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

Abstract

The object of the present invention is to provide a curable composition, a cured product, a laminate, and a method for producing a cured product that has good kneadability and yields a cured product with high gas barrier function and excellent adhesion. [Solution Method] A curable composition comprising a tetracarboxylic acid modified product (A), at least one of a silica filler (B) and an insulating thermal conductive filler (C), and a curing agent (D), wherein the tetracarboxylic acid modified product (A) is a reaction product of an aliphatic tetracarboxylic anhydride (a1) and a compound (a2) having one hydroxyl group at its terminus, and the curable composition contains 0.1 to 5% by mass of the tetracarboxylic acid modified product (A) and a total of 40 to 95% by mass of the silica filler (B) and insulating thermal conductive filler (C) in 100% by mass of the nonvolatile content of the curable composition.

Description

[Technical Field]

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

[0002] Integrated circuits (ICs) are essential components of electronic devices, such as microprocessors, transistors, and memory, and are incorporated into various electronic devices such as computers, smartphones, and flat-panel displays. Insulating resins such as encapsulants, adhesives, underfills, and potting materials are used in the packages on which ICs are mounted, or in the circuit boards on which ICs are mounted.

[0003] Patent Document 1 discloses a resin composition for use as a mold underfill material for WL-CS (wafer-level chip-size packages), comprising 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. Furthermore, Patent Document 2 proposes a sealing film containing one or more elastomers selected from the group consisting of butadiene-based rubber and silicone-based rubber, an epoxy resin, a curing agent, and an inorganic filler, wherein the elastomer component is present in a specific amount. Furthermore, Patent Document 3 discloses a radically polymerizable polyamide, which is a reaction product of a polyamide having a dimer structure composed of a dimer acid or dimer amine, and a phenolic hydroxyl group unit, and a hydroxyl group in the side chain, with a radically polymerizable epoxy. Also disclosed is a resin composition containing this radically polymerizable polyamide, a photopolymerization initiator, an epoxy resin, a phenolic resin, a silica filler, a solvent, etc. Furthermore, Patent Document 4 discloses a thermosetting resin composition containing a polyamide (A) having a dimer structure formed by polymerizing a polybasic acid monomer and a polyamine monomer, and having phenolic hydroxyl groups in its side chains, and a trifunctional or more compound (B) that can react with the phenolic hydroxyl groups. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2017-057313 [Patent Document 2] International Publication No. 2016 / 136741 [Patent Document 3] Japanese Patent Publication No. 2019-119886 [Patent Document 4] International Publication No. 2016 / 001949 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The manufacturing process for semiconductor packages involves multiple heating steps to form the redistribution layer. For example, fan-out wafer-level packages (FO-WLPs) are attracting attention as chip-size packages that can increase the number of pins. In the manufacturing process for typical face-down type FO-WLPs, the semiconductor chip is sealed on one side with a molding resin composition, and then the redistribution layer is repeatedly heated during the subsequent heating process. For this reason, there is a need for a resin composition with high heat and humidity resistance that can suppress foaming and cracking during heating.

[0006] Electronic components and electronic devices are widely used in automobiles, industrial machines, ships, aircraft, etc. In this case, there is a concern that moisture accumulates at the interface between the chip and the mold resin, causing package cracks due to water vapor expansion, wire breakage, metal corrosion, and electrochemical migration. Therefore, electronic components have a property of disliking substances that cause oxidation such as oxygen and water. In such a situation, a sealing material with high gas barrier properties is required. Generally, there is a method of increasing the blending amount of inorganic fillers to enhance the gas barrier properties. However, when a large amount of inorganic filler is blended, both the kneadability and the adhesive strength tend to decrease when obtaining the composition. In response to the trend of high performance of electronic components, a resin composition with high adhesive strength is required to increase the stability of the product. However, it is not easy to achieve both the gas barrier function that requires the rigidity of the resin and the adhesive strength that requires the flexibility of the polymer chain, as well as good kneadability.

[0007] The present invention has been made in view of the above background, and an object thereof is to provide a curable composition, a cured product, a laminate, and a method for producing a cured product, which have good kneadability and can obtain a cured product having a high gas barrier function and excellent adhesiveness.

Means for Solving the Problems

[0008] As a result of intensive studies by the present inventors, it has been found that the problems of the present invention can be solved in the following aspects, and the present invention has been completed. to.

[0009] The present invention relates to the following inventions [1] to [7].

[0010] (1) It contains a tetracarboxylic acid modified product (A), at least one of a silica filler (B) and an insulating heat conductive filler (C), and a curing agent (D). The tetracarboxylic acid modified product (A) is a reaction product of an aliphatic tetracarboxylic anhydride (a1) and a compound (a2) having one hydroxyl group at the terminal. A curable composition containing 0.01 to 5% by mass of a tetracarboxylic acid-modified product (A) and a total of 40 to 95% by mass of a silica filler (B) and an insulating heat-conductive filler (C) in 100% by mass of the non-volatile content of the curable composition.

