Curable composition, cured product, method for producing same, and layered product

Abstract

Provided are: a curable composition able to yield a cured product which exhibits excellent adhesive strength after a long period of time in a high temperature high humidity environment and excellent adhesive properties at 25°C; a cured product; a method for producing same; and a layered product. A curable composition according to the present disclosure contains: a specific quantity of a modified tetracarboxylic acid (A) of formula (I) and / or formula (II); a specific quantity of a silica filler (B) and / or a thermally conductive filler (C); a curing agent (D); and a specific quantity of a resin (E). (I): A product of a reaction between an aliphatic tetracarboxylic acid anhydride (I-a) and a compound (I-b1) having one terminal hydroxyl group. (II): A product of the reaction between an aromatic tetracarboxylic acid anhydride (II-a) and a hydroxyl group-containing compound (II-b) having an ether bond in the molecular structure, wherein the compound (II-b) is a compound (II-b1) having one hydroxyl group at its terminal and / or a compound (II-b2) having two hydroxyl groups at its terminal.

Description

Curable composition, cured product, method for producing the same, and laminate

[0001] The present disclosure relates to a curing agent composition, a cured product of the curable composition, a method for producing the same, and a laminate.

[0002] Integrated circuits (ICs) are essential components of electronic components, such as microprocessors, transistors, and memories, and are mounted in various electronic devices such as computers, smartphones, and flat panel displays. Packages containing ICs or mounting substrates on which ICs are mounted use insulating resins such as encapsulants, adhesives, underfill agents, and potting materials.

[0003] Patent Document 1 discloses a resin composition for use as a mold underfill material for wafer-level chip scale packages (WL-CS). The resin composition contains a polymer resin having a number-average molecular weight within a specific range and one or more structures selected from polybutadiene, polyisoprene, polycarbonate, (meth)acrylate, and polysiloxane structures, an inorganic filler, an epoxy resin, and a curing accelerator. Patent Document 2 also proposes an encapsulating film containing one or more elastomers selected from the group consisting of butadiene-based rubbers and silicone-based rubbers, an epoxy resin, a curing agent, and an inorganic filler, with the elastomer component contained in a specific amount. Patent Document 3 also discloses a radically polymerizable polyamide, which is a reaction product of a polyamide having a dimer structure consisting of a dimer acid or dimer diamine and a phenolic hydroxyl unit, and a hydroxyl group in its side chain, with a radically polymerizable epoxy. Patent Document 4 also discloses a resin composition containing the radically polymerizable polyamide, a photopolymerization initiator, an epoxy resin, a phenolic resin, a silica filler, a solvent, and the like. Furthermore, Patent Document 4 discloses a thermosetting resin composition containing a polyamide having a dimer structure, which is obtained by polymerizing a polybasic acid monomer and a polyamine monomer and has phenolic hydroxyl groups in its side chains, and a tri- or higher functional compound capable of reacting with the phenolic hydroxyl groups.

[0004] JP 2017-057313 A, International Publication No. 2016 / 136741, JP 2019-119886 A, International Publication No. 2016 / 001949

[0005] The manufacturing process of a semiconductor package involves multiple heating steps to form a rewiring layer. For example, fan-out wafer-level packaging (FO-WLP) has attracted attention as a chip-sized package that can increase the number of pins. The manufacturing process of a face-down WLP, a typical FO-WLP, involves sealing one side of a semiconductor chip with a molding resin composition, followed by repeated heating steps in the subsequent rewiring layer formation process. For this reason, there is a demand for resin compositions with high humidity and heat resistance.

[0006] Electronic components and devices are widely used in automobiles, industrial machinery, ships, aircraft, and other applications. In these applications, moisture can accumulate at the interface between the chip and the molding resin, potentially causing package cracks, wire breakage, metal corrosion, and electrochemical migration due to water vapor expansion. Therefore, in recent years, there has been a demand for encapsulating materials that demonstrate high adhesive reliability in long-term aging tests under high temperature and humidity. Meanwhile, in response to the trend toward higher performance electronic components, resin compositions with high adhesive strength at 25°C are required to enhance product stability. However, achieving both stable adhesive strength, which requires resin rigidity, and adhesive strength, which requires polymer chain flexibility, is not easy.

[0007] The present disclosure has been made in view of the above background, and aims to provide a curable composition, a cured product, a laminate, and a method for producing a cured product, which are capable of producing a cured product that has excellent adhesive strength after long-term storage at high temperature and high humidity, and excellent adhesiveness at 25°C.

[0008] As a result of extensive research, the present inventors have found that the problems of the present disclosure can be solved in the following aspects, and have completed the present disclosure as described below. [1]: A curable composition comprising a tetracarboxylic acid modified product (A), at least one of a silica filler (B) and a thermally conductive filler (C), a curing agent (D), and a resin (E), wherein the tetracarboxylic acid modified product (A) is at least one of the following (I) and (II): the resin (E) is a resin selected from the group consisting of a polyamide resin, a polyester resin, a polyether resin, an acrylic resin, an olefin resin, a maleimide resin, a styrene-containing elastomer, a chain olefin-containing elastomer, and a silicone resin, and the polyamide resin contains a dimer acid and a dimer diamine in a total amount of 50 to 99 mass% relative to 100 mass% of the monomers constituting the polyamide resin, and the curable composition contains, relative to 100 mass% of the nonvolatile content of the curable composition, 0.1 to 5 mass% of the tetracarboxylic acid modified product (A), 40 to 95 mass% of the silica filler (B) and the thermally conductive filler (C), and 0.1 to 40 mass% of the resin (E). (I): A reaction product of an aliphatic tetracarboxylic anhydride (I-a) and a compound (I-b1) having one terminal hydroxyl group. (II): A reaction product of an aromatic tetracarboxylic anhydride (II-a) and a hydroxyl-containing compound (II-b) having an ether bond in its molecular structure, wherein the hydroxyl-containing compound (II-b) is a compound (II-b1) having one terminal hydroxyl group and / or a compound (II-b2) having two terminal hydroxyl groups. [2]: The curable composition according to [1], wherein the compound (I-b1) having one terminal hydroxyl group contains at least one of an ether bond and an ester bond in part of its molecular structure and has a weight-average molecular weight of 500 to 10,000. [3]: The curable composition according to [1], wherein the compound (II-b1) having one terminal hydroxyl group and the compound (II-b2) having two terminal hydroxyl groups each independently have a weight average molecular weight of 500 to 10,000. [4]: ​​The curable composition according to any one of [1] to [3], wherein the resin (E) has a glass transition temperature of -10 to 90°C. [5]: The curable composition according to any one of [1] to [4], wherein the curing agent (D) contains an epoxy-based curing agent.[6]: The curable composition according to any one of [1] to [5], wherein the thermally conductive filler (C) comprises alumina. [7]: A cured product of the curable composition according to any one of [1] to [6]. [8]: A laminate comprising an adhesive layer made of the cured product according to [7] and a substrate. [9]: A method for producing a cured product, comprising the steps of thermally melting and molding the curable composition according to any one of [1] to [6], and thermally curing the cured product.

[0009] The present disclosure has the excellent effect of providing a curable composition, a cured product, a laminate, and a method for producing a cured product, which have excellent adhesive strength after long-term storage at high temperature and high humidity, and excellent adhesiveness at 25°C.

[0010] The present disclosure will be described in detail below. Needless to say, other embodiments are also included within the scope of the present disclosure as long as they are consistent with the spirit of the present disclosure. Furthermore, in this specification, a numerical range specified using "to" includes the lower and upper limits of the numerical values ​​written before and after "to." Furthermore, in this specification, "film" and "sheet" are not distinguished by thickness. In other words, in this specification, "sheet" includes thin film-like objects, and "film" in this specification includes thick sheet-like objects. Furthermore, unless otherwise noted, the various components in this specification may be used independently, either singly or in combination of two or more types. Furthermore, the numerical values ​​specified in this specification are values ​​obtained by the methods described in the embodiments or examples.

[0011] In this specification, "Mw" refers to the weight average molecular weight in terms of polystyrene, determined by gel permeation chromatography (GPC) measurement, which can be measured by the method described in the Examples section.

[0012] <Curable Composition> The curable composition of the present disclosure (hereinafter also referred to as the present composition) contains a tetracarboxylic acid modified product (A), at least one of a silica filler (B) and a thermally conductive filler (C), a curing agent (D), and a resin (E). The tetracarboxylic acid modified product (A) is at least one of the following (I) and (II): (I): A reaction product of an aliphatic tetracarboxylic acid anhydride (I-a) and a compound (I-b1) having one terminal hydroxyl group. (II): A reaction product of an aromatic tetracarboxylic acid anhydride (II-a) and a hydroxyl group-containing compound (II-b) having an ether bond in its molecular structure. The hydroxyl group-containing compound (II-b) is a compound (II-b1) having one terminal hydroxyl group and / or a compound (II-b2) having two terminal hydroxyl groups. As the hydroxyl group-containing compound (II-b), either (II-b1) or (II-b2) may be used, or a mixture of them may be used.

[0013] Resin (E) is a resin selected from the group consisting of polyester resins, polyether resins, acrylic resins, olefin resins, maleimide resins, styrene-containing elastomers, linear olefin-containing elastomers, silicone resins, and polyamide resins. The polyamide resin contains 50 to 99 mass% of dimer acid and dimer diamine in total, based on 100 mass% of the monomers constituting the polyamide resin (hereinafter referred to as polyamide resin (e1)). Note that "containing 50 to 99 mass% of dimer acid and dimer diamine in total, based on 100 mass% of the monomers constituting the polyamide resin" is synonymous with "using 50 to 99 mass% of dimer acid and dimer diamine-derived structural units in total, based on 100 mass% of the structural units derived from the monomers constituting the polyamide resin," and substantially corresponds to the feed ratio of the monomers used in the polymerization of polyamide resin (e1). When polyamide resin is synthesized by a condensation reaction of polycarboxylic acid and polyamine, water is dehydrated. However, when calculating the "total of dimer acid and dimer diamine per 100% by mass of the monomers constituting the polyamide resin," the mass of the dehydrated water is not taken into consideration, and the calculation is based on the mass ratio of the monomers.

[0014] The composition contains, based on 100% by mass of the nonvolatile content of the composition, 0.1 to 5% by mass of the tetracarboxylic acid modified product (A), 40 to 95% by mass in total of the silica filler (B) and the thermally conductive filler (C), and 0.1 to 40% by mass of the resin (E). Each component will be described below.

[0015] [Tetracarboxylic acid modified product (A)] As described above, the tetracarboxylic acid modified product (A) is at least one of (I) and (II). The content of the tetracarboxylic acid modified product (A) is 0.1 to 5 mass% and preferably 0.5 to 3 mass% based on 100 mass% of the nonvolatile content of the composition. By adjusting the content to 0.1 to 5 mass%, a good balance of adhesive strength after long-term storage under high temperature and high humidity conditions and adhesive strength at 25°C can be achieved. Note that the above content is the total value when (I) and (II) are mixed. Below, the above (I) and (II) will be explained in order.

[0016] <(I): Tetracarboxylic Acid Modified Product (A)> By using (I), a reaction product of an aliphatic tetracarboxylic acid anhydride (I-a) and a compound (I-b1) (hereinafter also referred to as compound (I-b1)) having one terminal hydroxyl group, as the tetracarboxylic acid modified product (A), the adhesive strength after prolonged aging under high temperature and high humidity is improved. This is thought to be due to the effect of the monool derived from compound (I-b1) and the carboxylic acid residue derived from the aliphatic tetracarboxylic acid anhydride (I-a1). In other words, these structures widen the hydrogen bond spacing of other components such as resin (E), optimizing the strength of the hydrogen bonds. For example, by combining polyamide resin (e1) with the tetracarboxylic acid modified product (A) of (I), the intermolecular interactions of the polyamide resin (e1) are reduced and uniformly distributed in the curable composition, thereby significantly improving the adhesive strength after prolonged aging under high temperature and high humidity.

[0017] <Aliphatic Tetracarboxylic Acid Anhydride (I-a)> The aliphatic tetracarboxylic acid anhydride (I-a) is a tetracarboxylic acid anhydride having a chain hydrocarbon structure and / or an alicyclic hydrocarbon structure adjacent to the acid anhydride. The "chain hydrocarbon structure" is a linear hydrocarbon structure and / or a branched hydrocarbon structure which may have an unsaturated bond. The "alicyclic hydrocarbon structure" is an alicyclic hydrocarbon which may have an unsaturated bond, and may be monocyclic or polycyclic. These may contain a substituent. Furthermore, the portion not adjacent to the acid anhydride may contain an aromatic group.

[0018] Specific examples of the aliphatic tetracarboxylic acid anhydride (I-a) include tetracarboxylic acid dianhydrides having a chain hydrocarbon structure such as 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 1,2,4,5-pentanetetracarboxylic acid, 1,2,3,4-hexanetetracarboxylic acid, and 1,2,5,6-hexanetetracarboxylic acid. Specific examples of the aliphatic tetracarboxylic acid anhydride (I-a) include cyclobutane-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, cyclohexane-1,2,3,4-tetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid, rel-dicyclohexyl-3,3',4,4'-tetracarboxylic acid, and tricyclo[4.2.2.0]tetracarboxylic acid. ２，５]dec-9-ene-3,4,7,8-tetracarboxylic acid, 5-carboxymethylbicyclo[2.2.1]heptane-2,3,6-tricarboxylic acid, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,6,7-tetracarboxylic acid, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid, bicyclo[3.3.0]octane-2,4,6,7-tetracarboxylic acid, 7,8-diphenylbicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 4,8-diphenyl-1,5-diazabicyclooctane-2,3,6,7-tetracarboxylic acid, 9-oxatricyclo[4.2.1.0 ２，５ ]nonane-3,4,7,8-tetracarboxylic acid, 9,14-dioxopentacyclo[8.2.11,11.14,7.02,10.0 ３，８cyclo-, bicyclo-, and tricyclotetracarboxylic acids such as 2,8-dioxaspiro[4.5]decane-1,3,7,9-tetracarboxylic acid; spiro ring-containing tetracarboxylic acids such as 2,8-dioxaspiro[4.5]decane-1,3,7,9-tetratone; and tetracarboxylic acid dianhydrides having an alicyclic hydrocarbon structure such as 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride. From the viewpoint of improving compatibility with the resin (E), the aliphatic tetracarboxylic acid anhydride (I-a) is preferably 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 1,2,3,4-butanetetracarboxylic acid, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, or bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid. In particular, by combining these compounds with the polyamide resin (e1), compatibility is significantly improved. The aliphatic tetracarboxylic acid anhydride (I-a) may be used alone or in combination of two or more.

