separate components other than components A and B. That is, in the present disclosure, as long as the two components are separated, the composition is considered to be "two-component," even if it contains, for example, three or more components.

[0011] <Radical polymerizable monomer> The component A of the two-component curable composition of the present disclosure contains a radically polymerizable monomer. The radically polymerizable monomer is not particularly limited, and examples thereof include alkyl (meth)acrylates, cycloalkyl (meth)acrylates, hydroxyl group-containing (meth)acrylates, aromatic monomers having a carbon-carbon double bond, carbon-carbon double bond-containing monomers having a carboxyl group, carbon-carbon double bond-containing monomers having a nitrogen atom, carbon-carbon double bond-containing monomers having an oxo group, carbon-carbon double bond-containing monomers having a fluorine atom, and carbon-carbon double bond-containing monomers having an epoxy group. However, the present invention is not limited to these examples. These other monomers may be used alone or in combination of two or more.

[0012] Among the radical polymerizable monomers, from the viewpoint of rapidly curing the resin composition at room temperature, alkyl(meth)acrylates, cycloalkyl(meth)acrylates, hydroxyl group-containing (meth)acrylates, aromatic monomers having a carbon-carbon double bond, and carbon-carbon double bond-containing monomers having a carboxyl group are preferred, alkyl(meth)acrylates, cycloalkyl(meth)acrylates, hydroxyl group-containing (meth)acrylates, and carbon-carbon double bond-containing monomers having a carboxyl group are more preferred, alkyl(meth)acrylates, cycloalkyl(meth)acrylates, and hydroxyl group-containing (meth)acrylates are even more preferred, alkyl(meth)acrylates and hydroxyl group-containing (meth)acrylates are even more preferred, and alkyl(meth)acrylates are even more preferred.

[0013] Examples of alkyl (meth)acrylates include alkyl (meth)acrylates having an alkyl group of 1 to 18 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, tridecyl (meth)acrylate, and n-lauryl (meth)acrylate, but the present invention is not limited to these examples. These alkyl (meth)acrylates may be used alone or in combination of two or more. Among these alkyl (meth)acrylates, alkyl (meth)acrylates in which the alkyl group has 1 to 8 carbon atoms are preferred, and n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are more preferred, from the viewpoint of increasing the flexibility of the heat dissipation material after curing and improving the ability of the heat dissipation material to conform to the heat generating element and the heat dissipation element.

[0014] From the viewpoint of increasing the flexibility of the heat dissipation material after curing and improving the ability of the heat dissipation material to conform to the heat generating element and the heat dissipation element, the content of alkyl (meth)acrylate in the radical polymerizable monomer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more, with the upper limit being 100% by mass. Therefore, the content of alkyl (meth)acrylate in the radical polymerizable monomer is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, even more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass.

[0015] Examples of cycloalkyl (meth)acrylates include cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate, but the present invention is not limited to these examples. These cycloalkyl (meth)acrylates may be used alone or in combination of two or more. Among these cycloalkyl (meth)acrylates, from the viewpoint of rapidly curing the resin composition at room temperature, cycloalkyl (meth)acrylates having a cycloalkyl group having 3 to 12 carbon atoms are preferred, cycloalkyl (meth)acrylates having a cycloalkyl group having 3 to 10 carbon atoms are more preferred, cycloalkyl (meth)acrylates having a cycloalkyl group having 4 to 8 carbon atoms are even more preferred, and cyclohexyl (meth)acrylate is even more preferred.

[0016] The content of cycloalkyl (meth)acrylate in the radical polymerizable monomer is 0% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and even more preferably 3% by mass or more, from the viewpoint of improving the toughness of the heat dissipation material after curing, and is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and even more preferably 20% by mass or less, from the viewpoint of increasing the flexibility of the heat dissipation material after curing and improving the conformability of the heat dissipation material to the heat generating element and the heat dissipation element. Therefore, the content of cycloalkyl (meth)acrylate in the radical polymerizable monomer is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, even more preferably 2 to 30% by mass, and even more preferably 3 to 20% by mass.

[0017] Examples of hydroxyl group-containing (meth)acrylates include hydroxyl group-containing (meth)acrylates having an ester moiety with 1 to 18 carbon atoms, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerin mono(meth)acrylate, but the present invention is not limited to these examples. These hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more. Among these hydroxyl group-containing (meth)acrylates, 2-hydroxyethyl (meth)acrylate and glycerin mono(meth)acrylate are preferred, with 2-hydroxyethyl (meth)acrylate being more preferred, and 2-hydroxyethyl acrylate being even more preferred, from the viewpoint of rapidly curing the resin composition at room temperature.

[0018] The content of the hydroxyl group-containing (meth)acrylate in the radical polymerizable monomer is 0% by mass or more, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoint of improving the dispersion stability of the resin composition, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, from the viewpoint of reducing the viscosity of the resin composition. Therefore, the content of the hydroxyl group-containing (meth)acrylate in the radical polymerizable monomer is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, and even more preferably 0.5 to 5% by mass.

[0019] Examples of aromatic monomers having a carbon-carbon double bond include styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, aralkyl (meth)acrylates, and vinyltoluene, but the present invention is not limited to these examples. Examples of aralkyl (meth)acrylates include aralkyl (meth)acrylates having an aralkyl group having 7 to 18 carbon atoms, such as benzyl (meth)acrylate, phenylethyl (meth)acrylate, methylbenzyl (meth)acrylate, and naphthylmethyl (meth)acrylate, but the present invention is not limited to these examples. These aromatic monomers may be used alone or in combination of two or more. Among these aromatic monomers, styrene is preferred from the viewpoint of rapidly curing the resin composition at room temperature.

[0020] The content of the aromatic monomer having a carbon-carbon double bond in the radical polymerizable monomer is 0% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more from the viewpoint of improving the toughness of the heat dissipation material after curing, and is preferably 10% by mass or less, more preferably 8% by mass or less from the viewpoint of quickly curing the resin composition at room temperature. Therefore, the content of the aromatic monomer in the radical polymerizable monomer is preferably 0 to 10% by mass, more preferably 1 to 10% by mass, even more preferably 2 to 8% by mass, and even more preferably 3 to 8% by mass.

[0021] Examples of the carbon-carbon double bond-containing monomer having a carboxyl group include aliphatic monomers having a carboxyl group or an acid anhydride group, such as (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and maleic anhydride, which contain a carbon-carbon double bond. However, the present invention is not limited to these examples. These carbon-carbon double bond-containing monomers having a carboxyl group may be used alone or in combination of two or more. Among these carbon-carbon double bond-containing monomers having a carboxyl group, (meth)acrylic acid is preferred from the viewpoint of rapidly curing the resin composition at room temperature.