[0011] 〔2〕The curable composition according to any one of the above items, wherein the compound (a2) having one hydroxyl group at the terminal contains at least one of an ether bond and an ester bond in a part of the molecular structure and has a weight average molecular weight of 500 to 10,000.

[0012] 〔3〕The curable composition, wherein the curing agent (D) contains an epoxy-based curing agent.

[0013] 〔4〕The curable composition, wherein the insulating heat-conductive filler (C) contains alumina.

[0014] 〔5〕A cured product formed from the curable composition.

[0015] 〔6〕A laminate comprising the adhesive layer made of the cured product and a substrate.

[0016] 〔7〕A curable composition containing a tetracarboxylic acid-modified product (A), at least one of a silica filler (B) and an insulating heat-conductive filler (C), and a curing agent (D), wherein the tetracarboxylic acid-modified polymer (A) is a reaction product of an aliphatic tetracarboxylic anhydride (a1) and a compound (a2) having one hydroxyl group at the terminal, A method for producing a cured product, comprising a step of molding a curable composition containing 0.01 to 5% by mass of a tetracarboxylic acid-modified product (A) and a total of 40 to 95% by mass of a silica filler (B) and an insulating heat-conductive filler (C) in 100% by mass of the non-volatile content of the curable composition by hot melting and then thermally curing.

Advantages of the Invention

[0017] According to the present invention, it is possible to provide a curable composition, a cured product, a laminate, and a method for producing a cured product, which have good kneadability and can obtain a cured product having excellent high gas barrier function and adhesiveness. [Modes for carrying out the invention]

[0018] The present invention will now be described in detail. It goes without saying that other embodiments are also included within the scope of the present invention, as long as they are consistent with the spirit of the invention. Furthermore, numerical ranges specified using "~" in this specification include the numerical values ​​before and after "~" as the lower and upper limits. Also, in this specification, "film" and "sheet" are not distinguished by thickness. In other words, "sheet" in this specification includes thin film-like materials, and "film" in this specification includes thick sheet-like materials. Furthermore, unless otherwise noted, the various components mentioned in this specification may be used individually or in combination of two or more.

[0019] In this specification, "Mw" and "Mn" are the weight-average molecular weight and number-average molecular weight in polystyrene terms, respectively, determined by gel permeation chromatography (GPC). These can be measured by the method described in the [Examples] section.

[0020] [Tetracarboxylic acid modified product (A)] Tetracarboxylic acid modified product (A) is a reaction product of an aliphatic tetracarboxylic anhydride (a1) and a compound (a2) having one hydroxyl group at its terminus. Because tetracarboxylic acid modified product (A) is a bulky polymer, the carboxylic acid residues widen the spacing between fillers, and the interaction with resin components such as the curing agent (D) improves dispersibility, resulting in improved kneadability, gas barrier properties, and adhesive strength.

[0021] The content of the tetracarboxylic acid modified product (A) is 0.01 to 5% by mass, and preferably 0.5 to 3% by mass, based on 100% by mass of the nonvolatile content of the curable composition. This ratio allows for a good balance between gas barrier properties and adhesive strength at 25°C.

[0022] <Aliphatic tetracarboxylic anhydride (a1)> The aliphatic tetracarboxylic anhydride (a1) may be a compound having a linear hydrocarbon structure or a compound having an alicyclic hydrocarbon structure. The "linear hydrocarbon structure" is a linear hydrocarbon structure and / or a branched hydrocarbon structure that may have unsaturated bonds. The "alicyclic hydrocarbon structure" is an alicyclic hydrocarbon that may have unsaturated bonds and may be monocyclic or polycyclic. These may contain substituents. Furthermore, the portion not adjacent to the acid anhydride may contain an aromatic group.

[0023] Examples of aliphatic tetracarboxylic anhydrides (a1) include tetracarboxylic dianhydrides having a chain-like 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. Also, 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, tricyclo[4.2.2.02,5]deca-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]octa-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]octa-7-ene-2,3,5,6 Cyclo, bicyclo, and tricyclotetracarboxylic acids such as -tetracarboxylic acids, 4,8-diphenyl-1,5-diazabicyclooctane-2,3,6,7-tetracarboxylic acid, 9-oxatricyclo[4.2.1.02,5]nonane-3,4,7,8-tetracarboxylic acid, 9,14-dioxopentacyclo[8.2.11,11.14,7.02,10.03,8]tetradecane-5,6,12,13-tetracarboxylic acid; spiro rings such as 2,8-dioxaspiro[4.5]decane-1,3,7,9-terotones. Examples of tetracarboxylic acid dianhydrides containing alicyclic hydrocarbon structures include 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexen-1,2-dicarboxylic acid 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 acid anhydride. Among these, 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, and bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid, which have good compatibility with the curing agent (D), are preferred. These compounds may be used individually or in combination of two or more.