[0019] <Compound (I-b1) Having One Terminal Hydroxyl Group> Examples of the compound (I-b1) include alcohol compounds having a long-chain alkyl group with an average carbon number of 25 to 50, monools derived from polyethylene glycol, monools derived from polypropylene glycol, and polyester monools. Among these, the compound (I-b1) preferably contains at least one of an ether bond and an ester bond as part of its molecular structure. Specifically, monools derived from polyethylene glycol and polyester monools are preferred. By using these, the adhesive strength can be well maintained even after long-term storage under high temperature and high humidity. In particular, the compound (e1) effectively widens the spacing between hydrogen bonds, optimizes the strength of the hydrogen bonds, and significantly improves the adhesive strength after long-term storage under high temperature and high humidity.

[0020] The weight-average molecular weight (Mw) of compound (I-b1) is preferably 500 to 10,000, and more preferably 2,000 to 8,000. By having an Mw of 500 to 10,000, the adhesive strength can be well maintained even after long-term storage under high temperature and high humidity conditions.

[0021] Examples of alcohol compounds having a long-chain alkyl group with an average carbon number of 25 to 50 include natural fatty acids such as heptacosanoic acid, octacosanoic acid, pentacosanoic acid, cerotic acid, melissic acid, nonacosanoic acid, and montanic acid, as well as purified compounds thereof, and alcohols derived from synthetic fatty acids within the above ranges. Commercially available alcohols derived from synthetic fatty acids include Unilin 350, Unilin 550, and Unilin 700, synthetic fatty acids manufactured by NuCeraSolutions, Inc.

[0022] Examples of monools derived from polyethylene glycol and polypropylene glycol include those obtained by polymerizing ethylene oxide (EO) or propylene oxide (PO) using alcohol as an initiator. Commercially available EO adducts of synthetic alcohols having an average carbon number of 20 to 50 include Unithox 450, Unithox 480, and Unithox 750 manufactured by NuCera Solutions.

[0023] Examples of polyester monools include polyester monools obtained by ring-opening polymerization of a cyclic compound using a monoalcohol or a monoamine as an initiator. The monoalcohol or monoamine used as the initiator is not particularly limited. From the viewpoint of improving compatibility with the resin (E), it is preferable to use a monoalcohol containing an aromatic ring or an alkyleneoxy unit and having a molecular weight of 300 or less, or a monoamine containing an aromatic ring or an alkyleneoxy unit and having a molecular weight of 300 or less.

[0024] Examples of aromatic ring-containing monoalcohols having a molecular weight of 300 or less include primary hydroxyl group-containing monoalcohols such as benzyl alcohol, phenoxyethanol, paracumylphenoxyethyl alcohol, piperonyl alcohol, and 1-naphthalenemethanol, and secondary hydroxyl group-containing monoalcohols such as 1-hydroxyindane and 1-phenyl-1-propanol. Among these, from the viewpoint of compatibility between the resin (E) and the tetracarboxylic acid modified product (A), benzyl alcohol and phenoxyethanol are preferred as initiators, and combinations of these initiators with the polyamide resin (e1) are more preferred.

[0025] Examples of alkyleneoxy unit-containing monoalcohols having a molecular weight of 300 or less include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether,Examples of the initiator include alkylene glycol monoalkyl ethers such as tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetradiethylene glycol monomethyl ether. Among these, from the viewpoint of compatibility with the resin (E), diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether are preferred, and combinations of these initiators with the polyamide resin (e1) are more preferred.

[0026] Examples of aromatic ring-containing monoamines having a molecular weight of 300 or less include benzylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methyl-6-benzylamine, 4-methylbenzylamine, 4-(aminomethyl)phenol, 4-fluorobenzylamine, 2-(benzyloxy)ethanamine, 1-aminoindan, etc. Among these, benzylamine is preferred from the viewpoint of compatibility with resin (E), and a combination of the initiator and polyamide resin (e1) is more preferred.

[0027] Examples of alkyleneoxy unit-containing monoamines having a molecular weight of 300 or less include 3,6,9,12-tetraoxadecanamine, tert-butyl 3-[2-(2-aminoethoxy)ethoxy]propanoate, etc. Among these, 3,6,9,12-tetraoxadecanamine is preferred from the viewpoint of compatibility with resin (E), and a combination of the initiator with polyamide resin (e1) is more preferred.

[0028] The initiator used to produce the polyester monool is preferably a monoalcohol. The monoalcohol and monoamine may be used alone or in combination of two or more kinds.

[0029] Examples of cyclic compounds that can be used in producing polyester monools include alkylene oxides, lactones, lactides, dicarboxylic acid anhydrides, epoxides, etc. The cyclic compounds can be used alone or in combination of two or more.

[0030] Examples of alkylene oxides that can be used include ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide, and combinations of two or more of these. When two or more alkylene oxides are used in combination, the bonding form may be either random and / or block. The number of polymerization moles of alkylene oxide per mole of initiator is preferably 0 to 100.

[0031] The polymerization of alkylene oxide can be carried out, for example, in the presence of an alkali catalyst at a temperature of 100 to 200° C. under pressure. Polymers (PeOH) obtained by polymerizing alkylene oxide with the hydroxyl group of a monoalcohol are commercially available, such as the Uniox series manufactured by NOF Corporation and the Blenmer series manufactured by NOF Corporation, and these can be used as the polymer (PeOH) in the production method of the present disclosure. Commercially available products include, for example, Uniox M-400, M-550, M-2000, Blenmar PE-90, PE-200, PE-350, AE-90, AE-200, AE-400, PP-1000, PP-500, PP-80, AP-150, AP-400, AP-550, AP-800, 50PEP-300, 70PEP-350B, AEP series, 55PET-400, 30PET-800, 55PET-800, AET series, 30PPT-800, 50PPT-800, 70PPT-800, APT series, 10PPB-500B, 10APB-500B, etc. In the present specification, the first step may be omitted by using these commercially available products.

[0032] Examples of lactones include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone. Among these, δ-valerolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone are preferred in terms of ring-opening polymerization properties. Lactones can be used without being limited to the above examples, and may be used alone or in combination of two or more types.

[0033] As the lactide, those represented by the following general formula (1) are preferred (including glycolide).

[0034] [In general formula (1), R ３１ and R ３２ are each independently selected from the group consisting of a hydrogen atom and a saturated or unsaturated, linear or branched alkyl group having 1 to 20 carbon atoms; R ３３ and R ３４ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, and a saturated or unsaturated, straight-chain or branched lower alkyl group having 1 to 9 carbon atoms.] The lactide is preferably lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) or glycolide (1,4-dioxane-2,5-dione). Of the lactones and lactides, lactones are more preferred.

[0035] The ring-opening polymerization of lactone and / or lactide can be carried out, for example, by charging an initiator, lactone and / or lactide, and a polymerization catalyst into a reactor connected to a dehydration tube and a condenser, and carrying out the reaction under a nitrogen stream. When a low-boiling monoalcohol is used, the reaction can be carried out under pressure using an autoclave. When a monoalcohol having an ethylenically unsaturated double bond is used, it is preferable to add a polymerization inhibitor and carry out the reaction under a dry air stream.

[0036] The number of moles of lactone and / or lactide to be polymerized per mole of initiator is preferably in the range of 1 to 60 moles, more preferably 2 to 20 moles, and particularly preferably 3 to 15 moles.

[0037] Examples of the polymerization catalyst include quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide; tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide; Examples of catalysts include quaternary phosphonium salts such as trimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodide, as well as phosphorus compounds such as triphenylphosphine, organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate, alkali metal alcoholates such as sodium alcoholate and potassium alcoholate, tertiary amines, organotin compounds, organoaluminum compounds, organotitanate compounds, and zinc compounds such as zinc chloride. The amount of catalyst used is 0.1 ppm to 3,000 ppm, preferably 1 ppm to 1,000 ppm, based on the mass of the lactone and / or lactide. By using a catalyst in an amount of 0.1 to 3,000 ppm, it is easy to obtain a colorless polymer at a polymerization rate suitable for production.

[0038] The ring-opening polymerization temperature of lactone and / or lactide is in the range of 100° C. to 220° C., preferably 110° C. to 210° C. By setting the temperature at 100 to 220° C., it is easy to obtain a polymer with few by-products at a polymerization rate suitable for production.

[0039] Examples of dicarboxylic acid anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, itaconic anhydride, glutaric anhydride, dodecenylsuccinic anhydride, and chlorendec anhydride.

[0040] Examples of epoxides include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, phenyl glycidyl ether, p-tertiary butylphenyl glycidyl ether, 2,4-dibromophenyl glycidyl ether, 3-methyl-dibromophenyl glycidyl ether (however, the substitution position of the bromo is optional), allyl glycidyl ether, ethoxyphenyl glycidyl ether, glycidyl (meth)acrylate, glycidyl phthalimide, and styrene oxide.

[0041] The method for producing the polyester monool is not particularly limited, but for example, an alkylene oxide can be polymerized with the initiator in the first stage, followed by polymerization of a lactone in the second stage, and then alternating polymerization of a dicarboxylic acid anhydride and an epoxide in the third stage. In this example, the initiator used for polymerization of the lactone in the second stage is the alkylene oxide polymer having a hydroxyl group at one end polymerized in the first stage. Furthermore, the initiator used for alternating polymerization of the dicarboxylic acid anhydride and the epoxide in the third stage is a block copolymer of the alkylene oxide polymer having a hydroxyl group at one end polymerized up to the second stage and the lactone polymer.

[0042] The reaction order of the cyclic compounds is not limited to the combination of alkylene oxide in the first step, lactone in the second step, and dicarboxylic acid anhydride and epoxide in the third step, and the combinations of alkylene oxide, lactone (and / or lactide), and dicarboxylic acid anhydride and epoxide can be carried out in any order, one or more times each. Alternatively, instead of carrying out ring-opening polymerization for all of the combinations of alkylene oxide, lactone (and / or lactide), and dicarboxylic acid anhydride and epoxide, any cyclic compound can be selected from them and subjected to ring-opening polymerization.

[0043] Here, the dicarboxylic anhydride and the epoxide are used simultaneously with the initiator and react alternately. At this time, the acid anhydride group of the dicarboxylic anhydride first reacts with the hydroxyl group, primary amino group, secondary amino group, or thiol group of the initiator to generate a carboxyl group, and then the epoxy group of the epoxide reacts with this carboxyl group to generate a hydroxyl group. Then, the acid anhydride group of the dicarboxylic anhydride reacts with this hydroxyl group, and so on, and the same reactions as above can be carried out sequentially thereafter. The polymerization mole numbers of the dicarboxylic anhydride and the epoxide per mole of the initiator are preferably 0 to 30 moles each. In addition, the reaction ratio of the dicarboxylic anhydride and the epoxide ([d ｍ ] / [e ｍ ]) is 0.8≦[d ｍ ] / [e ｍ ] ≦ 1.0 ([d ｍ ] is the number of moles of dicarboxylic acid anhydride, and [e ｍ When the above range is satisfied, it is easy to obtain a polymer having a hydroxyl group at one end while reducing the amount of the remaining epoxide raw material.

[0044] The alternating polymerization of dicarboxylic acid anhydride and epoxide is preferably carried out at a temperature in the range of 50° C. to 180° C., more preferably 60° C. to 150° C. By setting the temperature at 50° C. to 180° C., the reaction rate can be made appropriate.

[0045] For the polyester monool, lactone and / or lactide is preferably used as the cyclic compound from the viewpoints of simplicity of the production process, ease of molecular weight control, and high reaction rate.

[0046] A solvent can be used in the synthesis. Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, and propylene glycol monomethyl ether acetate. Two or more of these solvents may be mixed and used. After the reaction is completed, the solvent used may be removed by distillation or the like, or may be used as part of the product.

[0047] <Production Method of (I)> The tetracarboxylic acid-modified product (A) of (I) is obtained by reacting an aliphatic tetracarboxylic acid anhydride (I-a) with a compound (I-b1) having one terminal hydroxyl group. When the number of moles of the aliphatic tetracarboxylic acid anhydride (I-a) is <H> and the number of moles of the compound (I-b1) having one terminal hydroxyl group is <N>, the ratio of 1 <<N> / <H> < 2.4 is preferred, 1.4 <<N> / <H> < 2.2 is even more preferred, and <N> / <H> = 2 is particularly preferred. When the reaction is carried out with <N> / <H> less than 1, the remaining acid anhydride may be hydrolyzed with a required amount of water before use.

[0048] The reaction may be carried out in the presence of a catalyst, such as a tertiary amine compound, including triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene.

[0049] The above process may be carried out without a solvent or with an appropriate dehydrated organic solvent. After the reaction is completed, the solvent used in the reaction may be removed by distillation or the like, or may be used as it is as part of the product.

[0050] The reaction temperature in the above step is preferably 80° C. to 180° C., more preferably 90° C. to 160° C. By setting the reaction temperature to 80° C. or higher, the reaction rate can be maintained at an appropriate level, and by setting the reaction temperature to 180° C. or lower, it is possible to prevent the acid anhydride that has undergone ring-opening in the reaction from recyclizing and inhibiting the progress of the reaction.

[0051] The Mw of the tetracarboxylic acid modified product (A) is preferably 1000 to 20,000, more preferably 4,000 to 16,000. By adjusting the Mw to 1000 to 20,000, the adhesive strength after aging under high temperature and high humidity conditions is improved.