[0022] The content of the carbon-carbon double bond-containing monomer having a carboxyl group in the radical polymerizable monomer is 0% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, from the viewpoint of improving the dispersion stability of the resin composition, and is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, from the viewpoint of reducing the viscosity of the resin composition. Therefore, the content of the carbon-carbon double bond-containing monomer having a carboxyl group in the radical polymerizable monomer is preferably 0 to 5% by mass, more preferably 0.1 to 5% by mass, even more preferably 0.2 to 3% by mass, and even more preferably 0.3 to 2% by mass.

[0023] Examples of carbon-carbon double bond-containing monomers having nitrogen atoms include (meth)acrylamide, diacetone (meth)acrylamide, N-monomethyl (meth)acrylamide, N-monoethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, Nn-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, methylene bis (meth)acrylamide, N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and diacetone (meth)acrylamide (meth)acrylamide compounds, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, N-vinylpyrrolidone, and (meth)acrylonitrile, but the present invention is not limited to these examples. These carbon-carbon double bond-containing monomers having nitrogen atoms may be used alone or in combination of two or more.

[0024] Examples of carbon-carbon double bond-containing monomers having an oxo group include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate, 2-methoxytriethylene glycol (meth)acrylate, ethylene glycol (meth)acrylate, ethylene glycol methoxy (meth)acrylate, diethylene glycol (meth)acrylate, and (di)ethylene glycol (methoxy) (meth)acrylates such as diethylene glycol methoxy (meth)acrylate, but the present invention is not limited to these examples. These oxo group-containing monomers may be used alone or in combination of two or more.

[0025] Examples of the carbon-carbon double bond-containing monomer having a fluorine atom include fluoroalkyl(meth)acrylates having a fluoroalkyl group with 2 to 6 carbon atoms, such as trifluoroethyl(meth)acrylate, tetrafluoropropyl(meth)acrylate, and octafluoropentyl(meth)acrylate, but the present invention is not limited to these examples. These carbon-carbon double bond-containing monomers having a fluorine atom may be used alone or in combination of two or more.

[0026] Examples of the carbon-carbon double bond-containing monomer having an epoxy group include, but are not limited to, epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate. The carbon-carbon double bond-containing monomer having an epoxy group may be used alone or in combination of two or more types.

[0027] The glass transition temperature of the polymer obtained by polymerizing the radically polymerizable monomer is preferably −20° C. or lower, more preferably −30° C. or lower, from the viewpoint of increasing the flexibility of the heat dissipation material after curing and improving the ability of the heat dissipation material to conform to the heat generating element and the heat dissipation element. The lower limit of the glass transition temperature of the polymer is not particularly limited, but is preferably −180° C. or higher, more preferably −160° C. or higher.

[0028] <Compound (ii)> Part A of the two-part curable composition of the present disclosure contains at least one compound selected from a heterocycle-containing compound, an amino group-substituted aromatic ring-containing compound, a formyl group-substituted aromatic ring-containing compound, a compound having an alkanolamine skeleton, a thiourea structure-containing compound, and a metal salt of a carboxylic acid (hereinafter also referred to as compound (ii) of the present disclosure). The metal salt of carboxylic acid is preferably a salt of a metal having an atomic number of 20 to 56. The compound (ii) of the present disclosure preferably has a molecular weight of 500 or less, more preferably 400 or less, and even more preferably 300 or less.

[0029] Heterocycle-containing compounds of the present disclosure include imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-aminomethyl-2-methylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, and the like.

[0030] Examples of the amino group-substituted aromatic ring-containing compound of the present disclosure include aniline, N,N-dimethylaniline, N,N-diethylaniline, m-toluidine, p-toluidine, N-ethyl-m-toluidine, N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxypropyl)-p-toluidine, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, triethanolamine, diethylenetriamine, pyridine, piperidine, phenylmorpholine, and N,N-bis(hydroxyethyl)aniline.

[0031] Examples of the formyl group-substituted aromatic ring-containing compound of the present disclosure include 4-(N,N-dimethylamino)benzaldehyde, 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, and 4-(N-methyl-N-hydroxyethylamino)benzaldehyde.

[0032] Examples of compounds having an alkanolamine skeleton according to the present disclosure include diethanolaniline.

[0033] Examples of the thiourea structure-containing compound of the present disclosure include ethylene thiourea, diethyl thiourea, tetramethyl thiourea, N-acetyl thiourea, N-benzoyl thiourea, diphenyl thiourea, and dicyclohexyl thiourea.

[0034] Metal salts of carboxylic acids of the present disclosure include copper naphthenate, barium naphthenate, cobalt naphthenate, zinc octoate, vanadium octoate, cobalt octoate, and the like.

[0035] The compound (ii) of the present disclosure is preferably N,N-dimethylaniline, N,N-diethylaniline, m-toluidine, p-toluidine, N-ethyl-m-toluidine, N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, or N,N-bis(2-hydroxypropyl)-p-toluidine, more preferably N,N-dimethyl-p-toluidine, N-bis(2-hydroxyethyl)-p-toluidine, or N,N-bis(2-hydroxypropyl)-p-toluidine, and even more preferably N,N-dimethyl-p-toluidine or N-bis(2-hydroxyethyl)-p-toluidine.

[0036] The compound (ii) of the present disclosure is preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the radical polymerizable monomer, from the viewpoint of promoting the effect and rapidly curing the resin composition at room temperature.

[0037] <Peroxide> The B component of the two-component curable composition of the present disclosure is R 1 -C(=O)-OOC(=O)-R 2 It is preferable that the peroxide contains a peroxide represented by the formula (hereinafter also referred to as the peroxide of the present disclosure), where R 1 , R 2each independently represents an organic group having 1 to 20 carbon atoms. The peroxide of the present disclosure is not particularly limited, but typically functions as a polymerization initiator when the two-part curable composition of the present disclosure is cured. When the two-part curable composition of the present disclosure contains the peroxide of the present disclosure, the initial moldability (pot life) and curability (monomer conversion rate) tend to be improved.

[0038] The peroxides of the present disclosure are diacyl peroxide-based polymerization initiators, such as diacetyl peroxide, diisobutyryl peroxide, dioctanoyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide, diisononanoyl peroxide, and distearoyl peroxide.

[0039] The amount of peroxide polymerization initiator used in Liquid A per 100 parts by mass of radical polymerizable monomer is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, from the viewpoint of rapidly curing the resin composition at room temperature, and is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, from the viewpoint of extending the pot life of the resin composition and increasing the flexibility of the heat dissipation material after curing. Therefore, the amount of peroxide polymerization initiator used in Liquid A per 100 parts by mass of radical polymerizable monomer is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.

[0040] The mass ratio of the compound (ii) of the present disclosure to the peroxide polymerization initiator (reaction accelerator / peroxide polymerization initiator) is preferably 30 / 70 to 90 / 10, more preferably 40 / 60 to 85 / 15, and even more preferably 50 / 50 to 80 / 20, from the viewpoint of rapidly curing the resin composition at room temperature. Furthermore, the mass ratio of the reaction accelerator to the peroxide polymerization initiator (reaction accelerator / peroxide polymerization initiator) is preferably 30 / 70 to 90 / 10, more preferably 35 / 65 to 85 / 15, and even more preferably 40 / 60 to 80 / 20, from the viewpoint of rapidly curing the resin composition while maintaining the stability over time of the resin composition.