[0024] <A compound having one hydroxyl group at its terminus (a2)> Examples of compounds (a2) having one hydroxyl group at the terminal include alcohol compounds having long-chain alkyl groups with an average of 25 to 50 carbon atoms, monools derived from polyethylene glycol, monools derived from polypropylene glycol, and polyester monools. Among these, those that contain at least one of ether bonds and ester bonds in part of their molecular structure and have a weight-average molecular weight of 500 to 10,000 are preferred, and specifically polyethylene glycol and polyester monools are preferred. Compound (a2), which has one hydroxyl group at its terminus, 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. This improves its compatibility with the curing agent (D), enhances its kneadability, and allows it to maintain good barrier properties and adhesive strength. The weight-average molecular weight of compound (a2), which has one hydroxyl group at its terminus, is more preferably 2,000 to 8,000. This allows for better maintenance of adhesive strength over long periods of time under high temperature and high humidity conditions.

[0025] Compound (a2) having one hydroxyl group at the terminal end can be used in combination of two or more types. Using two types in combination further improves compatibility with the curing agent (D), resulting in high kneadability and barrier properties. The combination of (a2) may be carried out when reacting with the aliphatic tetracarboxylic anhydride (a1), or it may be added after the synthesis of the tetracarboxylic modified product (A).

[0026] Examples of commercially available polyethylene glycol products include Uniox M-550, Uniox M-1000, Uniox M-2500, Uniox M-3000, and Uniox M-4000, all manufactured by NOF Corporation.

[0027] Examples of alcohol compounds having long-chain alkyl groups with an average of 25 to 50 carbon atoms include natural fatty acids such as heptacosanoic acid, octacosanoic acid, pentacosanoic acid, cerotic acid, melisic acid, nonacosanoic acid, and montanic acid, as well as purified compounds thereof and synthetic fatty acid-derived alcohols within the above range. Examples of commercially available synthetic fatty acid-derived alcohols include Unilin350, Unilin550, and Unilin700 manufactured by Newcera Solutions Co., Ltd.

[0028] Examples of monools derived from polyethylene glycol and polypropylene glycol include those obtained by polymerization reactions of ethylene oxide (EO) or propylene oxide (PO) using an alcohol as an initiator. Commercially available EO adducts of synthetic alcohols with an average of 25 to 50 carbon atoms include, for example, UNITHOX450, UNITHOX480, and UNITHOX750 manufactured by Newcera Solutions Co., Ltd. The EO content is preferably 20 to 100% by mass, and more preferably 50 to 100% by mass. Good barrier properties can be obtained when the EO content is within the above range. The EO content is the ratio of the total mass of EO to the total mass of compound (a2) [(total mass of EO) / (total mass of compound (a2)) × 100] (unit: mass%).

[0029] Examples of polyester monools include those obtained by ring-opening polymerization of cyclic compounds using monoalcohols or monoamines as initiators. The monoalcohols and monoamines used as initiators are not particularly limited, but good compatibility with the curing agent (D) can be obtained by using monoalcohols with a molecular weight of 300 or less containing an aromatic ring or alkylene oxy unit, or monoamines with a molecular weight of 300 or less containing an aromatic ring or alkylene oxy unit.

[0030] Examples of monoalcohols containing aromatic rings and 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-hydroxyindan and 1-phenyl-1-propanol. Of these, benzyl alcohol and phenoxyethanol are preferred from the viewpoint of good compatibility with the curing agent (D).

[0031] Monoalcohols containing alkylene oxy units with a molecular weight of 300 or less include, for example, 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 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 tetraethylene glycol monomethyl ether. Of these, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether are preferred from the viewpoint of good compatibility with curing agent (D).

[0032] Examples of aromatic ring-containing monoamines with a molecular weight of 300 or less include benzylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methyl6-benzylamine, 4-methylbenzylamine, 4-(aminomethyl)phenol, 4-fluorobenzylamine, 2-(benzyloxy)ethaneamine, and 1-aminoindan. Of these, benzylamine is preferred from the viewpoint of good compatibility with the curing agent (D).

[0033] Monoamines containing alkylene oxy units with a molecular weight of 300 or less include, for example, 3,6,9,12-tetraoxadecanamine and tert-butyl 3-[2-(2-aminoethoxy)ethoxy]propanoate. Of these, 3,6,9,12-tetraoxadecanamine is preferred from the viewpoint of good compatibility with curing agent (D).

[0034] Monoalcohols are preferred as initiators for producing polyester monools. Monoalcohols and monoamines can be used individually or in combination of two or more.

[0035] Cyclic compounds that can be used in the production of polyester monools include alkylene oxides, lactones, lactides, dicarboxylic acid anhydrides, and epoxides. Cyclic compounds can be used individually or in combination of two or more.

[0036] Alkylene oxides used include, for example, 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 configuration can be random and / or block. The polymerization moles of alkylene oxide per mole of initiator are preferably 0 to 100.