[0052] <(II): Tetracarboxylic Acid Modified Product (A)> By using (II), a reaction product of an aromatic tetracarboxylic acid anhydride (II-a) and a hydroxyl-containing compound (II-b) (hereinafter also referred to as compound (II-b)) having an ether bond in its molecular structure, as the tetracarboxylic acid modified product (A), the adhesive strength after long-term aging under high temperature and high humidity is improved. Here, compound (II-b) is compound (II-b1) (hereinafter also referred to as compound (II-b1)) having one terminal hydroxyl group and / or compound (II-b2) (hereinafter also referred to as compound (II-b2)) having two terminal hydroxyl groups. By using, as the tetracarboxylic acid modified product (A), (i) the reaction product (A1) of aromatic tetracarboxylic acid anhydride (II-a) and compound (II-b1), (ii) the reaction product (A2) of aromatic tetracarboxylic acid anhydride (II-a) and compound (II-b2), and (iii) a mixture of the reaction products (A1) and (A2), the adhesive strength after long-term aging under high temperature and high humidity conditions is improved. Because the tetracarboxylic acid modified product (A) of (II) is bulky, its carboxylic acid residues increase the distance between the silica filler (B) and / or thermally conductive filler (C) and enhance the interaction with the curing agent (D) and resin (E), thereby improving the dispersibility of the filler. As a result, the adhesive strength at 25°C is improved.

[0053] <Aromatic Tetracarboxylic Acid Anhydride (II-a)> The aromatic tetracarboxylic acid anhydride (II-a) is a compound having an aromatic ring structure adjacent to the acid anhydride, and this aromatic ring may be monocyclic or polycyclic. These may contain a substituent. Furthermore, the portion not adjacent to the acid anhydride may contain an aliphatic structure, and examples of the aliphatic structure include a chain hydrocarbon structure and an alicyclic hydrocarbon structure.

[0054] Specific examples of the aromatic tetracarboxylic acid anhydride (II-a) include 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic acid dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)propane dianhydride, and 2,2'-bis(3,4-dicarboxyphenoxyphenyl) ) sulfone dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 9,9'-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 9,9'-bis (3,4-dicarboxyphenoxy) fluorene dianhydride, 1',2'-dianhydride; 4,4'- [4,4'- (propane-2,2-diyl) diphenoxy] diphthalic dianhydride, 4,4'- (4,4'-isopropylidenediphenoxy) diphthalic anhydride are exemplified. The aromatic tetracarboxylic acid anhydride (II-a) is not limited to the above, and may be used alone or in combination of two or more. Among them, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, which have good compatibility with the curing agent (D), are preferred.

[0055] <Hydroxyl Group-Containing Compound (II-b) Having an Ether Bond in its Molecular Structure> As described above, compound (II-b) is at least one of compound (II-b1) and compound (II-b2). By using compound (II-b) in tetracarboxylic acid-modified product (A) of (II), the carboxylic acid residue of tetracarboxylic acid-modified product (A) increases the distance between silica filler (B) and / or thermally conductive filler (C), and the adhesive strength can be better maintained after long-term storage under high temperature and high humidity.

[0056] [Compound (II-b1) Having One Terminal Hydroxyl Group] Examples of compound (II-b1) include monools derived from polyethylene glycol and monools derived from polypropylene glycol. Among these, those having a weight-average molecular weight (Mw) of 500 to 10,000 are preferred, and specifically, polyethylene glycol is preferred. When the Mw of compound (II-b1) is 500 to 10,000, compatibility with curing agent (D) is improved, kneading properties are improved, and adhesive strength can be maintained at a good level. The Mw of compound (II-b1) is more preferably 2,000 to 8,000. Adhesive strength can be maintained at a good level even after long-term storage at high temperatures and high humidity.

[0057] Two or more types of compound (II-b1) may be used in combination. The use of two or more types further improves compatibility with the curing agent (D), enabling the development of adhesive strength after long-term aging under high temperature and high humidity conditions and adhesive strength at 25°C. The compound (II-b1) may be used in combination during the reaction with the aromatic tetracarboxylic acid anhydride (II-a), or after the synthesis of the tetracarboxylic acid modified product (A), a tetracarboxylic acid modified product that is a reaction product of another compound (II-b1) and the aromatic tetracarboxylic acid anhydride (II-a) may be blended.

[0058] Commercially available polyethylene glycol products include, for example, Uniox M-550, Uniox M-1000, Uniox M-2500, Uniox M-3000, and Uniox M-4000 manufactured by NOF Corporation.

[0059] Examples of monools derived from polyethylene glycol or polypropylene glycol include those obtained by polymerizing ethylene oxide (EO) or propylene oxide (PO) using alcohol as an initiator. Commercially available EO adducts of synthetic alcohols having an average carbon number of 25 to 50 include UNITHOX 450, UNITHOX 480, and UNITHOX 750 manufactured by NuCeraSolutions, Inc. The EO content is preferably 20 to 100% by mass, more preferably 50 to 100% by mass. An EO content of 20 to 100% by mass ensures adhesive strength after long-term storage under high temperature and high humidity conditions. The EO content is the ratio of the total mass of EO to the total mass of compound (II-b1) [(total mass of EO) / (total mass of compound (II-b1)) × 100] (unit: mass%).

[0060] [Compound (II-b2) Having Two Terminal Hydroxyl Groups] Examples of compound (II-b2) include diols derived from polytetramethylene glycol, polyethylene glycol, and polypropylene glycol. Among these, those having a weight-average molecular weight (Mw) of 500 to 10,000 are preferred, and specifically, polytetramethylene ether glycol is preferred. When the Mw of compound (II-b2) is 500 to 10,000, compatibility with curing agent (D) is improved, and good adhesive strength can be maintained. The Mw of compound (II-b2) is more preferably 2,000 to 8,000. This allows for better maintenance of adhesive strength after long-term storage at high temperatures and high humidity.

[0061] <Production Method of (II)> The tetracarboxylic acid modified product (A) of (II) may be (A1) obtained by reacting an aromatic tetracarboxylic acid anhydride (II-a) with a compound (II-b1), or (A2) obtained by reacting an aromatic tetracarboxylic acid anhydride (II-a) with a compound (II-b2). These may be used alone, or a mixture of the reactants (A1) and (A2). When producing the reactant (A1), the ratio [N] / [H] is preferably 1.0<[N] / [H]<2.4, more preferably 1.4<[N] / [H]<2.2, and particularly preferably [N] / [H]=2.0, where [N] / [H] is the molar number of the aromatic tetracarboxylic acid anhydride (II-a) and [N] is the molar number of the compound (II-b1) having one terminal hydroxyl group. When the ratio [N] / [H] is less than 1.0, the remaining acid anhydride may be hydrolyzed with the required amount of water before use. Furthermore, when producing reactant (A2), where [H] is the number of moles of aromatic tetracarboxylic anhydride (II-a) and [N] is the number of moles of compound (II-b2) having two terminal hydroxyl groups, the relationship between [N] / [H] is preferably 0.5<[N] / [H]<3, more preferably 1.2<[N] / [H]<2.0, and particularly preferably [N] / [H]=1.5. When the reaction is carried out at an [N] / [H] ratio of less than 0.5, the remaining acid anhydride may be hydrolyzed with a required amount of water before use. The mixture of reactant (A1) and reactant (A2) may be prepared by mixing reactant (A1) and reactant (A2) separately, or may be prepared by simultaneously reacting aromatic tetracarboxylic anhydride (II-a) with compound (II-b1) and compound (II-b2) to obtain a reaction product containing reactant (A1) and reactant (A2).

[0062] A catalyst may be used in the above reaction. Specific examples of the catalyst are the same as those described in the production method (I) above.

[0063] The above steps may be carried out without a solvent or with an appropriate dehydrated organic solvent. After the reaction is complete, the solvent used in the reaction may be removed by distillation or the like, or may be used as is as part of the product.

[0064] The suitable reaction temperature for the above step is as described in the production method (I) above.

[0065] The weight average molecular weight (Mw) of the reaction product (A1) and the reaction product (A2) is preferably from 1,000 to 20,000, and more preferably from 3,500 to 16,000. When the Mw is from 1,000 to 20,000, the adhesive strength is improved.

[0066] [Silica Filler (B) and Thermally Conductive Filler (C)] The present composition contains at least one of silica filler (B) and thermally conductive filler (C). By including at least one of silica filler (B) and thermally conductive filler (C), the adhesive strength of the cured product after aging under high temperature and high humidity conditions is improved. That is, by combining at least one of silica filler (B) and thermally conductive filler (C) with tetracarboxylic acid modified product (A), curing agent (D), and resin (E), the adhesive strength after aging under high temperature and high humidity conditions is increased. From the viewpoint of further improving the adhesive strength after aging under high temperature and high humidity conditions, the combination of (I) tetracarboxylic acid modified product (A), silica filler (B), thermally conductive filler (C), curing agent (D), and polyamide resin (e1) is more preferred.

[0067] Examples of the silica filler (B) include silica fillers such as plate-like silica, rod-like silica, fused crushed silica, fused spherical silica, crystalline silica, and secondary agglomerated silica. Plate-like silica is preferred because it has excellent adhesive strength after long-term storage under high temperature and high humidity conditions. The thermally conductive filler (C) preferably has a high thermal conductivity at 20°C, and a filler with a thermal conductivity of 15 (W / (m·K)) or more is preferred. Furthermore, a filler with a volume resistivity of 10 to the power of 6 (Ω·cm) or more is preferred. Suitable examples of the thermally conductive filler (C) include alumina (aluminum oxide), aluminum nitride, silicon nitride, boron nitride, and silicon carbide. The type of boron nitride is not particularly limited. Examples include hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), and wurtzite boron nitride. Among these, hexagonal boron nitride (h-BN) is preferred from the viewpoint of thermal conductivity. The shape of the boron nitride is not limited, but a scale-like shape is preferred, and it may be either primary particles or secondary particles formed by aggregation of primary particles. Examples of the thermally conductive filler (C) include plate-like, rod-like, molten crushed bodies, molten spheres, crystals, secondary aggregates, etc. Among these, alumina (aluminum oxide) or boron nitride is preferred because of its ease of availability, and plate-like alumina is preferred because of its excellent adhesive strength after aging under high temperature and high humidity conditions.

[0068] The average particle size of both the silica filler (B) and the thermally conductive filler (C) is preferably in the range of 1 to 50 μm, more preferably 1 to 30 μm, and even more preferably 2 to 10 μm. By making the average particle size 1 μm or more, the flexibility and pliability of the cured product are further improved. By making the average particle size 50 μm or less, the adhesive strength after aging under high temperature and high humidity conditions is improved. The average particle size is the average particle size D ５０ The method for measuring the average particle size is described in detail in the Examples section.

[0069] The silica filler (B) and the thermally conductive filler (C) may each be independently treated (pretreated) with a silane coupling agent. Treatment with a silane coupling agent improves the affinity with other materials and further improves the dispersibility of the silica filler (B) and the thermally conductive filler (C). The silane coupling agent is a compound having a hydrolyzable group and a reactive functional group. Examples of the hydrolyzable group include alkoxy groups having 1 to 6 carbon atoms, such as methoxy and ethoxy groups; acetoxy groups; and 2-methoxyethoxy groups. Among these, methoxy groups are preferred because of the ease of removing volatile components such as alcohol generated by hydrolysis. Examples of the reactive functional group include vinyl groups, epoxy groups, styryl groups, methacrylic groups, acrylic groups, amino groups, ureido groups, mercapto groups, sulfide groups, and isocyanate groups, with epoxy groups being particularly preferred.

[0070] Examples of the silane coupling agent include vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy group-containing silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styryl group-containing silane coupling agents such as p-styryltrimethoxysilane; methacryl group-containing silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-acryloxypropyltrimethoxysilane; Examples of suitable silane coupling agents include amino group-containing silane coupling agents such as aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; ureido group-containing silane coupling agents such as 3-ureidopropyltriethoxysilane; mercapto group-containing silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; sulfide group-containing silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane. From the viewpoint of exhibiting excellent adhesive strength, phenylaminosilane treatment and / or vinylsilane treatment are preferred.

[0071] The method of treating the silica filler (B) with a silane coupling agent includes, for example, a wet method in which the silica filler (B) and the silane coupling agent are mixed in a solvent, and a dry method in which the silica filler (B) and the silane coupling agent are treated in a gas phase. The amount of the silane coupling agent to be treated is preferably about 0.1 to 1 part by mass per 100 parts by mass of the untreated silica filler (B).

[0072] The method for treating the thermally conductive filler (C) with the silane coupling agent and the amount of the treatment are the same as those for the silica filler (B) described above.

[0073] The total content of the silica filler (B) and the thermally conductive filler (C) is 40 to 95% by mass, based on 100% by mass of the nonvolatile content of the composition. It is preferably 60% by mass or more, and more preferably 70% by mass or more. A content of 40 to 95% by mass further improves the adhesive strength of the cured product after long-term storage under high temperature and high humidity conditions. The composition may include either the silica filler (B) or the thermally conductive filler (C), or both.

[0074] The silica filler (B) and the thermally conductive filler (C) may each independently be a single type or two or more types may be used in combination. From the viewpoint of improving adhesive strength, it is preferable to use two or more types of the same or different types. An embodiment containing two or more types of silica filler (B) includes a combination of any two or more types selected from plate-like silica, rod-like silica, fused crushed silica, fused spherical silica, crystalline silica, and secondary aggregated silica. Examples of embodiments containing two or more types of silica filler (B) include a combination of any two or more types with different average particle sizes, and a combination of two or more types of silica fillers with different surface treatments. Examples of embodiments containing two or more types of thermally conductive filler (C) include a combination of any two or more types selected from plate-like, rod-like, fused crushed, fused spherical, crystalline, and secondary aggregated. Examples of embodiments containing two or more types of thermally conductive filler (C) include a combination of two or more types with different average particle sizes, and a combination of two or more types of thermally conductive filler (C) with different surface treatments. The combined use of silica filler (B) and thermally conductive filler (C) makes different fillers with different electric charges more compatible with resin (E), improving kneadability and enabling good adhesiveness at 25° C. When polyamide resin (e1) is used, compatibility is improved and adhesiveness after long-term storage at high temperature and high humidity can be more suitably demonstrated, in addition to adhesive strength at 25° C.

[0075] [Curing Agent (D)] The present composition contains a curing agent (D). The curing agent (D) is a compound having a curable functional group (excluding compounds corresponding to the tetracarboxylic acid modified product (A) and the resin (E)). Suitable examples of the curing agent (D) include one or more selected from the group consisting of epoxy-based curing agents, acid anhydride group-containing compounds, isocyanate-based curing agents, aziridine-based curing agents, amine-based curing agents, phenol-based curing agents, and metal chelate-based curing agents. Among these, an epoxy-based curing agent is preferred. In particular, from the viewpoint of achieving both adhesive strength at 25°C and adhesive strength after long-term aging under high temperature and high humidity, a combination of an epoxy-based curing agent and a phenol-based curing agent, or a combination of an epoxy-based curing agent and an aziridine-based curing agent, is preferred. The curing agent (D) may be a polymeric or low molecular weight compound.