[0041] A suitable combination of the compound (ii) and a peroxide-based polymerization initiator is a combination of the compound (ii) containing an amino group-substituted aromatic ring-containing compound and a diacyl peroxide-based polymerization initiator, from the viewpoint of rapidly curing the resin composition at room temperature, and a combination of the compound (ii) containing an amino group-substituted aromatic ring-containing compound and dilauroyl peroxide is more preferred.

[0042] <Polymer of the present disclosure> The two-part curable composition of the present disclosure contains at least one polymer selected from the group consisting of a (meth)acrylic polymer, a polyester polymer, a polyurethane polymer, and a silicone polymer in at least one of Part A and Part B. The two-part curable composition of the present disclosure preferably contains a (meth)acrylic polymer in at least one of Part A and Part B.

[0043] The (meth)acrylic polymer of the present disclosure has a structural unit derived from a (meth)acrylic monomer. The structural unit derived from a (meth)acrylic monomer is a unit having a structure in which the carbon-carbon double bond of the (meth)acrylic monomer is replaced with a carbon-carbon single bond. The structural unit derived from a (meth)acrylic monomer can be introduced into the (meth)acrylic polymer by polymerizing the (meth)acrylic monomer.

[0044] Examples of (meth)acrylic monomers include alkyl (meth)acrylates and hydroxyl group-containing (meth)acrylates, but the present invention is not limited to these examples. These (meth)acrylic monomers may be used alone or in combination of two or more.

[0045] Examples of alkyl (meth)acrylates include alkyl (meth)acrylates having an alkyl group of 1 to 18 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, tridecyl (meth)acrylate, and n-lauryl (meth)acrylate, but the present invention is not limited to these examples. These alkyl (meth)acrylates may be used alone or in combination of two or more. Among these alkyl (meth)acrylates, alkyl (meth)acrylates in which the alkyl group has 1 to 8 carbon atoms are preferred, and n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are more preferred, from the viewpoint of increasing the flexibility of the heat dissipation material after curing and improving the ability of the heat dissipation material to conform to the heat generating element and the heat dissipation element.

[0046] From the viewpoint of increasing the flexibility of the heat dissipation material after curing and improving the ability of the heat dissipation material to conform to the heat generating element and the heat dissipation element, the content of alkyl (meth)acrylate in the (meth)acrylic monomer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more, with the upper limit being 100% by mass. Therefore, the content of alkyl (meth)acrylate in the (meth)acrylic monomer is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, even more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass.

[0047] Examples of hydroxyl group-containing (meth)acrylates include hydroxyl group-containing (meth)acrylates having an ester moiety with 1 to 18 carbon atoms, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerin mono(meth)acrylate, but the present invention is not limited to these examples. These hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more. Among these hydroxyl group-containing (meth)acrylates, 2-hydroxyethyl (meth)acrylate and glycerin mono(meth)acrylate are preferred, with 2-hydroxyethyl (meth)acrylate being more preferred, and 2-hydroxyethyl acrylate being even more preferred, from the viewpoint of rapidly curing the resin composition at room temperature. Furthermore, from the viewpoint of improving the dispersion stability of the thermally conductive material in Liquid A when the thermally conductive material described below is contained in Liquid A, 2-hydroxyethyl (meth)acrylate and glycerin mono(meth)acrylate are preferred, 2-hydroxyethyl (meth)acrylate is more preferred, and 2-hydroxyethyl acrylate is even more preferred.

[0048] The content of the hydroxyl group-containing (meth)acrylate in the (meth)acrylic monomer is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, from the viewpoints of improving the dispersion stability of the resin composition and lowering the viscosity of the resin composition, and is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, from the viewpoints of lowering the viscosity of the (meth)acrylic polymer and improving the compatibility between the (meth)acrylic monomer and the radically polymerizable monomer. Therefore, the content of the hydroxyl group-containing (meth)acrylate in the (meth)acrylic monomer is preferably 0.3 to 30% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1 to 20% by mass.

[0049] In addition to the above-mentioned monomers, the (meth)acrylic monomer may also include, within the scope that does not impair the object of the present invention, cycloalkyl (meth)acrylates such as cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; carbon-carbon double bond-containing monomers having a carboxyl group such as (meth)acrylic acid; carbon-carbon double bond-containing monomers having a silane group; carbon-carbon double bond-containing monomers having a nitrogen atom; carbon-carbon double bond-containing monomers having an oxo group; carbon-carbon double bond-containing monomers having a fluorine atom; carbon-carbon double bond-containing monomers having an epoxy group; carbon-carbon double bond-containing monomers having an aralkyl group; and aromatic monomers having a carbon-carbon double bond such as styrene.

[0050] Examples of polyester-based polymers of the present disclosure include polymers having a polyester main chain structure obtained by condensing a glycol such as ethylene glycol, propylene glycol, neopentyl glycol, or tetramethylene glycol with a dicarboxylic acid such as terephthalic acid, isophthalic acid, sebacic acid, succinic acid, phthalic acid, or adipic acid.

[0051] Examples of the polyurethane-based polymer of the present disclosure include polyurethane main chain structures obtained by reacting a polyol such as polyether polyol, polyester polyol, castor oil-based polyol, hydrogenated castor oil-based polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, or hydrogenated polyisoprene polyol with a diisocyanate such as xylylene diisocyanate, isophorone diisocyanate, methylene diphenyl diisocyanate, or toluylene diisocyanate.

[0052] <Crosslinking agent> The two-part curable composition of the present disclosure may contain a crosslinking agent in at least one of the A and B parts.

[0053] The crosslinking agent used in the present disclosure is at least one selected from the group consisting of (meth)acrylate crosslinking agents and allyl crosslinking agents. The (meth)acrylate crosslinking agents and allyl crosslinking agents may be used alone or in combination.

[0054] Examples of the (meth)acrylate crosslinking agent include (poly)ethylene glycol di(meth)acrylate such as tetraethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, urethane (meth)acrylate, triacryl isocyanurate, and triacryl cyanurate, but the present invention is not limited to these examples. These (meth)acrylate crosslinking agents may be used alone or in combination of two or more kinds.

[0055] Examples of allyl crosslinking agents include polyfunctional allyl esters and polyfunctional allyl ethers, but the present invention is not limited to these examples. These allyl crosslinking agents may be used alone or in combination of two or more. Allyl crosslinking agents have the advantage of being able to increase the mechanical strength of the crosslinked body of the heat dissipation material obtained from the resin composition, even in areas that are not covered with a masking film or the like when curing the resin composition.

[0056] The polyfunctional allyl ester is an allyl ester having two or more allyl groups in one molecule. Examples of the polyfunctional allyl ester include allyl group-containing cyanurate compounds such as triallyl isocyanurate and triallyl cyanurate; X-[COOCH2CH=CH2]n (II) (wherein X represents an n-valent aliphatic hydrocarbon group, and n represents the valence of the aliphatic hydrocarbon group), but the present invention is not limited to these examples. These polyfunctional allyl esters may be used alone or in combination of two or more.