[0037] Polymerization of alkylene oxides can be carried out, for example, at a temperature of 100-200°C under pressure in the presence of an alkaline catalyst. Polymers (PeOH) obtained by polymerizing alkylene oxides to the hydroxyl groups of monoalcohols are commercially available, such as the Uniox series from NOF Corporation and the Bremmer series from Nippon Oil & Fats Co., Ltd., and can be used as polymers (PeOH) in the production method of the present invention. Examples of commercially available products include Uniox M-400, M-550, M-2000, Bremmer 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 this specification, the first step may be omitted by using these commercially available products.

[0038] 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.

[0039] Lactones can be used in any way not limited to the examples given above, and may be used alone or in combination of two or more types.

[0040] As the lactide, those represented by the following general formula (1) are preferred (including glycolides).

[0041] [ka] [In general formula (1), R 31 and R 32 Each of these is independently a hydrogen atom, a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms, and R 33 and R 34 Each of these is independently a hydrogen atom, a halogen atom, and a saturated or unsaturated linear or branched lower alkyl group having 1 to 9 carbon atoms. In this specification, lactide refers to lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) and glycolide (1,4-dioxane-2,5-dione). Of the lactone or lactide, lactone is preferred.

[0042] Ring-opening polymerization of lactones and / or lactides can be carried out, for example, by charging an initiator, lactone and / or lactide, and polymerization catalyst into a reactor connected to a dehydration tube and condenser, and performing the reaction under a nitrogen atmosphere. When using low-boiling point monoalcohols, the reaction can be carried out under pressure using an autoclave. Furthermore, when using monoalcohols that have an ethylenically unsaturated double bond, it is preferable to add a polymerization inhibitor and carry out the reaction under a dry air atmosphere.

[0043] The number of moles of polymerization of lactone and / or lactide per mole of initiator is preferably in the range of 1 to 60 moles, more preferably 2 to 20 moles, and most preferably 3 to 15 moles.

[0044] Polymerization catalysts include, for example, quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodine, tetrabutylammonium iodine, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodine, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodine, tetrabutylphosphonium iodine, benzyl Examples of catalysts include quaternary phosphonium salts such as methylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodine, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodine, as well as phosphorus compounds such as triphenylphosphine, organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate, alkali metal alkoxides such as sodium alkoxide and potassium alkoxide, as well as tertiary amines, organotin compounds, organoaluminum compounds, organic titanate compounds, and zinc compounds such as zinc chloride. The amount of catalyst used is 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm, relative to the mass of lactone and / or lactide. When the above range is met, a colorless polymer can be easily obtained at a polymerization rate suitable for production.

[0045] The ring-opening polymerization temperature of lactones and / or lactides is carried out in the range of 100°C to 220°C, preferably 110°C to 210°C. Meeting this range makes it easier to obtain polymers with a polymerization rate suitable for production and with few by-products.

[0046] Examples of dicarboxylic acid anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, itaconic anhydride, glutaric anhydride, dodecenyl succinic anhydride, and chlorendic anhydride.

[0047] 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 (where the substitution position of bromo is arbitrary), allyl glycidyl ether, ethoxyphenyl glycidyl ether, glycidyl (meth)acrylate, glycidyl phthalimide, and styrene oxide.

[0048] The method for producing polyester monools is not particularly limited, but for example, in the first step, alkylene oxide can be polymerized on the initiator, in the second step lactone can be polymerized, and in the third step dicarboxylic acid anhydride and epoxide can be polymerized alternately. In this example, the initiator when polymerizing lactone in the second step is the alkylene oxide polymer having a hydroxyl group at one end that has been polymerized in the first step. Also, the initiator when polymerizing dicarboxylic acid anhydride and epoxide alternately in the third step is a block copolymer of the alkylene oxide polymer having a hydroxyl group at one end and the lactone polymer that has been polymerized up to the second step.

[0049] The reaction sequence of the aforementioned 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. 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 all ring-opening polymerizations for the combinations of alkylene oxide, lactone (and / or lactide), and dicarboxylic acid anhydride and epoxide, any cyclic compound can be selected from among them and carried out ring-opening polymerization.

[0050] Here, the dicarboxylic acid anhydride and epoxide are used simultaneously with the initiator and react alternately. In this reaction, the acid anhydride group of the dicarboxylic acid anhydride first reacts with the hydroxyl group, primary amino group, secondary amino group, or thiol group of the initiator to produce a carboxyl group, and then the epoxy group of the epoxide reacts with this carboxyl group to produce a hydroxyl group. Furthermore, the acid anhydride group of the dicarboxylic acid anhydride reacts with this hydroxyl group, and so on, and the reaction can proceed sequentially in the same manner as described above. The number of moles of polymerization of dicarboxylic acid anhydride and epoxide per mole of initiator is preferably 0 to 30 moles each. In addition, the reaction ratio ([X] / [Y]) of dicarboxylic acid anhydride and epoxide is preferably 0.8 ≤ [X] / [Y] ≤ 1.0 ([X] is the number of moles of dicarboxylic acid anhydride and [Y] is the number of moles of epoxide). Satisfying the above range makes it easier to obtain a polymer having a hydroxyl group at one end while reducing the amount of residual epoxide raw material.