[0076] Epoxy-based curing agents are compounds containing two or more epoxy groups, acid anhydride group-containing compounds are compounds containing two or more acid anhydride groups, isocyanate-based curing agents are compounds containing two or more isocyanate groups, aziridine-based curing agents are compounds containing two or more aziridine groups, amine-based curing agents are compounds containing two or more amino groups, and phenol-based curing agents are compounds having two or more structures in which hydroxy groups are directly bonded to aromatic groups (aromatic rings). Metal chelate-based curing agents are complexes formed by coordination of a multidentate ligand (chelate ligand) with a metal ion. Among the above, epoxy-based curing agents are particularly suitable for improving adhesive strength at 25°C and adhesive strength after long-term aging under high temperature and high humidity. The combined use of an epoxy-based curing agent and a phenol-based curing agent is particularly preferred because it can impart toughness to the coating film.

[0077] The epoxy-based curing agent is a thermosetting resin that can be thermally cured by having an epoxy group. If the epoxy-based curing agent itself has a reactive functional group such as a hydroxyl group, the epoxy-based curing agent can form a crosslinked structure by itself. In addition to or instead of single crosslinking, a preferred embodiment involves thermal crosslinking between the tetracarboxylic acid-modified product (A) and the epoxy-based curing agent. The three-dimensional crosslinked structure formed by thermal crosslinking between the tetracarboxylic acid-modified product (A) and the epoxy-based curing agent provides excellent adhesive strength at 25°C. Furthermore, a preferred embodiment involves thermal crosslinking between the epoxy-based curing agent and the polyamide resin (e1). The three-dimensional crosslinked structure formed by thermal crosslinking between the epoxy-based curing agent and the polyamide resin (e1) provides excellent adhesive strength at 25°C and after long-term aging under high temperature and high humidity. The curing agent (D) may be used alone or in combination of two or more types.

[0078] The mass ratio ((A) / (D)) of the tetracarboxylic acid modified product (A) to the curing agent (D) is preferably 0.04 to 30.00. This ratio allows the adhesive strength at 25°C and the adhesive strength after long-term storage under high temperature and high humidity to be well balanced. The ratio is more preferably 0.10 to 5.00.

[0079] The mass ratio of the polyamide resin (e1) to the curing agent (D) is preferably (e1):(D) = 5:95 to 50:50. This ratio allows for a good balance of adhesive strength at 25°C and adhesive strength after long-term storage under high temperature and high humidity conditions. The ratio is more preferably (e1):(D) = 10:90 to 30:70.

[0080] The epoxy-based curing agent preferably has a repeating unit containing an aromatic ring. Furthermore, it is preferable that at least a portion of the aromatic rings in the repeating unit contain an organic group containing an epoxy group as a substituent. The epoxy equivalent of the epoxy-based curing agent is preferably 100 to 300 g / eq., and is preferably 200 g / eq. or more from the viewpoints of increasing rigidity, effectively promoting microphase separation of the resin component during melt molding, suppressing foaming in the cured product, and further improving moist heat resistance. Combining the epoxy-based curing agent with resin (E) can improve adhesive strength after aging tests under high temperature and humidity. Furthermore, combining polyamide resin (e1) with resin (E) can improve crack resistance. The lower limit of the epoxy equivalent is more preferably 220 g / eq., and even more preferably 250 g / eq. The upper limit of the epoxy equivalent is more preferably 320 g / eq., and even more preferably 300 g / eq.

[0081] From the viewpoint of improving compatibility with resin (E) during kneading, the epoxy curing agent is preferably a monocyclic aromatic hydrocarbon having one ring, such as a benzene ring, rather than a polycyclic aromatic hydrocarbon such as naphthalene. Polyaromatic epoxy resins having multiple monocyclic aromatic hydrocarbons are also suitable. Furthermore, from the viewpoint of effectively forming a phase-separated structure between resin (E) and the epoxy curing agent during melt molding, an epoxy curing agent containing a repeating unit structure is preferred. Examples of epoxy curing agents include bisphenol-type epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol S-type epoxy resins; novolac-type epoxy resins such as o-cresol novolac-type epoxy resins; biphenyl-type epoxy resins, naphthalene-type epoxy resins, naphthalene-containing novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, phenol aralkyl-type epoxy resins, trisphenolmethane-type epoxy resins, and phenol-modified xylene resin-type epoxy resins. Examples of liquid epoxy compounds include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, biphenyl-type epoxy resins, novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, polyfunctional phenol-based epoxy resins, naphthalene-type epoxy resins, phenol aralkyl-modified epoxy resins, alicyclic and alcohol-based glycidyl ethers, alicyclic and alcohol-based glycidyl amine-based epoxy resins, and alicyclic and alcohol-based glycidyl ester-based epoxy resins.

[0082] Among these, from the viewpoint of improving the moist heat resistance and further improving the adhesive strength after an aging test under high temperature and high humidity, biphenyl type epoxy resins, o-cresol novolac type epoxy resins, trisphenolmethane type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene-containing novolac type epoxy resins, phenol aralkyl type epoxy resins, and phenol-modified xylene resin type epoxy resins are preferred.

[0083] Suitable examples include epoxy curing agents represented by the following chemical formulas (1) to (6): where n is an integer, preferably 1 to 10.

[0084] Two or more types of epoxy curing agents may be used in combination. Using two or more types in combination makes it easier to adjust the adhesive strength. For example, it is preferable to use a phenol aralkyl type epoxy resin and a phenol-modified xylene resin type epoxy resin, or a phenol aralkyl type epoxy resin and a trisphenolmethane type epoxy resin. Among these, using a combination of a phenol aralkyl type epoxy resin and a phenol-modified xylene resin type epoxy resin, or a phenol aralkyl type epoxy resin and a trisphenolmethane type epoxy resin in a mass ratio of 2:8 to 8:2 is preferred because it has appropriate compatibility with resin (E) and improves adhesive strength at 25°C and adhesive strength after long-term aging at high temperature and high humidity.

[0085] Examples of the acid anhydride group-containing compound include 1,2,4,5-benzenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-di Examples of acid dianhydrides include ethylene glycol bisanhydrotrimellitate, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4-bis(3,4-dicarboxyphenol)benzene dianhydride, p-phenylene bis(trimellitate anhydride), 4,4'-oxydiphthalic anhydride, 1,1'-biphenyl-2,3,3',4'-tetracarboxylic acid 2,3:3',4'-dianhydride, and dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride. Other examples include copolymers such as styrene-maleic anhydride copolymers and ethylene-maleic anhydride copolymers, and modified products such as acid anhydride-modified polypropylene. Commercially available products include Rikacid (registered trademark, manufactured by New Japan Chemical Co., Ltd.), Zybond (registered trademark, manufactured by Polyscope Polymers), SMA (registered trademark) Resin (manufactured by Claybury USA, Inc.), and Tafmer (registered trademark, manufactured by Mitsui Chemicals, Inc.).

[0086] The isocyanate curing agent is not particularly limited, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, etc. It is to be noted that a plurality of isocyanate group-containing compounds may be used in combination.

[0087] Examples of aromatic polyisocyanates include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4',4''-triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, and p-isocyanatophenylsulfonyl isocyanate.

[0088] Examples of aliphatic polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

[0089] Examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (H12-MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, and 2,6-norbornane diisocyanate.

[0090] Further examples include trimethylolpropane adducts of diisocyanates, biuret products obtained by reacting with water, and trimers having an isocyanurate ring.

[0091] The blocked isocyanate compound is not particularly limited, as long as it is a blocked isocyanate group-containing compound in which the isocyanate group in the isocyanate group-containing compound is protected with ε-caprolactam, MEK oxime, or the like. Specific examples include compounds in which the isocyanate group of the isocyanate group-containing compound is blocked with ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol, or the like. In particular, hexamethylene diisocyanate trimer having an isocyanurate ring and blocked with MEK oxime or pyrazole is highly preferred when used in this embodiment because it not only has excellent storage stability but also excellent adhesive strength at 25°C to bonding materials such as polyimide and copper, and adhesive strength after long-term aging under high temperature and high humidity.

[0092] Examples of the aziridine curing agent include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), N,N'-toluene-2,4-bis(1-aziridinecarboxamide), bisisophthaloyl-1-(2-methylaziridine), tri-1-aziridinylphosphine oxide, N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, tris-2,4,6-(1-aziridinyl)-1,3,5-triazine, trimethylolpropane tris[3-(1-aziridinyl)propionate], and trimethylolpropane. tris[3-(1-aziridinyl)butyrate], trimethylolpropane tris[3-(1-(2-methyl)aziridinyl)propionate], trimethylolpropane tris[3-(1-aziridinyl)-2-methylpropionate], 2,2'-bishydroxymethylbutanol tris[3-(1-aziridinyl)propionate], pentaerythritol tetra[3-(1-aziridinyl)propionate], diphenylmethane-4,4-bis-N,N'-ethyleneurea, 1,6-hexamethylene bis-N,N'-ethyleneurea, 2,4,6-(triethyleneimino)-Syn-triazine, bis[1-(2-ethyl)aziridinyl]benzene-1,3-carboxylic acid amide, and the like. In particular, 2,2'-bishydroxymethylbutanol tris[3-(1-aziridinyl)propionate] is suitable because it can increase adhesive strength.

[0093] Examples of the amine-based curing agent include polyamines having a dimer structure (dimer diamines) and other polyamines not having a dimer structure.

[0094] (Dimer diamine) Dimer diamine is a compound having a dimer structure and two amino groups, and a compound obtained by converting the carboxy group of the above-mentioned dimer acid to an amino group can be used. Examples of the conversion method include amidating a carboxylic acid, converting it to an amine by Hofmann rearrangement, and then distilling and purifying it. From the viewpoint of adhesive strength, dimer diamine is preferably a compound having 20 to 60 carbon atoms, more preferably a compound having 24 to 56 carbon atoms, and even more preferably a compound having 28 to 48 carbon atoms. From the viewpoint of availability, a compound having 36 to 44 carbon atoms is even more preferred.

[0095] Commercially available dimer diamines include, for example, "Priamine 1071," "Priamine 1073," "Priamine 1074," and "Priamine 1075" manufactured by Croda Japan, and "Versamine 551" manufactured by BASF Japan. The dimer diamines can be used alone or in combination of two or more.

[0096] (Other Polyamine Compounds) The other polyamine compounds are polyamine compounds other than dimer diamine, and examples thereof include diamine compounds and tri- or higher functional polyamine compounds.

[0097] Examples of the diamine compound include 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diamino-1,2-diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, and 4,4'-diaminodiphenyl Examples include aromatic diamines such as phenyl sulfone, 3,3'-diaminobenzophenone, and 3,3'-diaminodiphenyl sulfone; aliphatic diamines such as ethylene diamine, 1,3-propane diamine, 1,4-butane diamine, 1,6-hexane diamine, 1,7-heptane diamine, 1,9-nonane diamine, 1,12-dodecamethylene diamine, and meta-xylene diamine; and alicyclic diamines such as isophorone diamine, norbornane diamine, 1,2-cyclohexane diamine, 1,3-cyclohexane diamine, 1,4-cyclohexane diamine, 4,4'-diaminodicyclohexylmethane, and piperazine.

[0098] The type of phenolic curing agent is not particularly limited, but a phenolic resin having two or more phenolic hydroxyl groups per molecule is preferred. Examples of such phenolic resins include bisphenol A phenolic resins, bisphenol F phenolic resins, phenol aralkyl phenolic resins, dicyclopentadiene phenolic resins, triphenylmethane phenolic resins, novolac phenolic resins, dicyclopentadiene phenolic resins, xylylene phenolic resins, and biphenyl phenolic resins.

[0099] Specific examples of metal chelate curing agents include aluminum chelate compounds, titanium chelate compounds, and zirconium chelate compounds. The central metal may be various metals such as iron, cobalt, and indium.

[0100] [Curing Accelerator] When an epoxy-based curing agent is used as the curing agent (D), a curing accelerator can be used in combination with the epoxy-based curing agent. Examples of curing accelerators used in combination with the epoxy-based curing agent include urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Among these, imidazole-based curing accelerators are preferred from the viewpoint of improving crosslinkability. The other curing accelerators may be used alone or in combination of two or more. When a curing accelerator is used, its content is, for example, 0.05 to 0.5% by mass, preferably 0.1 to 0.3% by mass, based on 100% by mass of the total nonvolatile content of the composition.

[0101] Examples of urea-based curing accelerators include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, and 3-(2-methylphenyl)-1,1-dimethylurea. , 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea.

[0102] Examples of guanidine curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0103] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole. phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, Examples thereof include imidazole compounds such as 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins.

[0104] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0105] Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0106] [Resin (E)] The present composition contains resin (E). Resin (E) is a resin with stress relaxation properties and is selected from the group consisting of polyester resins, polyether resins, acrylic resins, olefin resins, maleimide resins, styrene-containing elastomers, linear olefin-containing elastomers, silicone resins, and polyamide resins. The polyamide resin contains a total of 50 to 99 mass% of dimer acid and dimer diamine relative to 100 mass% of the monomers constituting the polyamide resin (hereinafter referred to as polyamide resin (e1)). Among these, resin (E) is preferably selected from the group consisting of styrene-containing elastomers, linear olefin-containing elastomers, silicone resins, and polyamide resin (e1) from the viewpoint of adhesive strength.

[0107] The content of resin (E) is 0.1 to 40% by mass, preferably 0.6 to 10% by mass, based on 100% by mass of the nonvolatile content of the composition. By having the content within this range, the adhesive strength at 25°C and the adhesive strength after long-term storage under high temperature and high humidity conditions are further improved.

[0108] The Tg of resin (E) is preferably -10 to 90°C from the viewpoint of effectively bringing out stress relaxation properties. The upper limit of the Tg is more preferably 80°C, even more preferably 70°C. The lower limit of the Tg is more preferably -7°C, even more preferably 0°C. The Tg is the temperature at which the value (tan δ) obtained by dividing the viscosity term by the elasticity term, measured for polyamide resin (e1) using a dynamic viscoelasticity measuring device, shows a maximum. By setting the Tg of resin (E) to 0 to 90°C, compatibility with curing agent (D), silica filler (B) and / or thermally conductive filler (C) is further improved in the step of forming a melt of the present composition, and the filler is uniformly dispersed in the system, making it easier to obtain good adhesive strength after long-term aging under high temperature and high humidity.