[0057] Examples of aliphatic polyfunctional allyl esters represented by formula (II) include diallyl oxalate, diallyl malonate, diallyl succinate, diallyl glutarate, diallyl adipate, diallyl pimelate, diallyl suberate, diallyl azelaate, diallyl sebacate, diallyl fumarate, diallyl maleate, triallyl citrate, diallyl tartrate, diallyl itaconate, and diallyl citraconate, but the present invention is not limited to these examples.

[0058] The polyfunctional allyl ether is an allyl ether having two or more allyl groups in one molecule. Examples of polyfunctional allyl ethers include glycerin diallyl ether, glycerin triallyl ether, 1,4-butanediol diallyl ether, nonanediol diallyl ether, 1,4-cyclohexane dimethanol diallyl ether, triethylene glycol diallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, sorbitol diallyl ether, 1,3-bis(allyloxy)adamantane, 1,3,5-tris(allyl ether), Examples of suitable aryl ethers include (oxy)adamantane, bisphenol S diallyl ether, bisphenol A diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, 2,5-diallylphenol allyl ether, allyl ether of novolac phenol, allylated polyphenylene oxide, a compound in which the glycidyl group of an epoxy resin has been substituted with an allyl group, 1,1,2,2-tetraallyloxyethane, ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, and hexanediol diallyl ether, but the present invention is not limited to these examples.

[0059] Among the crosslinking agents, from the viewpoints of increasing the flexibility of the heat dissipation material after curing, improving the ability of the heat dissipation material to conform to the heat generating element and the heat dissipation element, and increasing the mechanical strength of the crosslinked heat dissipation material obtained from the resin composition, allyl crosslinking agents are preferred, and allyl group-containing cyanurate compounds are more preferred, and from the viewpoint of increasing curability, triallyl isocyanurate and triallyl cyanurate are even more preferred, and triallyl cyanurate is even more preferred.

[0060] Furthermore, when a (meth)acrylate crosslinking agent and an allyl crosslinking agent are used in combination as the crosslinking agent, the synergistic effect of the combination of the two increases the flexibility of the heat dissipating material after curing, improves the heat dissipating material's ability to conform to the heat generating element and the heat dissipating element, and further increases the mechanical strength of the crosslinked product (also called the cured product) of the heat dissipating material obtained from the resin composition. When a (meth)acrylate crosslinking agent and an allyl crosslinking agent are used in combination, the mass ratio of the allyl crosslinking agent to the (meth)acrylate crosslinking agent [allyl crosslinking agent / (meth)acrylate crosslinking agent] is preferably 1.5 / 1 to 5 / 1, more preferably 2 / 1 to 5 / 1, from the viewpoint of increasing the flexibility of the heat dissipating material after curing and improving the heat dissipating material's ability to conform to the heat generating element and the heat dissipating element due to the synergistic effect of the combination of the two.

[0061] The crosslinking agent may include, for example, diene-based crosslinking agents such as 1,5-hexadiene, 1,9-decadiene, 1,3-diisopropenylbenzene, and 1,4-diisopropenylbenzene, as long as the object of the present invention is not impaired.

[0062] The amount of crosslinking agent per 100 parts by mass of radical polymerizable monomer is preferably 0.001 parts by mass or more, more preferably 0.05 parts by mass or more, from the viewpoint of rapidly curing the resin composition at room temperature, and is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, from the viewpoint of ensuring the toughness of the crosslinked body of the heat dissipation material. Therefore, the amount of crosslinking agent per 100 parts by mass of radical polymerizable monomer is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass.

[0063] <Plasticizer> The two-part curable composition of the present disclosure may contain a plasticizer in at least one of the parts A and B.Examples of the plasticizer include trimellitic acid ester plasticizers such as tri-2-ethylhexyl trimellitate, tri-n-octyl trimellitate, and triisononyl trimellitate; phthalic acid ester plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, diisononyl phthalate, di-2-ethylhexyl phthalate, dibenzyl phthalate, diisodecyl phthalate, ditridecyl phthalate, and diundecyl phthalate; di-n-butyl adipate, diisobutyl adipate, Adipate ester plasticizers such as dibutoxyethyl adipate, di-n-octyl adipate, diisooctyl adipate, diisononyl adipate, bis-2-ethylhexyl adipate, and diisodecyl adipate; phosphate ester plasticizers such as tributyl phosphate, tri(2-ethylhexyl) phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate, and tricresyl phosphate; sebacates such as dibutyl sebacate, dioctyl sebacate, and di-2-ethylhexyl sebacate. Phosphate ester plasticizers; azelaic acid ester plasticizers such as dihexyl azelate and dioctyl azelate; citrate ester plasticizers such as triethyl citrate, acetyl triethyl citrate, and tri-n-butyl citrate; glycolic acid ester plasticizers such as methyl phthalyl ethyl glycolate and ethyl phthalyl ethyl glycolate; trimellitic acid ester plasticizers such as trioctyl trimellitate, tri-n-octyl-n-decyl trimellitate, and trialkyl trimellitate (alkyl group carbon number: 4 to 11); methyl acetyl Examples of suitable plasticizers include ricinoleate ester-based plasticizers such as ricinoleate, butyl acetyl ricinoleate, and glycerin monoricinoleate; maleate ester-based plasticizers such as di-n-butyl maleate; itaconate ester-based plasticizers such as monobutyl itaconate; oleate ester-based plasticizers such as butyl oleate; and glycerin-based plasticizers such as glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, and glycerin diacetomonooleate, but the present invention is not limited to these examples.These plasticizers may be used alone or in combination of two or more. Among these plasticizers, trimellitic acid ester plasticizers are preferred from the viewpoint of preventing evaporation of the plasticizer and improving the thermal stability of the plasticizer over a long period of time.

[0064] The amount of plasticizer per 100 parts by mass of the total amount of the (meth)acrylic polymer used in liquid A and liquid B is preferably 50 to 700 parts by mass, more preferably 80 to 600 parts by mass, and even more preferably 100 to 500 parts by mass, from the viewpoint of increasing the flexibility of the heat dissipation material after curing and improving the ability of the heat dissipation material to conform to the heat generating element and the heat dissipation element.