[0051] The alternating polymerization of dicarboxylic acid anhydrides and epoxides is preferably carried out in the range of 50°C to 180°C, more preferably 60°C to 150°C. The reaction rate is extremely slow if the reaction temperature is below 50°C or above 180°C.

[0052] In terms of ease of manufacturing, ease of molecular weight control, and high reaction rate, it is preferable to use lactones or lactides as cyclic compounds for the aforementioned polyester monoalls.

[0053] Solvents can be used in the above synthesis. Examples of solvents 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 used in mixture form. After the reaction is complete, the solvents used can be removed by distillation or other means, or they can be used as part of the dispersant product.

[0054] <Method for producing tetracarboxylic acid modified product (A)> The tetracarboxylic acid modified product (A) is obtained by the reaction of an aliphatic tetracarboxylic anhydride (a1) with a compound (a2) having one hydroxyl group at its terminus. The number of moles of aliphatic tetracarboxylic anhydride (a1) <h>The number of moles of compound (a2) having one hydroxyl group at its terminal end. <n>When 1< <n> / <h><2.4 is preferred, and more preferably 1.4< <n> / <h><2.2, most preferably <n> / <h>This is the case where = 2. <n> / <h>If the reaction is carried out with a ratio of less than 1, the remaining acid anhydride may be hydrolyzed with the required amount of water and used.

[0055] A catalyst may be used in the above reaction. Examples of catalysts include tertiary amine compounds, such as triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene.

[0056] The above process may be carried out without solvents, or a suitable dehydrated organic solvent may be used. After the reaction is complete, the solvent used in the reaction can be removed by distillation or other means, or it can be used as part of the dispersant product.

[0057] The reaction temperature for the above steps is preferably in the range of 80°C to 180°C, more preferably 90°C to 160°C. If the reaction temperature is below 80°C, the reaction rate is slow, and if it exceeds 180°C, the acid anhydride that has reacted and opened its ring may regenerate a cyclic anhydride, making it difficult to complete the reaction.

[0058] The weight-average molecular weight of the tetracarboxylic acid modified product (A) is preferably 1,000 to 20,000, and more preferably 3,500 to 16,000. Being within this range improves gas barrier properties and adhesive strength.

[0059] [Silica filler (B) and insulating thermal conductive filler (C)] The curable composition of this embodiment contains at least one of silica filler (B) and insulating thermal conductive filler (C). The inclusion of at least one of silica filler (B) and insulating thermal conductive filler (C) improves the adhesion of the cured product over time under high temperature and high humidity conditions. Furthermore, it enhances the gas barrier properties.

[0060] Silica filler (B) can be any silica filler such as plate-shaped silica, rod-shaped silica, molten crushed silica, molten spherical silica, crystalline silica, or secondary aggregated silica. Plate-shaped silica is preferred because it has excellent gas barrier properties. The insulating thermal conductive filler (C) is preferably one with a high thermal conductivity at 20°C, and a filler with a thermal conductivity of 15 (W / m·K) or higher is preferred. Furthermore, a filler with a volume resistivity of 10⁶ (Ω·cm) or higher is preferred. Suitable examples of the insulating thermal conductive filler (C) include alumina (aluminum oxide), aluminum nitride, silicon nitride, or boron nitride and silicon carbide. Among these, alumina (aluminum oxide) or boron nitride is preferred due to its availability, with alumina being the most preferred. The type of boron nitride is not particularly limited. For example, hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), wurtzite-type boron nitride, etc., can be cited. 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 flaky shape is preferred, and it may be primary particles or secondary particles formed by the aggregation of primary particles. Examples of insulating and thermally conductive fillers (C) include plates, rods, molten crushed bodies, molten spherical bodies, crystalline bodies, and secondary aggregates. Among these, plate-shaped alumina is preferred because it exhibits excellent adhesive strength over time under high temperature and high humidity conditions.

[0061] The silica filler (B) and the insulating thermal conductive filler (C) both preferably have an average particle diameter in the range of 1 to 50 μm, more preferably 1 to 30 μm, and even more preferably 2 to 10 μm. An average particle diameter of 1 μm or more further improves the flexibility and pliability of the cured product. An average particle diameter of 30 μm or less improves the adhesive strength over time under high temperature and high humidity conditions. Note that the average particle diameter is the average particle diameter D. 50 The method for measuring the average particle size is described in detail in the Examples section.

[0062] The silica filler (B) and the insulating thermal conductive filler (C) may each be treated (pretreated) independently 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 insulating thermal conductive filler (C). Silane coupling agents are compounds having a hydrolyzable group and a reactive functional group. Examples of hydrolyzable groups 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 they easily remove volatile components such as alcohols produced by hydrolysis. Examples of the reactive functional groups include vinyl groups, epoxy groups, styryl groups, methacrylic groups, acrylic groups, amino groups, ureido groups, mercapto groups, sulfide groups, and isocyanate groups, but epoxy groups are preferred among them.