[0109] The weight average molecular weight (Mw) of the resin (E) is preferably 15,000 to 100,000, and more preferably 17,000 to 78,000. When the Mw is 15,000 or more, an appropriate crosslinking density is obtained when the resin is cured, and the adhesive strength to the semiconductor chip is further improved. When the Mw is 100,000 or less, the wettability to the adherend is improved, and the adhesive strength is further improved.

[0110] The styrene-containing elastomer may be any of a homopolymer, a random copolymer, a block copolymer, and a gradient copolymer, but a block copolymer is preferred from the viewpoint of adhesive strength. Suitable examples include hydrogenated styrene-based elastomers such as styrene-ethylene-butylene block copolymer (SEB), styrene-ethylene-propylene block copolymer (SEP), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-butylene-styrene-styrene block copolymer (SEBSS), styrene-isobutylene-styrene block copolymer (SIBS), and styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), as well as modified products of the above elastomers with acid anhydrides such as maleic acid and citraconic acid, or modified acid anhydrides further modified with monoamines or diamines to change the functional groups.

[0111] Examples of chain olefin-containing elastomers include polymers using ethylene, propylene, butadiene, isoprene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, etc. as monomers, and may also be copolymerized with 2-phenyl-butadiene, 1,3-cyclohexadiene, 1,3,7-octatriene, myrcene, farnesene, chloroprene, etc. Furthermore, the functional groups may be changed by modifying the above polymers with acid anhydrides such as maleic acid or citraconic acid, or by further modifying the modified acid anhydrides with a monoamine or diamine.

[0112] The silicone resin is preferably a resin containing a siloxane bond, specifically a linear polymer containing a dimethylsiloxane structure, and is preferably a modified silicone oil in which some of the methyl substituents of the dimethylsiloxane are substituted with substituents such as alkyl groups, epoxy groups, carboxyl groups, and amino groups.

[0113] The polyamide resin (e1) is a polymer containing a repeating structural unit containing an amide group, such as a polymer of a polybasic acid compound, a polyamine compound, and optionally other monomers, or a modified product of such a polymer. Here, the term "modified product" refers to a derivative obtained by modifying a portion of the molecular structure of the polymer (e.g., by modifying a functional group, substituting with another compound, or adding another compound). The dimer structure can be introduced into the polyamide resin (e1) by using a monomer having a dimer structure, and suitable examples of such monomers include dimer acid, which is a polybasic acid compound, and / or dimer diamine, which is a polyamine compound. The total content of dimer acid and dimer diamine is 50 to 99% by mass, preferably 60 to 95% by mass, and more preferably 70 to 90% by mass, based on 100% by mass of the monomers constituting the polyamide resin (e1).

[0114] Since the feed rate of the monomers used in the polymerization of polyamide resin (e1) substantially matches the proportion of the monomer-derived constituents of polyamide resin (e1), the total feed rate of dimer acid and dimer diamine based on 100% by mass of all monomers used in the polymerization of polyamide resin (e1) may be 50 to 99% by mass. This ensures that the proportion of constituents derived from dimer acid and dimer diamine in polyamide resin (e1) is substantially 50 to 99% by mass, allowing the effects of the dimer structure to be fully exerted. In the case of modified products, the content of the dimer structure is determined by the virtual monomer having the modified structure. For unmodified monomers, the content can be determined from the content (mass%) of the monomer having the dimer structure based on 100% by mass of all monomers using raw material monomers. The content of the virtual monomer having the modified structure can be determined by taking into account the reactivity with respect to the polymer. For example, in the case where the side group derived from monomer a is modified after obtaining a polymer, the content of the dimer structure of other monomers can be determined in the same manner as in the determination of the polymer described above, using the monomer amount (mass) X calculated by "charge amount of monomer a (mol) × modification rate of side group / 100 × molecular weight of a hypothetical monomer having a structure after the side group has been modified" and the monomer amount (mass) Y calculated by "charge amount of monomer a (mol) × (1 - modification rate of side group / 100) × molecular weight of monomer a".

[0115] The dimer structure has a hydrocarbon chain or ring structure and is less polar than the curable resin, such as an epoxy resin, that is blended, thereby suppressing moisture absorption from outside the system. Furthermore, strong hydrogen bonds originating from the amide bonds of the polyamide resin (e1) are present. Due to the high cohesiveness of the hydrogen bonds, good adhesive strength can be expected even after long-term storage under high temperature and high humidity conditions. Additionally, the flexible skeleton improves adhesive strength at 25°C.

[0116] The polyamide resin (e1) preferably has a functional group capable of crosslinking with the curing agent (D) by heat. Examples of the functional group include a carboxy group, an amino group, and a hydroxyl group. These functional groups may be derived from the monomers of the polyamide resin (e1), or the functional group may be introduced as a modified product after the polymer is obtained. The functional group may be present at the terminal of the polymer, or may be present on a side group and / or a side chain. A preferred example is a polymer having a functional group such as a carboxy group or an amino group at the terminal. Another example is a polymer having at least one functional group such as a carboxy group, an amino group, or a hydroxyl group on a side group or a side chain. Note that if the functional group contains a photopolymerizable group, the composition containing the polyamide resin may become over-crosslinked, resulting in reduced adhesion, or may undergo a thermal radical reaction when the composition is thermally melted and molded, resulting in reduced moldability. Therefore, it is preferable that the composition does not contain a photopolymerizable group.

[0117] When the polyamide resin (e1) has a hydroxyl group, a phenolic hydroxyl group is preferred. The presence of a phenolic hydroxyl group allows a crosslinked structure to be formed with the curing agent (D), resulting in a cured product with excellent barrier properties. The phenolic hydroxyl group can be easily introduced by using a polybasic acid compound having a phenolic hydroxyl group and / or a polyamine compound having a phenolic hydroxyl group. The aromatic ring of this phenolic hydroxyl group is preferably contained in the main chain skeleton of the polyamide resin (e1). Furthermore, from the viewpoint of adhesive strength, it is preferred to use a polybasic acid compound having a phenolic hydroxyl group as a monomer for the polyamide resin (e1).

[0118] The polyamide resin (e1) may be a polyamideimide having imide groups in part thereof or a polyamideester having ester groups in part thereof, within the scope of the present disclosure.

[0119] <Polybasic Acid Compound> The polybasic acid compound used as a raw material for the polyamide resin (e1) is a dibasic or higher carboxylic acid. A portion of the polybasic acid compound may be an acid anhydride. Examples of the polybasic acid compound include dimer acid and polybasic acid compounds other than dimer acid. When a dimer acid is used as the polybasic acid compound, the content of the dimer acid in 100% by mass of the polybasic acid compound is preferably 60 to 100% by mass, and more preferably 80% by mass or more. When the content of the dimer acid in 100% by mass of the polybasic acid compound is 60% by mass or more, the moist heat resistance is improved, the stress relaxation effect due to the dimer structure is fully exhibited, and better adhesive strength at 25°C can be exhibited.

[0120] (Dimer Acid) Dimer acid is a polybasic acid compound having a dimer structure, and is a dimer of a fatty acid (hereinafter referred to as a fatty acid dimer).

[0121] The fatty acid dimer is preferably a compound having 20 to 60 carbon atoms, more preferably a compound having 24 to 56 carbon atoms, even more preferably a compound having 28 to 48 carbon atoms, and particularly preferably a compound having 36 to 44 carbon atoms. The fatty acid dimer is preferably a dicarboxylic acid compound having a branched structure obtained by subjecting a fatty acid to a Diels-Alder reaction. The branched structure preferably includes an aliphatic chain or an aliphatic chain and a cyclic structure, and more preferably includes an aliphatic chain and a cyclic structure. The cyclic structure is preferably one or more aromatic rings or an alicyclic structure, and more preferably an alicyclic structure. The alicyclic structure may have one double bond within the ring or may have no double bond. The above carbon number and branched structure enable the development of excellent adhesive strength at 25°C and the maintenance of adhesive strength after long-term storage at high temperatures and high humidity.

[0122] Examples of polybasic acid compounds having a dimer structure include those represented by the following chemical formulas (7) to (10): It goes without saying that the polybasic acid compounds having a dimer structure are not limited to the following structures.

[0123]

[0124] The fatty acid is preferably an unsaturated fatty acid having 10 to 30 carbon atoms, more preferably an unsaturated fatty acid having 10 to 24 carbon atoms. The unsaturated fatty acid has one or more carbon-carbon double bonds or one or more carbon-carbon triple bonds. Examples of the fatty acid include natural fatty acids such as soybean oil fatty acids, tall oil fatty acids, and rapeseed oil fatty acids, as well as oleic acid, linoleic acid, linolenic acid, and erucic acid, which are refined from these fatty acids. When synthesizing the fatty acid dimer, in addition to the fatty acid dimer, a fatty acid trimer and sometimes a fatty acid tetramer are also produced. Therefore, polybasic acid compounds containing a dimer skeleton are mixtures containing not only the fatty acid dimer as the main component, but also fatty acid trimers and, in some cases, the raw fatty acids. The fatty acid dimer preferably accounts for 70% by mass or more of 100% by mass of the dimer acid, more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0125] Since dimer acids use unsaturated fatty acids as raw materials, unsaturated bonds may remain. In such cases, hydrogenation (also called a hydrogenation reaction) can be performed to reduce the number of unsaturated bonds. This improves the reaction stability when synthesizing polyamide resin (e1), and further improves the adhesive strength of the cured product of the present composition containing polyamide resin (e1). Dimer acids can be used alone or in combination of two or more types.

[0126] Commercially available dimer acids include, for example, "Pripol 1004," "Pripol 1006," "Pripol 1009," "Pripol 1013," "Pripol 1015," "Pripol 1017," "Pripol 1022," "Pripol 1025," and "Pripol 1040" manufactured by Croda Japan; and "Empol 1008," "Empol 1012," "Empol 1016," "Empol 1026," "Empol 1028," "Empol 1043," "Empol 1061," and "Empol 1062" manufactured by BASF Japan. Among these, the use of "Pripol 1009," which has 36 carbon atoms, makes it easier to obtain a polyamide resin (e1) with better adhesion to the adherend. Furthermore, the use of "Pripol 1004," which has 44 carbon atoms, makes it easier to obtain a polyamide resin (e1) with good flexibility.

[0127] (Other Polybasic Acid Compounds) The other polybasic acid compounds are polybasic acid compounds other than dimer acids, and are bifunctional or higher functional compounds. The polybasic acid compounds can be used alone or in combination of two or more kinds.

[0128] Examples of dibasic acid compounds include aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, and 4,4'-biphenyldicarboxylic acid; aliphatic dibasic acids such as oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, thiomalic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexadecanedioic acid, and diglycolic acid; and alicyclic dibasic acids such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. Among these, isophthalic acid and 1,4-cyclohexanedicarboxylic acid are preferred as dibasic acid compounds.

[0129] Examples of trifunctional or higher functional polybasic acid compounds include trimellitic acid, hydrogenated trimellitic acid, pyromellitic acid, hydrogenated pyromellitic acid, trimesic acid, and 1,4,5,8-naphthalenetetracarboxylic acid. The use of a trifunctional or higher functional polybasic acid compound allows a branched structure to be introduced into the polyamide resin (e1), thereby improving the cohesive strength of the cured product and allowing the adhesive strength to be maintained even after long-term storage under high temperature and high humidity conditions.

[0130] Other suitable examples of polybasic acid compounds include polybasic acid compounds having a phenolic hydroxyl group. A polybasic acid compound having a phenolic hydroxyl group is a compound that, like phenol, has a hydroxyl group (also referred to as a phenolic hydroxyl group) directly bonded to an aromatic ring and has two or more acidic functional groups. Examples of the acidic functional group include a carboxyl group. By using a polybasic acid compound having a phenolic hydroxyl group, the crosslinked structure of the polyamide resin (e1) and the curing agent (D) can be easily adjusted during the curing treatment. As a result, strong crosslinks can be formed, effectively improving the adhesive strength after long-term aging under high temperature and high humidity.

[0131] Examples of polybasic acid compounds having a phenolic hydroxyl group include monohydroxyisophthalic acids such as 2-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, and 5-hydroxyisophthalic acid; dihydroxyisophthalic acids such as 2,5-dihydroxyisophthalic acid, 2,4-dihydroxyisophthalic acid, and 4,6-dihydroxyisophthalic acid; monohydroxyterephthalic acids such as 2-hydroxyterephthalic acid; dihydroxyterephthalic acids such as 2,3-dihydroxyterephthalic acid and 2,6-dihydroxyterephthalic acid; hydroxyphthalic acids such as 3-hydroxyphthalic acid and 4-hydroxyphthalic acid; and dihydroxyphthalic acids such as 3,4-dihydroxyphthalic acid, 3,5-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, and 3,6-dihydroxyphthalic acid. Among these, 5-hydroxyisophthalic acid is preferred as a polybasic acid compound having a phenolic hydroxyl group in terms of copolymerizability, ease of availability, etc. In the polybasic acid compound having a phenolic hydroxyl group, the carboxy group of the compound exemplified above may form an acid anhydride group, or the carboxy group may form an ester.

[0132] <Polyamine Compound> The polyamine compound used as a raw material for the polyamide resin (e1) is a compound having two or more amino groups. Suitable examples of the polyamine compound include dimer diamine and polyamine compounds other than dimer diamine. When dimer diamine is used as the polyamine compound, the content of dimer diamine in 100% by mass of the polyamine compound is preferably 50 to 100% by mass, and more preferably 90% by mass or more. By ensuring that the content of dimer diamine in 100% by mass of the polyamine compound is 50% by mass or more, the stress relaxation properties due to the dimer structure can be fully exerted, and better adhesive strength can be achieved.

[0133] (Dimer diamine) Dimer diamine is a compound having a dimer structure and two amino groups, and a compound obtained by converting the carboxy group of the above-mentioned dimer acid to an amino group can be used. Examples of the conversion method include amidating a carboxylic acid, converting it to an amine by Hofmann rearrangement, and then distilling and purifying it. From the viewpoint of adhesive strength, dimer diamine is preferably a compound having 20 to 60 carbon atoms, more preferably a compound having 24 to 56 carbon atoms, and even more preferably a compound having 28 to 48 carbon atoms. From the viewpoint of availability, a compound having 36 to 44 carbon atoms is even more preferred.