[0065] <Thermal conductive materials> The two-part curable composition of the present disclosure may contain a thermally conductive material in at least one of Part A and Part B. Examples of thermally conductive materials include alkali metal carbonate particles such as sodium carbonate particles, sodium bicarbonate particles, potassium carbonate particles, and potassium bicarbonate particles; alkaline earth metal carbonate particles such as magnesium carbonate particles, calcium carbonate particles, and barium carbonate particles; carbonate particles such as ammonium carbonate particles and ammonium bicarbonate particles; zinc oxide particles, aluminum oxide particles, magnesium oxide particles, beryllium oxide particles, calcium oxide particles, zirconium oxide particles, aluminum oxide (alumina) particles, titanium dioxide particles, silica particles, magnesium hydroxide particles, aluminum hydroxide particles, calcium silicate particles, aluminum silicate particles, silicon carbide particles, silicon nitride particles, boron nitride particles, calcium sulfate particles, barium sulfate particles, magnesium carbonate particles, glass particles, kaolin, talc, mica powder, metal particles, and carbon black particles, but the present invention is not limited to these examples. These thermally conductive materials may be used alone or in combination of two or more. Among these thermally conductive materials, aluminum oxide (alumina) particles are preferred from the viewpoint of improving the thermal conductivity of the heat dissipation material obtained using the two-component resin composition of the present invention.

[0066] The average particle size of the thermally conductive material is preferably 0.3 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more, from the viewpoint of preventing aggregation of the thermally conductive material. From the viewpoint of improving the dispersion stability of the thermally conductive material, it is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 μm or less. Therefore, the average particle size of the thermally conductive material is preferably 0.3 to 100 μm, more preferably 0.5 to 80 μm, and even more preferably 1 to 50 μm. The average particle size of the thermally conductive material refers to the volume-average particle size measured using a laser diffraction / scattering particle size distribution analyzer (manufactured by Beckman Coulter, Inc., product number LS13320).

[0067] The amount of thermally conductive material per 100 parts by weight of the combined total of (meth)acrylic polymer and radical polymerizable monomer is preferably 400 parts by weight or more, more preferably 500 parts by weight or more, and even more preferably 600 parts by weight or more, from the viewpoint of improving the thermal conductivity of the heat dissipation material obtained using the two-component resin composition; and from the viewpoint of reducing the viscosity of the two-component resin composition and improving the flexibility of the heat dissipation material after curing, it is preferably 1800 parts by weight or less, more preferably 1600 parts by weight or less, even more preferably 1400 parts by weight or less, and even more preferably 1200 parts by weight or less. Therefore, the amount of thermally conductive material per 100 parts by weight of the combined total of (meth)acrylic polymer and radical polymerizable monomer is preferably 400 to 1800 parts by weight, more preferably 500 to 1600 parts by weight, even more preferably 600 to 1400 parts by weight, and even more preferably 600 to 1200 parts by weight.

[0068] <Other ingredients> Each of Solutions A and B may contain additives to the extent that the object of the present invention is not impaired. Examples of additives include colorants such as pigments, leveling agents, UV absorbers, UV stabilizers, antioxidants, polymerization inhibitors, fillers, coupling agents, rust inhibitors, antibacterial agents, metal deactivators, wetting agents, antifoaming agents, surfactants, reinforcing agents, plasticizers, lubricants, antifogging agents, anticorrosion agents, pigment dispersants, flow control agents, peroxide decomposers, mold decolorizing agents, fluorescent brighteners, organic flame retardants, inorganic flame retardants, anti-dripping agents, melt flow modifiers, antistatic agents, anti-algae agents, anti-fungal agents, flame retardants, slip agents, metal chelating agents, anti-blocking agents, heat stabilizers, processing stabilizers, dispersants, thickeners, rheology control agents, foaming agents, antioxidants, preservatives, antistatic agents, silane coupling agents, antioxidants, and film-forming aids. However, the present invention is not limited to these examples. These additives may be used alone or in combination of two or more kinds.

[0069] <Composition and physical properties of the two-component curable composition of the present disclosure> Part A of the two-part curable composition of the present disclosure preferably contains 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more of radical polymerizable monomers in total, relative to 100% by mass of Part A. Furthermore, Part A of the disclosed two-part curable composition preferably contains 90% by mass or less of radical polymerizable monomers in total, relative to 100% by mass of Part A, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0070] The component A of the two-component curable composition of the present disclosure preferably contains a total of 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.05% by mass or more of the compound (ii) of the present disclosure relative to 100% by mass of the component A. Furthermore, the component A of the disclosed two-component curable composition preferably contains a total of 5% by mass or less of the compound (ii) of the present disclosure relative to 100% by mass of the component A, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

[0071] The two-part curable composition of the present disclosure preferably contains a total of 0.1% by mass or more of the peroxide of the present disclosure relative to 100% by mass of Part B of the two-part curable composition of the present disclosure, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. Furthermore, the two-part curable composition of the present disclosure preferably contains a total of 10% by mass or less of the peroxide of the present disclosure relative to 100% by mass of Part B of the two-part curable composition of the present disclosure, more preferably 7% by mass or less, and even more preferably 5% by mass or less.

[0072] The two-part curable composition of the present disclosure preferably contains 70 mass% or more of the peroxide of the present disclosure in total, relative to 100 mass% of the peroxides (peroxides of the present disclosure and peroxides other than the peroxides of the present disclosure) contained in Part B of the two-part curable composition of the present disclosure, more preferably 80 mass% or more, and even more preferably 90 mass% or more, and may be substantially 100 mass%.

[0073] The two-part curable composition of the present disclosure preferably contains a total of 5% by mass or more of the polymer of the present disclosure, based on 100% by mass of the total of Parts A and B of the two-part curable composition of the present disclosure, more preferably 10% by mass or more, and even more preferably 15% by mass or more. Furthermore, the two-part curable composition of the present disclosure preferably contains 90% by mass or less of the polymer of the present disclosure, based on 100% by mass of the total of Parts A and B of the two-part curable composition of the present disclosure, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0074] The two-part curable composition of the present disclosure preferably contains 70% by mass or more of (meth)acrylic polymers in total, relative to 100% by mass of the polymers of the present disclosure contained in the two-part curable composition of the present disclosure, more preferably 80% by mass or more, and even more preferably 90% by mass or more, and may be substantially 100% by mass.

[0075] In the two-part curable composition of the present disclosure, the content of silicone polymer contained in the two-part curable composition of the present disclosure is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less, relative to 100% by mass of the total polymers of the present disclosure, and particularly preferably substantially none.

[0076] The two-part curable composition of the present disclosure preferably contains a crosslinker in a total amount of 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, relative to 100% by mass of the combined total of Parts A and B of the two-part curable composition of the present disclosure. Furthermore, the two-part curable composition of the present disclosure preferably contains 10% by mass or less of the crosslinker in total, relative to 100% by mass of the combined total of Parts A and B of the two-part curable composition of the present disclosure, more preferably 7% by mass or less, and even more preferably 5% by mass or less.

[0077] The two-part curable composition of the present disclosure preferably contains a plasticizer in a total amount of 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to 100% by mass of the combined total of Parts A and B of the two-part curable composition of the present disclosure. Furthermore, the two-part curable composition of the present disclosure preferably contains a plasticizer in a total amount of 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, relative to 100% by mass of the combined total of Parts A and B of the two-part curable composition of the present disclosure.