[0063] Silane coupling agents include, for example, 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; and N-2-(aminoethyl)-3- Examples of amino group-containing silane coupling agents include minopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; ureido group-containing silane coupling agents include 3-ureidopropyltriethoxysilane; mercapto group-containing silane coupling agents include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; sulfide group-containing silane coupling agents include bis(triethoxysilylpropyl)tetrasulfide; and isocyanate group-containing silane coupling agents include 3-isocyanatetopropyltriethoxysilane. From the viewpoint of exhibiting excellent adhesive strength and gas barrier properties, phenylaminosilane treatment and / or vinylsilane treatment are preferred.

[0064] Methods for treating silica filler (B) with a silane coupling agent include, for example, a wet method in which silica filler (B) and the silane coupling agent are mixed in a solvent, and a dry method in which silica filler (B) and the silane coupling agent are treated in the gas phase. Preferably, the amount of silane coupling agent used is about 0.1 to 1 part by mass of silane coupling agent per 100 parts by mass of untreated silica filler (B).

[0065] The method and amount of treatment for the insulating thermally conductive filler (C) with a silane coupling agent are the same as those for the silica filler (B) described above.

[0066] The total content of silica filler (B) and insulating thermal conductive filler (C) is 40 to 95% by mass of 100% by mass of the nonvolatile content of the curable composition. 60% by mass or more is preferred, and 70% by mass or more is more preferred. A content of 40% by mass or more further improves the barrier properties of the cured product. This curable composition may contain only one of silica filler (B) or insulating thermal conductive filler (C), or both.

[0067] Silica filler (B) and insulating thermal conductive filler (C) may be used independently, as a single type or in combination of two or more types, but from the viewpoint of improving adhesive strength, it is preferable to include two or more types. Embodiments containing two or more types of silica filler (B) include embodiments in which any two or more types from plate-shaped silica, rod-shaped silica, molten crushed silica, molten spherical silica, crystalline silica, and secondary aggregated silica are used in combination. Examples also include embodiments in which two or more types with different average particle sizes are used in combination, and embodiments in which two or more types of silica fillers with different surface treatments are used in combination. Embodiments comprising two or more types of insulating thermal conductive fillers (C) include embodiments in which any two or more types are used in combination from plate-shaped, rod-shaped, molten crushed, molten spherical, crystalline, and secondary aggregates. Examples also include embodiments in which two or more types with different average particle sizes are used in combination, and embodiments in which two or more insulating thermal conductive fillers (C) with different surface treatments are used in combination. By using silica filler (B) and insulating thermal conductive filler (C) in combination, the different types of fillers with different charges become more compatible with the curing agent (D), improving kneadability and enabling good adhesion at 25°C as well as gas barrier properties.

[0068] [Hardening agent (D)] The curable composition of the present invention contains a curing agent (D). The curing agent (D) is preferably one or more selected from the group consisting of epoxy curing agents, acid anhydride group-containing compounds, isocyanate curing agents, aziridine curing agents, amine curing agents, phenolic curing agents, and metal chelating curing agents. In particular, it is preferable to include an epoxy curing agent, and especially from the viewpoint of achieving both adhesive strength at 25°C and adhesive strength after long periods of time under high temperature and high humidity, a combination of an epoxy curing agent and a phenolic curing agent is preferred. The curing agent (D) may be a polymer compound or a low molecular weight compound.

[0069] Epoxy curing agents are compounds containing two or more epoxy groups, acid anhydride group-containing compounds are compounds having two or more acid anhydride groups, isocyanate curing agents are compounds containing two or more isocyanate groups, aziridine curing agents are compounds having two or more aziridine groups, amine curing agents are compounds having two or more amino groups, and phenol curing agents are compounds having two or more structures in which a hydroxyl group is directly attached to an aromatic group (aromatic ring). Metal chelate curing agents are complexes formed when a polydentate ligand (chelate ligand) coordinates to a metal ion. Among the above, epoxy curing agents are most suitable for improving adhesion at 25°C and adhesion after long periods of time under high temperature and high humidity conditions.

[0070] Epoxy-based curing agents are thermosetting resins that can be heat-cured due to the presence of epoxy groups. If the epoxy resin itself contains reactive functional groups such as hydroxyl groups, the epoxy curing agent alone can form a crosslinked structure. In addition to or instead of single crosslinking, thermal crosslinking of the epoxy curing agent is also preferred. A three-dimensional crosslinked structure formed by thermal crosslinking of the tetracarboxylic acid-modified polymer (A) and the epoxy curing agent provides high adhesion and barrier properties at 25°C. Furthermore, one type of curing agent or a combination of two or more types may be used.

[0071] The content of tetracarboxylic acid metabolite (A) per 100 parts by mass of curing agent (D) is preferably 0.04 to 30.00, and more preferably 0.10 to 5.00. This allows for a good balance between adhesive strength at 25°C and adhesive strength after long periods of time under high temperature and high humidity conditions.