[0134] Commercially available dimer diamines include, for example, "Priamine 1071," "Priamine 1073," "Priamine 1074," and "Priamine 1075" manufactured by Croda Japan, and "Versamine 551" manufactured by BASF Japan. The dimer diamines can be used alone or in combination of two or more.

[0135] (Other Polyamine Compounds) The other polyamine compounds are polyamine compounds other than dimer diamine, and examples thereof include diamine compounds and tri- or higher functional polyamine compounds.

[0136] Examples of the diamine compound include 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diamino-1,2-diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, and 4,4'-diamino Examples of the diamine include aromatic diamines such as diphenyl sulfone, 3,3'-diaminobenzophenone, and 3,3'-diaminodiphenyl sulfone; aliphatic diamines such as ethylene diamine, 1,3-propane diamine, 1,4-butane diamine, 1,6-hexane diamine, 1,7-heptane diamine, 1,9-nonane diamine, 1,12-dodecamethylene diamine, and meta-xylene diamine; and alicyclic diamines such as isophorone diamine, norbornane diamine, 1,2-cyclohexane diamine, 1,3-cyclohexane diamine, 1,4-cyclohexane diamine, 4,4'-diaminodicyclohexylmethane, and piperazine.

[0137] Further, as other polyamine compounds, polyamine compounds having phenolic hydroxyl groups can be mentioned. Polyamide resin (e1) using a polyamine compound having a phenolic hydroxyl group is preferred in terms of adhesive strength. Use of a polyamine compound having a phenolic hydroxyl group is preferred because it allows phenolic hydroxyl groups to be introduced into the polyamide resin (e1). By introducing phenolic hydroxyl groups, it becomes possible to obtain a tougher cured product by three-dimensional crosslinking with the blended curing agent (D). The polyamine compound having a phenolic hydroxyl group has multiple amino groups and also has a phenolic hydroxyl group. Examples of polyamine compounds having phenolic hydroxyl groups include polyamines represented by the following general formula (2):

[0138]

[0139] In the formula R １represents a direct bond or a group containing carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen. Examples of the group include a divalent hydrocarbon group having 1 to 30 carbon atoms, a divalent hydrocarbon group having 1 to 30 carbon atoms in which some or all of the hydrogen atoms have been substituted with halogen atoms, -(C=O)-, -SO ２ Examples thereof include -, -O-, -S-, -NH-(C=O)-, -(C=O)-O-, a group represented by the following general formula (3) and a group represented by the following general formula (4).

[0140]

[0141] In the formula, r and s each independently represent an integer of 1 to 20; ２ represents a hydrogen atom or a methyl group.

[0142] Examples of polyamines represented by general formula (2) include 2,2-bis(3-amino-4-hydroxyphenyl)propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 4,4'-diamino-3,3'-dihydroxybisphenyl.

[0143] Examples of amines having three or more amino groups and no phenolic hydroxyl group include 1,2,4-triaminobenzene and 3,4,4'-triaminodiphenyl ether.

[0144] Among these, isophoronediamine or norbornanediamine is preferred as the other polyamine compound in terms of improving the wet heat resistance and further improving the adhesive strength and adhesive strength after long-term storage under high temperature and high humidity conditions.

[0145] <Method for Producing Polyamide Resin (e1)> Polyamide resin (e1) can be produced by, for example, melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid-state polymerization, or a combination of these. Among these, solution polymerization is preferred. Solution polymerization can be carried out using the above-mentioned polybasic acid compound, polyamine compound, and, if necessary, other monomers, in the presence or absence of a catalyst. For example, a nitrogen-filled flask is charged with a predetermined amount of dimer acid, other acid monomers, dimer diamine, other amine-based monomers, and ion-exchanged water, and the mixture is heated and stirred at 20 to 100°C to achieve a uniform solution or dispersion. The mixture is then gradually heated to 230°C while removing the ion-exchanged water and water generated by the reaction. Upon reaching 230°C, the pressure is reduced to approximately 15 mmHg and maintained at this pressure for approximately one hour to obtain polyamide resin (e1). The heating temperature is, for example, 150 to 300°C, and the heating time can be approximately 1 to 24 hours. To accelerate the synthesis reaction, it is preferable to carry out a dehydration or dealcoholization reaction, and to avoid coloration and decomposition reactions due to high temperatures, it is preferable to carry out the reaction at 180 to 270° C. under reduced pressure.

[0146] When producing the polyamide resin (e1), a monoamine may be used in addition to the polyamine. The monoamine acts as a reaction terminator, making it easy to adjust the molecular weight of the polyamide resin (e1). In addition, a portion of the main chain terminal of the polyamide resin (e1) is no longer a reactive functional group, improving stability over time. Examples of the monoamine include aniline, benzylamine, 4-aminophenol, and 2-ethylhexylamine.

[0147] <Physical Properties of Polyamide Resin (e1)> The glass transition temperature (Tg) of the polyamide resin (e1) is preferably −10 to 90° C., more preferably −7 to 80° C., and even more preferably 0 to 70° C. By setting the Tg of the polyamide resin (e1) to 0 to 90° C., compatibility with the curing agent (D), the silica filler (B) and / or the thermally conductive filler (C) is further improved in the step of forming a melt of the curable composition, and the filler is dispersed uniformly in the system, making it easier to obtain good adhesive strength after long-term aging under high temperature and high humidity conditions.

[0148] The weight average molecular weight (Mw) of the polyamide resin (e1) is preferably 15,000 to 100,000, and more preferably 17,000 to 78,000. When the Mw is 15,000 or more, an appropriate crosslinking density is obtained when the resin is cured, and the adhesive strength with the semiconductor chip is further improved. When the Mw is 100,000 or less, the wettability with the adherend is improved, and the adhesiveness is further improved.

[0149] The acid value of the polyamide resin (e1) is preferably 2 to 30 mgKOH / g, more preferably 3 to 25 mgKOH / g, and even more preferably 4 to 20 mgKOH / g. By adjusting the acid value to 2 to 30 mgKOH / g, the cured product can have an appropriate crosslink density, and the adhesive strength to the semiconductor chip at 25°C and after long-term storage at high temperature and high humidity can be further improved.

[0150] [Release Agent (F)] The present composition may further contain a release agent (F). Addition of the release agent (F) is particularly preferred when molding using a mold. The use of the release agent (F) improves releasability from the mold of the thermoforming device. Examples of the release agent (F) include natural waxes and synthetic waxes. Examples of natural waxes include carnauba wax and candelilla wax. Examples of synthetic waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and polyethylene wax. When using a release agent (F), a single agent may be used, or two or more agents may be used in combination. When using a release agent (F), its content is, for example, 0.1 to 0.5% by mass, preferably 0.2 to 0.3% by mass, based on 100% by mass of the total nonvolatile content of the present composition.

[0151] [Other Fillers (G)] The present composition may contain other fillers (G) other than the silica filler (B) and the thermally conductive filler (C). Examples of the other fillers (G) include flame-retardant fillers and electromagnetic shielding fillers. Examples of the other fillers (G) include quartz glass, talc, aluminum hydroxide, magnesium hydroxide, and ferrite. The preferred average particle diameter D of the other fillers (G) is ５０The surface treatment method is the same as that for the silica filler (B) described above. From the viewpoint of exhibiting other properties such as electromagnetic shielding, the content ratio (mass ratio) of the silica filler (B) and the thermally conductive filler (C) to the other filler (G) is preferably ((B) + (C)):(G) = 50:50 to 90:10. However, it is preferable that the total of the silica filler (C) and the thermally conductive filler (C) and the other filler (G) does not exceed 95 mass% of 100 mass% of the nonvolatile content of the composition.

[0152] Other components that can be used include thermoplastic resins (elastomers), dyes, pigments (e.g., carbon black), flame retardants, antioxidants, polymerization inhibitors, antifoaming agents, leveling agents, ion scavengers, moisturizing agents, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, and electromagnetic wave shielding agents.

[0153] [Method for producing curable composition] The present composition is obtained by kneading the respective blended components. For example, a solventless curable composition can be obtained by mixing the respective blended components and then melt-kneading them in a state that substantially does not contain a solvent. At this time, the composition may be formed into a desired shape such as a sheet, granules, pellets, powder, or tablet. Alternatively, the blended composition may be melt-kneaded to form an amorphous solid.

[0154] A sheet-like curable composition can be obtained, for example, by blending the components of a substantially solvent-free curable composition, melt-kneading them using a roll or kneader, forming the kneaded mixture into a sheet, and then cooling it. Melt-kneading can be performed using a known kneader such as a mixing roll, a pressure kneader, or an extruder. Regarding the kneading conditions, the temperature is preferably equal to or higher than the softening point of each of the above-mentioned components, for example, 30 to 150°C. Considering the thermosetting properties of the epoxy resin, it is preferably 40 to 140°C, more preferably 60 to 120°C. The kneading time is, for example, 1 to 30 minutes, preferably 5 to 15 minutes. Kneading is preferably performed under reduced pressure, which allows for degassing and prevents gas from entering the kneaded mixture. The pressure under reduced pressure is preferably 0.1 kg / cm. ２or less, more preferably 0.05 kg / cm ２ The lower limit of the reduced pressure is not particularly limited, but is, for example, 1×10 －４ kg / cm ２ That's all.

[0155] When the kneaded material is subjected to plastic processing to form a curable composition sheet, it is preferable to perform plastic processing on the kneaded material after melt kneading while it is still in a high-temperature state without cooling. The plastic processing method is not particularly limited, and examples thereof include flat plate pressing, T-die extrusion, screw die extrusion, roll rolling, roll kneading, inflation extrusion, co-extrusion, and calendar molding. Examples of molding machines include T-die screw molding machines, compression mold molding machines, and calendar molding machines. The plastic processing temperature is preferably equal to or higher than the softening points of the above-mentioned components, and, taking into account the thermosetting and moldability of the epoxy resin, is, for example, 40 to 150°C, preferably 50 to 140°C, and more preferably 70 to 130°C. A protective film may be laminated on the surface of the sheet-form curable composition. The sheet-form curable composition may also be in the form of a sheet or a rewound roll.

[0156] The thickness of the sheet of the sheet-shaped curable composition can be adjusted appropriately depending on the application, but is preferably 50 μm or more, more preferably 70 μm or more. By making the thickness 50 μm or more, when used for sealing, for example, an IC chip and its surrounding wiring layer and insulating layer together, it becomes easy to completely cover the target to be covered, and an excellent cured product can be obtained.

[0157] The resulting sheet-like curable composition may be pulverized into powder or granules, and the powder or granules may be compressed into tablets.

[0158] The powdery, granular, or tablet-like curable composition may be produced directly from a kneaded mixture by melt-kneading using a roll or kneader without passing through a sheet. This method can be carried out using, for example, a kneader, a roll mill, a super mixer, a Henschel mixer, a Schuggie mixer, a vertical granulator, a high-speed mixer, a Farmatrix, a ball mill, a steel mill, a sand mill, a vibration mill, an attritor, a Banbury mixer, or a batch kneader; a twin-screw extruder, a single-screw extruder, or a rotor-type twin-screw kneader.

[0159] Specifically, examples of such methods include a method in which a melt-kneaded curable composition is supplied to the inside of a rotor consisting of a cylindrical outer periphery having a plurality of small holes and a disk-shaped bottom, and the curable composition is forced to pass through the small holes by centrifugal force generated by rotating the rotor; a method in which the raw material components of the curable composition are premixed in a mixer, then heated and kneaded using a kneading machine such as a roll, kneader, or extruder, and then cooled and pulverized to produce a pulverized product, from which coarse particles and fine powder are removed using a sieve; and a method in which the raw material components of the curable composition are premixed in a mixer, then heated and kneaded using an extruder equipped with a die having a plurality of small diameters at the tip of the screw, and the molten resin extruded in the form of strands through the small holes arranged in the die is cut with a cutter that rotates and slides approximately parallel to the die surface to obtain the curable composition.

[0160] When the composition is in granular form, the particle size is preferably 70 to 500 μm. By setting the particle size to 70 to 500 μm, it becomes easier to adjust the thickness of the composition after curing while suppressing contamination by powder. The particle size is measured by extracting and quantifying particles using an image binarization method under a microscope.

[0161] Alternatively, the respective components may be mixed with a solvent to prepare a varnish, or the raw material components may be kneaded to obtain a curable composition, and the resulting varnish may be dissolved or dispersed in an organic solvent or the like to prepare a varnish, which may then be applied and dried to obtain a sheet-like curable composition. Examples of application methods include coating methods using a coater such as a comma coater or a die coater, and printing methods such as stencil printing and gravure printing.

[0162] Furthermore, as described above, the sheet-shaped curable composition produced via the varnish may be further pulverized into granules or powder. Furthermore, the granules or powder may be molded into a desired shape such as a tablet (pellet). The varnish may also be spray-dried to form granules, powder, or the like. The shape of the composition can be appropriately selected depending on the application. For example, from the viewpoint of mold filling ability, granules or powder are preferred, and from the viewpoint of productivity, a sheet is preferred.

[0163] <<Cured Product and Manufacturing Method Thereof>> The cured product of the present disclosure can be obtained by curing the composition. For example, the composition can be applied to a substrate, dried, and thermally polymerized, or subjected to hot melt molding and curing treatment to obtain a cured product. Hot melt molding and curing treatment can be performed simultaneously, or the curing treatment can be performed after hot melt molding. The term "cured product" as used herein refers to a state in which the composition has been cured to the extent that further heating does not substantially promote the curing reaction. During melt kneading to produce the curable composition, a portion of the composition may react and harden, but the state in which further heating can harden is not included in the term "cured product." When the curable composition is used to seal, for example, an IC chip, stress relaxation occurs during the process of applying heat to soften and flow the molded body. However, the stress is dispersed in the in-plane and longitudinal directions of the sealed body, resulting in an effect of suppressing a decrease in adhesive strength. Pressure may be applied during melt molding. The use of polyamide resin (e1) can further effectively suppress foaming and cracking.

[0164] The heat curing temperature is preferably 150 to 230°C, and the heating time is preferably 30 to 180 minutes. The curing process forms three-dimensional crosslinks to form a cured product. Pressure may be applied in addition to heat when melting the material. The application of heat and pressure makes it easier to soften and fluidize the material. The use of resin (E) can promote stress relaxation.