[0078] The two-part curable composition of the present disclosure preferably contains a thermally conductive material in a total amount of 50% by mass or more, more preferably 100% by mass or more, and even more preferably 200% by mass or more, relative to 100% by mass of the combined total of Parts A and B of the two-part curable composition of the present disclosure. Furthermore, the two-part curable composition of the present disclosure preferably contains the thermally conductive material in a total amount of 2000% by mass or less, more preferably 1700% by mass or less, and even more preferably 1500% by mass or less, relative to 100% by mass of the combined total of Parts A and B of the two-part curable composition of the present disclosure.

[0079] In the two-component curable composition of the present disclosure, the mass ratio of the A component to the B component is preferably 10:90 to 90:10, and more preferably 20:80 to 80:20.

[0080] The two-component curable composition of the present disclosure is preferably a two-component curable composition containing a radical polymerizable monomer, in which the monomer conversion rate after mixing the two components at room temperature (25°C) is less than 20% after 1 hour and 80% or more after 24 hours.

[0081] In the present disclosure, the amount of liquid A excluding the thermally conductive material per 100 parts by mass of liquid B is preferably about 3 to 300 parts by mass, taking into consideration the convenience when mixing liquid A and liquid B.

[0082] The monomer conversion rate after mixing the two liquids at room temperature (25°C) is preferably less than 20% after 1 hour, more preferably less than 15%, and even more preferably less than 10%.

[0083] The monomer conversion rate after mixing the two liquids of the present disclosure at room temperature (25°C) for 24 hours is preferably 80% or more, more preferably 90% or more, even more preferably 95% or more, and particularly preferably 98% or more.

[0084] The monomer conversion rate after mixing the two liquids of the present disclosure at room temperature (25°C) for 48 hours is preferably 90% or more, more preferably 95% or more, even more preferably 98% or more, and particularly preferably 99%.

[0085] The monomer conversion rate of the present disclosure can be measured by the method described in the Examples.

[0086] [Uses of the two-part curable composition of the present disclosure] The two-component curable composition of the present disclosure can be used as a raw material for heat dissipation agents, adhesives, pressure-sensitive adhesives, gap fillers, greases, etc. The crosslinked product of the present disclosure has good initial moldability (pot life) and good curability (monomer conversion) even at room temperature, and therefore can be preferably used in applications where it is interposed between a heat-generating body such as an automobile battery and a heat dissipating body such as a heat sink, a heat dissipating fin, a resin film, or a metal plate to dissipate heat generated from the heat-generating body.

[0087] [Method of using the two-part curable composition of the present disclosure] The two-component curable composition of the present disclosure can be cured to form a crosslinked product by mixing the A-component and the B-component.

[0088] A stirring device can be used when mixing liquid A and liquid B. Examples of stirring devices include a batch mixer, a tumbler, a Henschel mixer, a Banbury mixer, a roll, a kneader, a single-screw extruder, and a twin-screw extruder, but the present invention is not limited to these examples. The temperature when mixing liquid A and liquid B is not particularly limited, but from the viewpoint of efficiently producing a crosslinked product without using devices such as a heating device or a cooling device, room temperature is preferable. Here, room temperature varies depending on the region and cannot be determined in general, but it is usually 0 to 40°C, preferably 0 to 35°C, and more preferably 1 to 30°C. Furthermore, the temperature when mixing liquid A and liquid B may be a temperature above or below room temperature as necessary. From the viewpoint of efficiently producing a crosslinked product, a temperature of about 0 to 50°C is preferable, and it may be 0 to 40°C, 0 to 35°C, or 1 to 30°C. Furthermore, the atmosphere when mixing liquid A and liquid B is not particularly limited and may be air, but from the viewpoint of avoiding the influence of oxygen gas contained in the air, it may be an inert gas such as nitrogen gas or argon gas.

[0089] When Liquid A and Liquid B of the present disclosure are mixed, the resulting mixed liquid begins to harden, and hardening typically completes within about 2 to 12 hours at room temperature. The end point of hardening of the mixed liquid can be the tack-free time of the surface of the crosslinked product obtained from the mixed liquid. The tack-free time refers to the time from the time Liquid A and Liquid B are mixed until the time when the surface of the crosslinked product formed by hardening of the mixed liquid of Liquid A and Liquid B is touched with a human finger that has been degreased with ethanol or the like, and the mixed liquid no longer adheres to the finger.

[0090] [Crosslinked Product of the Present Disclosure] The crosslinked product of the present disclosure is a crosslinked product obtained by contacting the A-liquid and B-liquid of the two-part curable composition of the present disclosure. More preferably, it is a crosslinked product obtained by a process including a step of mixing the A-liquid and B-liquid of the two-part curable composition of the present disclosure.

[0091] The shape of the crosslinked product obtained using the two-component resin composition of the present invention is not particularly limited. Examples of the shape of the crosslinked product include sheet (film), tape, cylinder, and desired molded product shapes, but the present invention is not limited to these shapes. A crosslinked product having a sheet or tape shape can be produced, for example, by mixing liquid A and liquid B, forming a coating on a substrate with the resulting mixture using, for example, a brush, bar coater, applicator, air spray, airless spray, roll coater, or flow coater, and then curing the resulting coating. Alternatively, a crosslinked product having a cylindrical shape can be produced by mixing liquid A and liquid B, extruding the resulting mixture through a T-die from an extrusion molding machine to form a cylindrical crosslinked product, and then curing the product. A crosslinked product having a desired molded shape can be produced, for example, by mixing liquid A and liquid B, and molding the resulting mixture into the desired shape using an injection molding machine or the like. [Example]

[0092] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0093] <Liquidity evaluation> The time required from the time when liquid A and liquid B were mixed in the atmosphere at 25°C until the viscosity increased was measured by stirring the mixed liquid obtained by mixing liquid A and liquid B with a glass stirring rod, and the pot life was evaluated based on the following evaluation criteria. (Evaluation criteria) ○: Pot life exceeds 60 minutes. ×: Pot life is 60 minutes or less.

[0094] <Evaluation of curability> The time from the time when Liquids A and B were mixed in the atmosphere at 25°C until the surface of the crosslinked body formed by curing the mixed liquid obtained by mixing Liquids A and B was touched with the fingers of a human hand from which oils and fats had been removed with ethanol, and the adhesion of the crosslinked body disappeared (tack-free time) was measured, and the curability was evaluated based on the following evaluation criteria. (Evaluation criteria) ◎: Tack-free time is within 12 hours. ○: Tack-free time is more than 12 hours and less than 80 hours. ×: Tack-free time exceeds 80 hours.

[0095] <Thermal conductivity> Liquid A, Liquid B, and a thermally conductive filler were mixed in the atmosphere at 25°C, and the resulting mixture was applied to a smooth polyester film with a bar coater to a thickness of 3 mm. The resulting coating was sandwiched between two polyester films to prevent air from entering, and left to stand in the atmosphere at 25°C for 48 hours to obtain a crosslinked film. The thermal conductivity of the resulting crosslinked film was measured using a Kyoto Electronics Manufacturing Co., Ltd. rapid thermal conductivity meter (product number: QTM-500), and the thermal conductivity was evaluated based on the following evaluation criteria.