[0072] The epoxy curing agent is preferably in an embodiment having repeating units containing aromatic rings. Furthermore, it is preferable that at least a portion of the aromatic rings in the repeating units contain an organic group containing an epoxy group as a substituent. The epoxy equivalent of the epoxy curing agent is preferably 100 to 300 g / eq., and is preferably 200 g / eq. or more from the viewpoint of increasing rigidity, effectively promoting microphase separation of resin components during melt molding, suppressing foaming in the cured product, and further improving crack resistance and heat and moisture resistance. More preferably 220 to 300 g / eq. or more, and even more preferably 250 to 300 g / eq. or more.

[0073] From the viewpoint of improving compatibility with the tetracarboxylic acid modified product (A) during kneading, monocyclic aromatic hydrocarbons having a single ring, such as a benzene ring, are preferred over polycyclic aromatic hydrocarbons such as naphthalene. Furthermore, polycyclic aromatic epoxy resins having multiple monocyclic aromatic hydrocarbons are also suitable. Moreover, from the viewpoint of effectively forming a phase separation structure between the polyamide resin (A) and the epoxy curing agent during melt molding, epoxy curing agents containing repeating unit structures are preferred. Examples of epoxy curing agents include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin; novolac-type epoxy resins such as o-cresol novolac-type epoxy resin; biphenyl-type epoxy resin, naphthalene-type epoxy resin, naphthalene-containing novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, phenol aralkyl-type epoxy resin, trisphenolmethane-type epoxy resin, and phenol-modified xylene resin-type epoxy resin. Examples of liquid epoxy compounds include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, biphenyl-type epoxy resin, novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, polyfunctional phenol-based epoxy resin, naphthalene-type epoxy resin, phenol aralkyl-modified epoxy resin, glycidyl ethers such as alicyclic and alcohol-based, glycidylamine-based epoxy resins such as alicyclic and alcohol-based, and glycidyl ester-based epoxy resins such as alicyclic and alcohol-based.

[0074] Among these, 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 from the viewpoint of improving moisture and heat resistance and further enhancing barrier properties.

[0075] As preferred examples, epoxy curing agents represented by the following chemical formulas (1) to (6) can be cited. In the formulas, n is an integer, for example, 1 to 10 is preferred. [ka] [ka] [ka] [ka] [ka] [ka]

[0076] Two or more types of epoxy curing agents may be used in combination. Using two or more types makes it easier to adjust the adhesive strength and barrier properties. For example, it is preferable to include 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 particular, it is preferable to use 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, as this provides appropriate compatibility with the tetracarboxylic acid-modified polymer (A) and improves the adhesive strength at 25°C and the adhesive strength after long periods of time under high temperature and high humidity.

[0077] Examples of acid anhydride group-containing compounds include 1,2,4,5-benzenetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and 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 bis-anhydrotrimellitate, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4-bis(3,4-dicarboxyphenol)benzenedioanhydride, p-phenylenebis(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. Copolymers such as styrene-maleic anhydride copolymer and ethylene-maleic anhydride copolymer, and modified products such as acid anhydride-modified polypropylene can also be mentioned. Examples of commercially available products include Ricacid (registered trademark, manufactured by Shin-Nippon Rika Co., Ltd.), Zybond (registered trademark, manufactured by Polyscope Polymers Corporation), SMA (registered trademark) resin (manufactured by Claybury USA), and Tuffmer (registered trademark, manufactured by Mitsui Chemicals, Inc.).

[0078] The isocyanate-based curing agent is not particularly limited, but examples include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Furthermore, multiple types of isocyanate group-containing compounds may be used in combination.

[0079] Examples of aromatic polyisocyanates include 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 2,4-tolylenediisocyanate (TDI), 2,6-tolylenediisocyanate, 4,4'-diphenylmethanediisocyanate (MDI), 2,4-diphenylmethanediisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylenediisocyanate, 4,4',4''-triphenylmethanetriisocyanate, m-isocyanatophenylsulfonyl isocyanate, and p-isocyanatophenylsulfonyl isocyanate.

[0080] 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.

[0081] 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.

[0082] Other examples include the trimethylolpropane adduct of diisocyanate, the biuret compound obtained by reaction with water, and trimers having an isocyanurate ring.

[0083] 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. Specifically, examples include those 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 trimers having an isocyanurate ring and blocked with MEK oxime or pyrazole are very preferred when used in this embodiment because, when used, they have excellent storage stability, as well as excellent adhesive strength to bonding materials such as polyimide and copper at 25°C and adhesive strength after long periods of time under high temperature and high humidity.