[0165] The glass transition temperature (Tg) of the cured product is preferably 100 to 200° C., more preferably 140 to 180° C. By adjusting the temperature to 100 to 200° C., the adhesive strength is improved.

[0166] When the composition is in the form of a sheet, for example, the sheet is placed on a semiconductor chip, melt-molded by thermocompression bonding, and cured to obtain an IC package in which the semiconductor chip is covered with a cured product that functions as an encapsulating resin. When the composition is in the form of a tablet, for example, the tablet is poured into a mold in which a semiconductor chip is set while being melted and flowed, and an IC package in which the cured product of the curable composition serves as the encapsulating resin is obtained through a molding step and a curing step.

[0167] <<Laminate>> A laminate comprises an adhesive layer formed from the present composition and a substrate. A laminate can be obtained by sandwiching an adhesive or adhesive sheet made from the present composition between plastic films such as polyester or polyimide films, metal foil, or the like, and then applying heat and pressure. The thickness of the adhesive layer formed from the present composition is preferably 5 to 500 μm, more preferably 10 to 100 μm, in order to exert sufficient adhesiveness and from the standpoint of ease of handling.

[0168] When a plastic film is used as the substrate, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0169] When a metal foil is used as the substrate, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. As the copper foil, a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0170] The method for applying the curable composition to the substrate is not particularly limited, and examples thereof include comma coating, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure printing, flexographic printing, dip coating, spray coating, and spin coating.

[0171] The present disclosure will be described in more detail below, but the following examples do not limit the scope of the present disclosure. In the examples, "parts" means "parts by mass," "%" means "% by mass," and "RH" means "relative humidity." The blending amounts in the tables are in parts by mass.

[0172] <Acid Value Measurement> Approximately 1 g of sample was precisely weighed into a stoppered Erlenmeyer flask and dissolved in 100 mL of cyclohexanone solvent. Phenolphthalein test solution was added as an indicator and the mixture was left to stand for 30 seconds. The solution was then titrated with 0.1 N alcoholic potassium hydroxide solution until it turned a pale pink color. The acid value was calculated using the following formula (unit: mg KOH / g): Acid value (mg KOH / g) = (5.611 x a x F) / S, where S is the amount of sample collected (g), a is the amount of 0.1 N alcoholic potassium hydroxide solution consumed (mL), and F is the titer of the 0.1 N alcoholic potassium hydroxide solution.

[0173] [Method for measuring weight-average molecular weight (Mw)] Mw was measured using a GPC (gel permeation chromatography) "GPC-101" manufactured by Showa Denko K.K. GPC is a liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on differences in their molecular size. Measurements in this disclosure were performed using two "KF-805L" (Showa Denko K.K.: GPC column: 8 mm ID x 300 mm size) columns connected in series, under conditions of a sample concentration of 1 mass%, a flow rate of 1.0 mL / min, a pressure of 3.8 MPa, and a column temperature of 40°C, and the weight-average molecular weight (Mw) was determined in polystyrene terms. Data analysis was performed using the manufacturer's built-in software to calculate the calibration curve, molecular weight, and peak area, and the weight-average molecular weight was determined using a retention time range of 17.9 to 30.0 minutes as the analysis target.

[0174] <Method for measuring the glass transition temperature (Tg) of resin (E)> Resin (E) was dissolved in cyclohexanone to a non-volatile content of 35%, to prepare a resin (E) varnish. This varnish was applied to a heat-resistant release film using a 10 mil doctor blade and dried at 130°C for 10 minutes to obtain a 25 μm thick film of resin (E), which was used as a sample for measuring the glass transition temperature. Tan δ was measured using a dynamic viscoelasticity measuring device in a temperature range of -50 to 200°C, and the glass transition temperature (Tg) was determined. Dynamic viscoelasticity measuring device: DVA-200 (manufactured by IT Measurement & Control Co., Ltd.) Heating rate: 10°C / min Measurement frequency: 10 Hz Grip length: 15 mm Width: 5 mm

[0175] [Average particle diameter D ５０ Measurement method] The average particle diameter was measured in a dry state using a laser diffraction particle size distribution analyzer SALD-2300 manufactured by Shimadzu Corporation. The refractive indexes of the silica filler (B) and the thermally conductive filler (C) were taken as literature values ​​for the refractive index of the silica filler (B) and the thermally conductive filler (C), and for example, the analysis was performed with a refractive index parameter of 1.77 for aluminum oxide. From the measurement results, the particle size (median diameter) at a cumulative mass percentage of 50% was calculated, and the average particle diameter D of the powder was determined. ５０ It was decided.

[0176] <Synthesis of Tetracarboxylic Acid Modified Product (A)> [Tetracarboxylic Acid Modified Product (I)-1-1] A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 31 parts of 2-(benzyloxy)ethanamine, 177.6 parts of ε-caprolactone, and 0.1 parts of monobutyltin(IV) oxide as a catalyst. The atmosphere was purged with nitrogen gas, and the mixture was heated and stirred at 120°C for 4 hours. After measuring the nonvolatile content, it was confirmed that 98% had reacted. 20.5 parts of BTA (1,2,3,4-butanetetracarboxylic dianhydride) and 0.1 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) were added, and the mixture was reacted at 100°C for 5 hours to obtain tetracarboxylic acid modified product (I)-1-1.

[0177] [Tetracarboxylic acid modified products ((I)-1-2) to ((I)-1-7), (A'-1)] Synthesis was carried out in the same manner as in ((I)-1-1) according to the compositions and charged mass parts in Table 5, to obtain tetracarboxylic acid modified products ((I)-1-2) to ((I)-1-7) and (A'-1).

[0178]

[0179] [Tetracarboxylic acid modified product ((I)-1-8)] A four-necked flask equipped with a stirrer, a reflux condenser equipped with a Dean-Stark apparatus, a nitrogen inlet tube, and a thermometer was charged with 100 parts of UNILIN 350 and 33 parts of MCTC (5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride), and the temperature was raised to 120°C with stirring. The temperature was maintained for 6 hours to complete the reaction, yielding a tetracarboxylic acid modified product ((I)-1-8).

[0180] [(I)-1-9) to ((I)-1-13)] Synthesis was carried out in the same manner as in ((I)-1-8) according to the compositions and charged mass parts in Table 2, to obtain tetracarboxylic acid modified products ((I)-1-9) to ((I)-1-13).

[0181] The abbreviations in Tables 1 and 2 are shown below. BTA: 1,2,3,4-butanetetracarboxylic dianhydride MCTC: 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride TDA-100: 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione BOA: bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid PMA: pyromellitic dianhydride UNILIN350: aliphatic alcohol with an average carbon number of C25 UNILIN700: aliphatic alcohol with an average carbon number of C50 UNITHOX480: number average molecular weight 2,300, weight average molecular weight 3,000, ethoxylated alcohol, EO content 80% by mass UNITHOX420: Number average molecular weight 575, weight average molecular weight 800, ethoxylated alcohol, EO content 20% by mass UNITHOX450: Number average molecular weight 920, weight average molecular weight 1,200, ethoxylated alcohol, EO content 50% by mass

[0182]

[0183] <Compound (b'1) Having an Ester Moiety and One Terminal Hydroxyl Group> A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 31 parts of benzyl alcohol, 177.6 parts of ε-caprolactone, and 0.1 parts of monobutyltin (IV) oxide as a catalyst, and after purging with nitrogen gas, the mixture was heated and stirred at 120°C for 4 hours. Measurement of the nonvolatile content confirmed that 98% had reacted, yielding compound (b'1) having an ester moiety and one terminal hydroxyl group.

[0184] Synthesis of <Tetracarboxylic Acid Modified Product (A)> [Tetracarboxylic Acid Modified Product ((II)-1-1)] 100 parts of UNITHOX 480 and 5.4 parts of PMA (pyromellitic dianhydride) were charged into a four-necked flask equipped with a stirrer, a reflux condenser equipped with a Dean-Stark apparatus, a nitrogen inlet tube, and a thermometer, and the temperature was raised to 120°C with stirring. The temperature was maintained for 6 hours to complete the reaction, thereby obtaining a tetracarboxylic acid modified product ((II)-1-1).

[0185] [Tetracarboxylic acid modified products ((II)-1-2) to ((II)-1-7), ((II)-2-1) to ((II)-2-5), (A'-2)] Synthesis was carried out in the same manner as in ((II)-1) according to the compositions and charged mass parts in Tables 3 and 4, to obtain tetracarboxylic acid modified products ((II)-1-2) to ((II)-1-7), ((II)-2-1) to ((II)-2-5), and (A'-2).

[0186] The abbreviations in Tables 3 and 4 are shown below. <Aromatic tetracarboxylic anhydrides (II-a)> PMA: pyromellitic dianhydride BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride BISDA: 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride <Compounds (II-b1) having one terminal hydroxyl group> UNIOX M4000: weight average molecular weight 5,600, polyoxyethylene monomethyl ether UNIOX M2000: weight average molecular weight 2,600, polyoxyethylene monomethyl ether For UNITHOX480, UNITHOX420, and UNITHOX450, the explanation of the abbreviations in Tables 1 and 2 is used by reference. UNITHOX750: weight average molecular weight 1,800, ethoxylated alcohol, EO content 50% by mass <Compound (II-b2) having two terminal hydroxyl groups> PTMG2000: polytetramethylene ether glycol, weight average molecular weight 3,100 PTMG1000: polytetramethylene ether glycol, weight average molecular weight 1,400

[0187]

[0188]

[0189] <Synthesis of Resin (E) and the Like> [Other Resins (Polyamide Resin (E'-1))] A four-necked flask equipped with a stirrer, a reflux condenser equipped with a Dean-Stark apparatus, a nitrogen inlet tube, and a thermometer was charged with 481 g (0.901 mol) of DA (Priamine 1075) as a dimer diamine having 36 carbon atoms, 187.5 g (0.938 mol) of DAPE (3,4'-diaminodiphenyl ether) as another diamine, 139.1 g (0.952 mol) of AdA (adipic acid) as a polybasic acid, and 192.4 g (0.952 mol) of SeA (sebacic acid), and the mixture was stirred. Once the heat generation had subsided, the mixture was gradually heated to allow the reaction to proceed. While removing water generated as the reaction proceeded from the system, the internal temperature was raised to 230°C, and the temperature was maintained, and the reaction was continued for 4 hours. The mixture was then maintained at the same temperature for 2 hours under a reduced pressure of approximately 2 kPa to complete the reaction. Polyamide resin (E'-1) having a weight average molecular weight of 30,000, an acid value of 11.4 mgKOH / g, and a Tg of 28°C was obtained. The total content of dimer diamine and dimer acid in 100% by mass of the monomers constituting polyamide resin (E'-1) was 48.1% by mass.

[0190] [Resin (E) (Polyamide Resins (E-1) to (E-11), (E-13) to (E-15))] Polyamide resins were obtained by synthesis in the same manner as for polyamide resin (E'-1) according to the compositions and parts by mass of ingredients shown in Tables 5 and 6. The properties of the polyamide resins are shown in Tables 5 and 6.

[0191] [Resin (E) (Polyamide Resin (E-12))] In a four-neck flask equipped with a stirrer, a reflux condenser equipped with a Dean-Stark apparatus, a nitrogen inlet tube, and a thermometer, 672.6 parts of DA (Priamine 1075) as a dimer diamine having 36 carbon atoms, 59.1 parts of DAPE (3,4'-diaminodiphenyl ether) as another diamine, 194.5 parts of AdA (adipic acid) as a polybasic acid, and 59.1 parts of sebacic acid were charged and stirred. Once the heat generation subsided, the mixture was gradually heated to allow the reaction to proceed. While removing water generated as the reaction proceeded from the system, the internal temperature was raised to 230 ° C., and the temperature was maintained at that temperature, and the reaction was continued for 4 hours. The reaction was then allowed to proceed for 2 hours at a reduced pressure of about 2 kPa. Thereafter, the internal temperature was lowered to 180°C, 14.7 parts of BzA (benzylamine) was added, and the temperature was gradually raised to 240°C to complete the reaction. Polyamide resin (E-12) having a weight average molecular weight of 30,000, an acid value of 0.5 mgKOH / g, and a Tg of 26°C was obtained. Note that the total content of dimer diamine and dimer acid in 100% by mass of the monomers constituting polyamide resin (e1) was 67.4% by mass.

[0192]

[0193]

[0194] The abbreviations in Tables 5 and 6 are as follows: Dacid: dimer acid having 36 carbon atoms and a ring structure having 6 carbon atoms (dimer structure ratio: 95% or more, acid value: 197 mg KOH / g, "Pripol 1009", Croda Japan Co., Ltd.) AdA: adipic acid SeA: sebacic acid 5-HIP: 5-hydroxyisophthalic acid IPA: isophthalic acid DA: dimer diamine having 36 carbon atoms and a ring structure having 6 carbon atoms (dimer structure ratio: 95% or more, "Priamine 1075", Croda Japan Co., Ltd.) DAPE: 3,4'-diaminodiphenyl ether BzA: benzylamine

[0195] [Resin (E) (Polyamide Resin (E-21))] In a four-neck flask equipped with a stirrer, a reflux condenser equipped with a Dean-Stark apparatus, a nitrogen inlet tube, and a thermometer, 613.9 g (1.33 mol) of DA (Priamine 1075; manufactured by Croda Japan) as a dimer diamine having 36 carbon atoms, 36.5 g (0.18 mol) of DAPE (3,4'-diaminodiphenyl ether) as another diamine, 190.3 g (1.30 mol) of AdA (adipic acid) as a polybasic acid, and 57.8 g (0.28 mol) of SeA (sebacic acid) were charged and stirred. Once the heat generation subsided, the reaction was allowed to proceed by gradually heating. While removing water generated as the reaction proceeded from the system, the internal temperature was raised to 230 ° C., and the temperature was maintained at that temperature, and the reaction was continued for 4 hours. The reaction was then completed by maintaining the temperature at that temperature for 2 hours under a reduced pressure of approximately 2 kPa. A polyamide resin (E-21) was obtained having a weight-average molecular weight of 30,000, an acid value of 10.4 mgKOH / g, and a Tg of 12° C. The total content of dimer diamine and dimer acid in 100% by mass of the monomers constituting the polyamide resin (E-21) was 71.5% by mass.