[0096] The thermally conductive filler used in this evaluation was alumina powder (average particle size: 10 μm), and the amount of thermally conductive filler added was 615 parts by mass per 100 parts by mass of the total amount of Liquid A and Liquid B. (Evaluation criteria) ◎: Thermal conductivity is 1.5 W / m·K or higher. Good: Thermal conductivity is 1.0 W / m·K or more and less than 1.5 W / m·K. ×: Thermal conductivity is less than 1.0 W / m·K.

[0097] <Monomer conversion rate measurement> Liquids A, B, and a thermally conductive filler were mixed in air at 25°C. The resulting mixture was applied to a smooth polyester film to a thickness of 1 mm. The mixture was then sandwiched between two layers of polyester film to prevent air infiltration and allowed to stand at 25°C for a set period (e.g., 1 hour, 24 hours, or 48 hours) to obtain a crosslinked film. 1 g of the resulting crosslinked film was placed in a screw tube, and 0.010 g of tridecane (internal standard) was added. 10 g of ethyl acetate containing a polymerization inhibitor (p-methoxyphenol) was added, and the mixture was stirred on a hot stirrer at 50°C to precipitate the polymer. The mixture was then filtered through a 0.45 μl syringe filter and measured. Calibration curves were prepared using solutions of each monomer and the internal standard tridecane diluted with ethyl acetate. The conversion (mass%) of each monomer was determined using the internal standard method of JIS K1023:2018.

[0098] The thermally conductive filler used in this evaluation was alumina powder (average particle size: 10 μm), and the amount of thermally conductive filler added was 615 parts by mass per 100 parts by mass of the total amount of Liquid A and Liquid B. <Analysis conditions> GC: SIMADZU GC-2010Plus Column: GL Sciences InertCap1, inner diameter 0.25 mm, film thickness 0.25 μm, 30 m Column temperature: 40°C for 10 minutes → Increase temperature by 10°C per minute to 330°C INJ: 250°C, DET: 330°C Conversion rate (mass%) = (1 - amount of remaining monomer in crosslinked product (mass%) / amount of monomer in crosslinked product before curing (mass%)) x 100

[0099] Example 1 (Adjustment of solution A) 2.8 g of 2-ethylhexyl / 2-hydroxyethyl acrylate copolymer (2-ethylhexyl / 2-hydroxyethyl acrylate (mass ratio) = 95 / 5, weight average molecular weight: 250,000, glass transition temperature: approximately -68 ° C) as a (meth)acrylic polymer, 7.1 g of trimellitic ester plasticizer, 9.8 g of 2-ethylhexyl acrylate, 0.39 g of N,N-bis(2-hydroxyethyl)-p-toluidine as a reaction accelerator, and a mixture of 0.05 g of triacryl isocyanurate and 0.20 g of triallyl isocyanurate were mixed at room temperature (approximately 25 ° C) in air until a uniform composition was obtained. 172.0 g of alumina powder (average particle size: 10 μm) was further added to the mixture and mixed until a uniform composition was obtained, thereby obtaining a two-part curable composition (1) of the present disclosure.

[0100] (Adjustment of solution B) 2.2 g of 2-ethylhexyl / 2-hydroxyethyl acrylate copolymer (2-ethylhexyl / 2-hydroxyethyl acrylate (mass ratio) = 95 / 5, weight average molecular weight: 250,000, glass transition temperature: approximately -68°C) as a (meth)acrylic polymer, 5.4 g of a trimellitic acid ester plasticizer, and 0.22 g of dilauroyl peroxide (manufactured by NOF Corporation, trade name: Perloyl L) as a peroxide polymerization initiator were mixed at room temperature (approximately 25°C) in the air to obtain part B of the two-part curable composition (1) of the present disclosure.

[0101] (evaluation) The fluidity, curability, and thermal conductivity of the two-component curable composition (1) of the present disclosure were investigated using the components A and B according to the criteria described above. The results are shown in Table 1. In Table 1, the two-component curable composition (1) of the present disclosure is referred to as composition (1).

[0102] <Example 2> (Adjustment of solution A) 2.8 g of 2-ethylhexyl / 2-hydroxyethyl acrylate copolymer (2-ethylhexyl / 2-hydroxyethyl acrylate (mass ratio) = 95 / 5, weight average molecular weight: 250,000, glass transition temperature: approximately -68 ° C) as a (meth)acrylic polymer, 7.1 g of trimellitic ester plasticizer, 9.8 g of 2-ethylhexyl acrylate, 0.39 g of N,N-bis(2-hydroxyethyl)-p-toluidine as a reaction accelerator, and a mixture of 0.05 g of triacryl isocyanurate and 0.20 g of triallyl isocyanurate were mixed at room temperature (approximately 25 ° C) in air until a uniform composition was obtained. 172.0 g of alumina powder (average particle size: 10 μm) was further added to the mixture and mixed until a uniform composition was obtained, thereby obtaining a two-component curable composition (2) A of the present disclosure.

[0103] (Adjustment of solution B) 2.2 g of 2-ethylhexyl / 2-hydroxyethyl acrylate copolymer (2-ethylhexyl / 2-hydroxyethyl acrylate (mass ratio) = 95 / 5, weight average molecular weight: 250,000, glass transition temperature: approximately -68°C) as a (meth)acrylic polymer, 5.4 g of a trimellitic acid ester plasticizer, and 0.15 g of dilauroyl peroxide (manufactured by NOF Corporation, trade name: Perloyl L) as a peroxide polymerization initiator were mixed at room temperature (approximately 25°C) in the air to obtain part B of the two-part curable composition (1) of the present disclosure.

[0104] (evaluation) The fluidity, curability, and thermal conductivity of the two-component curable composition (2) of the present disclosure were investigated using the components A and B according to the criteria described above. The results are shown in Table 1. In Table 1, the two-component curable composition (2) of the present disclosure is referred to as composition (2).

[0105] Example 3 (Adjustment of solution A) 2.8 g of 2-ethylhexyl / 2-hydroxyethyl acrylate copolymer (2-ethylhexyl / 2-hydroxyethyl acrylate (mass ratio) = 95 / 5, weight average molecular weight: 250,000, glass transition temperature: approximately -68 ° C) as a (meth)acrylic polymer, 7.1 g of trimellitic ester plasticizer, 9.8 g of 2-ethylhexyl acrylate, 0.39 g of N,N-bis(2-hydroxyethyl)-p-toluidine as a reaction accelerator, 0.05 g of triacryl isocyanurate, 0.20 g of triallyl isocyanurate, and 0.015 g of t-butylcatechol were mixed at room temperature (approximately 25 ° C) in air until a uniform composition was obtained. 172.0 g of alumina powder (average particle size: 10 μm) was further added to the mixture and mixed until a uniform composition was obtained, thereby obtaining a two-component curable composition (3) of the present disclosure.

[0106] (Adjustment of solution B) 2.2 g of 2-ethylhexyl / 2-hydroxyethyl acrylate copolymer (2-ethylhexyl / 2-hydroxyethyl acrylate (mass ratio) = 95 / 5, weight average molecular weight: 250,000, glass transition temperature: approximately -68°C) as a (meth)acrylic polymer, 5.4 g of trimellitic acid ester plasticizer, and 0.35 g of dilauroyl peroxide (manufactured by NOF Corporation, trade name: Perloyl L) as a peroxide polymerization initiator were mixed at room temperature (approximately 25°C) in the air to obtain part B of two-part curable composition (3) of the present disclosure.

[0107] (evaluation) The fluidity, curability, and thermal conductivity of the two-component curable composition (3) of the present disclosure were investigated using the components A and B according to the criteria described above. The results are shown in Table 1. In Table 1, the two-component curable composition (3) of the present disclosure is referred to as composition (3).

[0108] <Comparative Example 1> (Adjustment of solution A) 2.8 g of 2-ethylhexyl / 2-hydroxyethyl acrylate copolymer (2-ethylhexyl / 2-hydroxyethyl acrylate (mass ratio) = 95 / 5, weight average molecular weight: 250,000, glass transition temperature: approximately -68°C) as a (meth)acrylic polymer, 7.1 g of trimellitic ester plasticizer, 9.8 g of 2-ethylhexyl acrylate, 0.5 g of hexoate cobalt as a reaction accelerator, and a mixture of 0.05 g of triacryl isocyanurate and 0.20 g of triallyl isocyanurate were mixed at room temperature (approximately 25°C) in air until a uniform composition was obtained. 172.0 g of alumina powder (average particle size: 10 μm) was added to the mixture and mixed until a uniform composition was obtained, thereby obtaining a comparative two-part curable composition (1) as part A.

[0109] (Adjustment of solution B) 2.2 g of 2-ethylhexyl / 2-hydroxyethyl acrylate copolymer (2-ethylhexyl / 2-hydroxyethyl acrylate (mass ratio) = 95 / 5, weight average molecular weight: 250,000, glass transition temperature: approximately -68°C) as a (meth)acrylic polymer, 5.4 g of a trimellitic ester plasticizer, and 0.20 g of cumene hydroperoxide (manufactured by NOF Corporation, trade name: Percumyl H) as a peroxide polymerization initiator were mixed at room temperature (approximately 25°C) in the air to obtain component B of a comparative two-component curable composition (1).

[0110] (evaluation) The flowability, curability, and thermal conductivity of the comparative two-component curable composition (1) were investigated using components A and B according to the criteria described above. The results are shown in Table 1. In Table 1, the comparative two-component curable composition (1) is referred to as comparative composition (1).

[0111] <Comparative Example 2> (Adjustment of solution A) 2.8 g of 2-ethylhexyl / 2-hydroxyethyl acrylate copolymer (2-ethylhexyl / 2-hydroxyethyl acrylate (mass ratio) = 95 / 5, weight average molecular weight: 250,000, glass transition temperature: approximately -68°C) as a (meth)acrylic polymer, 7.1 g of trimellitic ester plasticizer, 9.8 g of 2-ethylhexyl acrylate, 0.5 g of hexoate cobalt as a reaction accelerator, and a mixture of 0.05 g of triacryl isocyanurate and 0.20 g of triallyl isocyanurate were mixed at room temperature (approximately 25°C) in air until a uniform composition was obtained. 172.0 g of alumina powder (average particle size: 10 μm) was added to the mixture and mixed until a uniform composition was obtained, thereby obtaining a comparative two-part curable composition (2) for Part A.

[0112] (Adjustment of solution B) 2.2 g of 2-ethylhexyl / 2-hydroxyethyl acrylate copolymer (2-ethylhexyl / 2-hydroxyethyl acrylate (mass ratio) = 95 / 5, weight average molecular weight: 250,000, glass transition temperature: approximately -68°C) as a (meth)acrylic polymer, 5.4 g of a trimellitic ester plasticizer, and 0.05 g of cumene hydroperoxide (manufactured by NOF Corporation, trade name: Percumyl H) as a peroxide polymerization initiator were mixed at room temperature (approximately 25°C) in the air to obtain component B of a comparative two-component curable composition (2).

[0113] (evaluation) The flowability, curability, and thermal conductivity of the comparative two-component curable composition (2) were investigated using components A and B according to the criteria described above. The results are shown in Table 1. In Table 1, the comparative two-component curable composition (2) is referred to as comparative composition (2).

[0114] [Table 1]

[0115] From the above, it has become clear that the two-component curable composition of the present disclosure has good initial moldability (pot life) and good curability (monomer conversion) even at room temperature. Furthermore, it has become clear that the two-component curable composition of the present disclosure also has good thermal conductivity and can therefore be suitably used, for example, as a two-component resin composition.

Claims

1. a solution A containing (i) a radical polymerizable monomer and (ii) at least one compound selected from a heterocycle-containing compound, an amino group-substituted aromatic ring-containing compound, a formyl group-substituted aromatic ring-containing compound, a compound having an alkanolamine skeleton, a thiourea structure-containing compound, and a metal salt of a carboxylic acid; (iii) R １ -C(=O)-O-O-C(=O)-R ２ Peroxides represented by the formula (wherein R １ , R ２ each independently represents an organic group having 1 to 20 carbon atoms; and At least one of the components A and B comprises (iv) at least one polymer selected from the group consisting of a (meth)acrylic polymer, a polyester polymer, a polyurethane polymer, and a silicone polymer.

2. The two-part curable composition according to claim 1, wherein Part A further contains a plasticizer.

3. The two-component curable composition according to claim 1 or 2, wherein the component A further contains a thermally conductive material.

4. The two-component curable composition according to any one of claims 1 to 3, wherein Part A further contains a crosslinking agent.

5. A crosslinked product obtained by using the two-component curable resin composition according to any one of claims 1 to 4.

6. A laminate comprising the crosslinked product according to claim 5 and a resin or a metal.

7. a solution A containing (i) a radical polymerizable monomer and (ii) at least one compound selected from a heterocycle-containing compound, an amino group-substituted aromatic ring-containing compound, a formyl group-substituted aromatic ring-containing compound, a compound having an alkanolamine skeleton, a thiourea structure-containing compound, and a metal salt of a carboxylic acid; (iii) R １ -C(=O)-O-O-C(=O)-R ２ Peroxides represented by the formula (wherein R １ , R ２ each independently represents an organic group having 1 to 20 carbon atoms), At least one of the liquids A and B (iv) contains at least one polymer selected from the group consisting of (meth)acrylic polymers, polyester polymers, polyurethane polymers, and silicone polymers.

8. A two-component curable composition containing a radical polymerizable monomer, wherein the monomer conversion rate after mixing the two components at room temperature (25°C) is less than 20% after 1 hour and is 80% or more after 24 hours.

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