[0196] [Resin (E) (Polyamide Resin (E-22))] A four-necked flask equipped with a stirrer, a reflux condenser equipped with a Dean-Stark apparatus, a nitrogen inlet tube, and a thermometer was charged with 613.9 g (1.14 mol) of DA (Priamine 1075; manufactured by Croda Japan) as a dimer diamine having 36 carbon atoms, 249.2 g (0.43 mol) of Dacid (Pripol 1009; manufactured by Croda Japan) as a polybasic acid, 53.3 g (0.36 mol) of AdA (adipic acid), and 84.6 g (0.41 mol) of SeA (sebacic acid) and stirred. Once the heat generation subsided, the reaction was allowed to proceed by gradually heating. While removing water generated as the reaction proceeded from the system, the internal temperature was raised to 230 ° C., and the temperature was maintained at that temperature, and the reaction was continued for 4 hours. The reaction was then completed by maintaining the temperature at that temperature for 2 hours under a reduced pressure of about 2 kPa. A polyamide resin (E-22) was obtained having a weight-average molecular weight of 30,000, an acid value of 10.2 mgKOH / g, and a Tg of −5° C. The total content of dimer diamine and dimer acid in 100% by mass of the monomers constituting the polyamide resin (E-22) was 86.3% by mass.

[0197] Example 1 2.4 parts of polyamide resin (E-1), 0.6 parts of tetracarboxylic acid modified product ((I)-12), 79.9 parts of plate-like silica (B-1), 12 parts of biphenyl type epoxy resin (D-5) and 5 parts of triphenylmethane type phenolic resin (D-9) as curing agents, and 0.1 parts of imidazole compound (F-1) as a curing catalyst were blended and kneaded in a kneader at 100°C for 10 minutes under reduced pressure (0.01 kg / cm ２ The resulting mixture was then molded by a platen press method to obtain a sheet-like curable composition having a thickness of 300 μm.

[0198] [Examples 2 to 44], [Comparative Examples 1 to 5] The ingredients were blended as shown in Tables 7 to 10 in the same manner as in Example 1 to obtain kneaded products, and then sheet-shaped curable compositions were obtained in the same manner as in Example 1.

[0199] Example 101 0.6 parts of tetracarboxylic acid modified product ((II)-1-2), 69.9 parts of plate-like silica (B-1), 10 parts of fused spherical silica (B-2), 12 parts of biphenyl-type epoxy resin (D-5) and 5 parts of triphenylmethane-type phenolic resin (D-9) as curing agents, 2.5 parts of resin (E-21), and 0.1 parts of imidazole compound (F-2) as a curing accelerator were blended, and the mixture was kneaded at 80° C. under reduced pressure (0.01 kg / cm ２ The resulting kneaded mixture was then molded by a flat plate press method to obtain a sheet-like curable composition having a thickness of 300 μm.

[0200] Examples 102 to 131 and Comparative Examples 101 to 109 The ingredients shown in Tables 11 to 14 were blended in the same manner as in Example 101, and sheet-shaped curable compositions were obtained in the same manner as in Example 101.

[0201] Details of the materials used in the examples and comparative examples are shown below. Silica filler (B) B-1: Plate-like silica (manufactured by AGC, Sun Lovely, average particle diameter D ５０ B-2: Fused spherical silica (manufactured by Admatechs Co., Ltd., SO-25R, average particle diameter D ５０ : 0.5 μm)

[0202] Thermally conductive filler (C) C-1: Plate-shaped alumina (manufactured by Kinseimatec Co., Ltd., Seraph 02025, average particle diameter D ５０ C-2: Plate-shaped alumina (Kinseimatec Co., Ltd., Seraph 05070, average particle diameter D ５０ C-3: Boron nitride (manufactured by Tomoe Chemical Co., Ltd., PT120, average particle diameter D ５０ : 12 μm)

[0203] Curing agents (D) D-1: Trisphenolmethane type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., EPPN-501H, epoxy equivalent (EPW) = 167 g / eq. D-2: Phenol aralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., NC-3000, EPW = 275 g / eq. D-3: Phenol-modified xylene resin type epoxy resin, manufactured by Mitsubishi Chemical Corporation, YX7700, EPW = 270 g / eq. D-4: Dicyclopentadiene type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., XD-1000, EPW = 253 g / eq. D-5: Biphenyl type epoxy resin, manufactured by Mitsubishi Chemical Corporation, YX4000HK, EPW = 185 g / eq. D-6: Tetrakisphenolethane type epoxy resin, manufactured by Mitsubishi Chemical Corporation, jER1031S, EPW = 200 g / eq. D-7: Naphthalene type epoxy resin, manufactured by DIC Corporation, HP-6000, EPW = 250 g / eq. D-8: Naphthalene-containing novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., NC-7000L, EPW = 231 g / eq. D-9: Triphenylmethane type phenol resin, manufactured by Meiwa Kasei Co., Ltd., MEH-7500, hydroxyl group equivalent = 97 g / eq. D-10: 2,2'-bishydroxymethylbutanol tris[3-(1-aziridinyl)propionate] D-11: Tris(2,3-epoxypropyl)isocyanurate

[0204] Resin (E) E-23: Polypropylene polyethylene copolymer (LICOCENE PP 1602, manufactured by Clariant): Chain olefin-containing elastomer, Mw 29,700, Tg approximately 0°C E-24: Hydrogenated styrene-butadiene rubber (Dynaron 2324P, manufactured by ENEOS): Styrene-containing elastomer, Tg approximately -50°C E-25: SEP (Kraton G1702, manufactured by Kraton): Styrene-containing elastomer, Mw 149,000, Styrene% = 28 E-26: SEBS (Kraton G1652, manufactured by Kraton): Styrene-containing elastomer, Mw 100,000, Styrene% = 30 E-27: SEBSS (Kraton A1536, manufactured by Kraton): Styrene-containing elastomer, Mw 130,000, Styrene% = 42 E-28: Maleic acid-modified SEBS (Tuftec M1913, manufactured by Asahi Kasei Corporation): styrene-containing elastomer, Mw 120,000, styrene% = 30 E-29: Maleic acid-modified polybutadiene (RICON 130MA8, manufactured by CRAY VALLEY): chain olefin-containing elastomer, Mw 4,300 E-30: Epoxy-modified silicone oil (DOWSIL FZ-3736, manufactured by Dow-Toray Industries, Inc.): silicone resin In the above, "styrene%" refers to the content (mass%) of structural units derived from styrene in 100 mass% of structural units derived from monomers that constitute the styrene-containing elastomer.

[0205] Curing catalyst (F) F-1: Imidazole compound (2P4MZ, manufactured by Shikoku Chemicals Corporation) F-2: Imidazole compound (2PHZ-PW, manufactured by Shikoku Chemicals Corporation)

[0206] For the cured products of the curable compositions of each Example and Comparative Example, the glass transition temperature was measured and the adhesive strength at 25°C and the adhesive strength after aging under high temperature and high humidity were evaluated. The measurement methods and evaluation criteria were as follows. The evaluation results are shown in Tables 7 to 14.

[0207] <Method for measuring the glass transition temperature (Tg) of the cured product> Each of the prepared 300 μm thick sheet-shaped curable compositions was thermally cured on a heat-resistant release film at 180°C for 60 minutes to prepare a sample for measuring the glass transition temperature. Tan δ was measured using a dynamic viscoelasticity measuring device in the temperature range of -50 to 200°C to determine the glass transition temperature (Tg). Dynamic viscoelasticity measuring device: DVA-200 (manufactured by IT Measurement & Control Co., Ltd.) Heating rate: 10°C / min Measurement frequency: 10 Hz Grip length: 15 mm Width: 5 mm

[0208] <Preparation of Adhesion Strength Evaluation Samples and Test Pieces> Each 300 μm thick sheet-shaped curable composition prepared in the Examples and Comparative Examples was cut into a 50 mm × 50 mm piece, and a total of nine 5 mm × 5 mm × 300 μm gold-plated silicon chips were arranged on top of it, in three vertical and three horizontal rows, at equal intervals. The sheet-shaped curable composition was placed in contact with the silicon surface of the silicon chip. To ensure close contact of the sheet-shaped curable composition in contact with the silicon chip, a 38 μm polyethylene terephthalate sheet treated with silicone release was placed opposite the silicon chip, and the two were thermally laminated (temperature 80° C., cylinder pressure 0.3 MPa) using a thermal lamination tester. After thermal lamination, an incision was made around the periphery of the silicon chip with a cutter knife, and a sheet-shaped curable composition was temporarily adhered to one side of the silicon chip to prepare an adhesion strength evaluation sample. A gold-plated copper frame substrate was prepared as an adherend, and a silicon chip with a sheet-like curable composition temporarily adhered thereto was placed on top of it. The substrate was then heat-pressed (150°C x 1 MPa x 1 min) and subsequently post-baked (170°C x 2 hours) to prepare a test specimen.

[0209] <25°C Adhesion Strength> Each test piece prepared above was evaluated using a bond tester (product name: Dage4000-PXY, manufactured by Nordson Advanced Technologies). Measurement conditions were a measurement speed of 100 μm / sec, 25°C, 60% RH, and a measurement height of 100 μm. Adhesion strength was measured for three test pieces, and the arithmetic mean value (X) of the adhesive strength was calculated. The larger the value, the higher the adhesiveness of the cured product to the silicon chip and the adherend. The evaluation criteria are as follows: 5: (X) is 10 N / mm or more: very excellent. 4: (X) is 7 N / mm or more but less than 10 N / mm: better. 3: (X) is 5 N / mm or more but less than 7 N / mm: excellent. 2: (X) is 3 N / mm or more but less than 5 N / mm: acceptable for practical use. 1: (X) is less than 3 N / mm: target not achieved.

[0210] <Adhesion Strength After Aging at 135°C and 85% RH> A pressure cooker bias test (PCBT) was performed on each of the test pieces prepared above under the following conditions. [PCBT Test Conditions] Temperature: 135°C, Relative Humidity: 85% RH, Bias Voltage: 25 V, Test Time: 500 hours. The adhesion strength of each test piece after the pressure cooker bias test was measured using a bond tester. The measurement conditions were a measurement speed of 100 μm / sec, a measurement height of 100 μm, and conditions of 25°C and 60% RH. The adhesion strength was measured on three test pieces, and the arithmetic mean value (Y) of the adhesion strength was calculated. The adhesion strength after aging at high temperature and high humidity was evaluated based on the ratio ((Y) / (X)) of the arithmetic mean value (Y) to the arithmetic mean value (X) of the adhesion strength at 25°C. The larger the value, the higher the adhesion of the cured product to the silicon chip and adherend after long-term aging at high temperature and high humidity. The evaluation criteria are as follows. 5: (Y) / (X) is 0.9 or more: very excellent. 4: (Y) / (X) is 0.7 or more and less than 0.9: better. 3: (Y) / (X) is 0.5 or more and less than 0.7: excellent. 2: (Y) / (X) is 0.3 or more and less than 0.5: acceptable for practical use. 1: (Y) / (X) is less than 0.3: target not achieved.

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219] The cured products obtained from the curable compositions of this example exhibited superior adhesiveness at 25°C compared to Comparative Examples 1 to 5 and 101 to 109, and it was confirmed that good adhesive strength was obtained even after an aging test under high temperature and high humidity conditions.

[0220] [Industrial Applicability] The curable composition of the present disclosure exhibits excellent adhesive strength after long-term storage under high temperature and high humidity conditions, and excellent adhesiveness at 25°C, and can therefore be suitably used as insulating resin materials, including semiconductor chip encapsulants, adhesives, underfill materials, potting materials, etc. Furthermore, the composition can be applied to fields requiring high humidity and heat resistance, such as organic thin-film solar cells and organic devices such as display elements, and is expected to be used in a wide range of fields.

[0221] This application claims priority based on Japanese Patent Application No. 2024-092101, filed June 6, 2024, and Japanese Patent Application No. 2025-072889, filed April 25, 2025, the disclosures of which are incorporated herein in their entireties.

Claims

1. A curable composition comprising a tetracarboxylic acid modified product (A), at least one of a silica filler (B) and a thermally conductive filler (C), a curing agent (D), and a resin (E), wherein the tetracarboxylic acid modified product (A) is at least one of the following (I) and (II): the resin (E) is a resin selected from the group consisting of polyamide resin, polyester resin, polyether resin, acrylic resin, olefin resin, maleimide resin, styrene-containing elastomer, linear olefin-containing elastomer, and silicone resin, wherein the polyamide resin contains a total of 50 to 99 mass% of dimer acid and dimer diamine based on 100 mass% of the monomers constituting the polyamide resin; and the curable composition contains, based on 100 mass% of the nonvolatile content of the curable composition, 0.1 to 5 mass% of the tetracarboxylic acid modified product (A), 40 to 95 mass% of the silica filler (B) and the thermally conductive filler (C), and 0.1 to 40 mass% of the resin (E). (I): A reaction product of an aliphatic tetracarboxylic anhydride (I-a) and a compound (I-b1) having one terminal hydroxyl group. (II): A reaction product of an aromatic tetracarboxylic anhydride (II-a) and a hydroxyl-containing compound (II-b) having an ether bond in its molecular structure, the hydroxyl-containing compound (II-b) being a compound (II-b1) having one terminal hydroxyl group and / or a compound (II-b2) having two terminal hydroxyl groups.

2. The curable composition according to claim 1, wherein the compound (I-b1) having one terminal hydroxyl group contains at least one of an ether bond and an ester bond in part of its molecular structure and has a weight-average molecular weight of 500 to 10,000.

3. The curable composition according to claim 1, wherein the weight-average molecular weight of the compound (II-b1) having one terminal hydroxyl group and the compound (II-b2) having two terminal hydroxyl groups is each independently 500 to 10,000.

4. The curable composition according to claim 1, wherein the glass transition temperature of the resin (E) is -10 to 90°C.

5. The curable composition of claim 1, wherein the curing agent (D) comprises an epoxy-based curing agent.

6. The curable composition of claim 1, wherein the thermally conductive filler (C) comprises alumina.

7. A cured product of the curable composition according to any one of claims 1 to 6.

8. A laminate comprising an adhesive layer made of the cured product according to claim 7 and a substrate.

9. A method for producing a cured product, comprising the steps of: molding the curable composition according to any one of claims 1 to 6 by thermal melting; and thermally curing the composition.

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