[0084] Examples of aziridine-based curing agents include N,N'-diphenylmethane-4,4'-bis(1-aziridinyl carboxite), N,N'-toluene-2,4-bis(1-aziridinyl carboxite), bisisophthaloyl-1-(2-methylaziridine), tri-1-aziridinylphosphine oxide, N,N'-hexamethylene-1,6-bis(1-aziridinyl carboxite), trimethylolpropane-tri-β-aziridinyl propionate, tetramethylolmethane-tri-β-aziridinyl propionate, tris-2,4,6-(1-aziridinyl)-1,3,5-triazine, trimethylolpropane-tris[3-(1-aziridinyl)propionate], and trimethylolpropane. Examples include lis[3-(1-aziridinyl)butyrate], trimethylolpropanetris[3-(1-(2-methyl)aziridinyl)propionate], trimethylolpropanetris[3-(1-aziridinyl)-2-methylpropionate], 2,2'-bishydroxymethylbutanoltris[3-(1-aziridinyl)propionate], pentaerythritoltetra[3-(1-aziridinyl)propionate], diphenylmethane-4,4-bis-N,N'-ethyleneurea, 1,6-hexamethylenebis-N,N'-ethyleneurea, 2,4,6-(triethyleneimino)-Syn-triazine, and bis[1-(2-ethyl)aziridinyl]benzene-1,3-carboxylic acid amide. In particular, 2,2'-bishydroxymethylbutanoltris[3-(1-aziridinyl)propionate] is preferred because it can achieve both adhesive strength and barrier properties.

[0085] Examples of amine-based curing agents include polyamines having a dimer structure and other polyamines that do not have a dimer structure.

[0086] The type of phenolic curing agent is not particularly limited, but a phenolic resin having two or more phenolic hydroxyl groups in one molecule is preferred. Examples of such phenolic resins include bisphenol A type phenolic resin, bisphenol F type phenolic resin, phenol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, triphenylmethane type phenolic resin, novolac type phenolic resin, dicyclopentadiene type phenolic resin, xylylene type phenolic resin, and biphenyl type phenolic resin.

[0087] Specific examples of metal chelating hardening agents include aluminum chelating compounds, titanium chelating compounds, and zirconium chelating compounds. The central metal can be various metals such as iron, cobalt, and indium.

[0088] [Curing catalyst (E)] When an epoxy-based curing agent is used as the curing agent (D), a curing catalyst can be used in combination with the epoxy-based curing agent. Examples of curing catalysts used in combination with epoxy-based curing agents 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. Other curing accelerators may be used individually or in combination of two or more. When a curing catalyst (E) is used, its content is, for example, 0.05 to 0.5% by mass, preferably 0.1 to 0.3% by mass, of 100% by mass of the total nonvolatile content of the curable composition.

[0089] Examples of urea-based curing accelerators include aliphatic dimethylureas such as 1,1-dimethylurea, 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. Examples include 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, and 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea.

[0090] Examples of guanidine-based 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]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 1-methylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0091] Examples of imidazole-based curing accelerators 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-methylimidazole. Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium 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 isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, Examples 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, as well as adducts of imidazole compounds with epoxy resins.

[0092] Examples of metal-based hardening 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 organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0093] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0094] [Release agent (F)] The curable composition of the present invention may further contain a release agent (F). Addition of a release agent (F) is particularly preferable when molding using a mold. The use of a release agent (F) improves the release properties from the mold of the thermoforming apparatus. Examples of release agents (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), only one type may be used, or two or more types may be used in combination. When a release agent (F) is used, its content is, for example, 0.1 to 0.5% by mass, preferably 0.2 to 0.3% by mass, of 100% by mass of the total nonvolatile content of the curable composition.

[0095] [Other fillers (G)] The curable composition of the present invention may contain other fillers (G) other than silica filler (B) and insulating thermal conductive filler (C). Examples of other fillers (G) include flame retardant fillers and electromagnetic shielding fillers. Examples of other fillers (G) include quartz glass, talc, aluminum hydroxide, magnesium hydroxide, and ferrite. Preferred average particle size D of other fillers (G) 50 The surface treatment method is the same as that for silica filler (B) described above. From the viewpoint of exhibiting other properties such as electromagnetic shielding, the content ratio (mass ratio) of silica filler (B), insulating thermal conductive filler (C), and other fillers (G) is preferably ((B)+(C)):(G)=50:50 to 90:10. However, it is preferable that the total of silica filler (C), insulating thermal conductive filler (C), and other fillers (G) does not exceed 95% by mass of 100% by mass of the nonvolatile content of the curable composition.

[0096] In addition, thermoplastic resins (elastomers) can be used as other components. Other examples include dyes, pigments (e.g., carbon black), flame retardants, antioxidants, polymerization inhibitors, defoamers, leveling agents, ion capture agents, humectants, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, and electromagnetic shielding agents.

[0097] [Method for producing a curable composition] A curable composition is obtained by kneading each component. For example, a solvent-free curable composition can be obtained by melt-kneading the mixed components in a substantially solvent-free state. In this case, it may be in the desired shape such as a sheet, granules, pellets, powder, or tablet. Alternatively, the compounded composition may be a solid of any shape obtained by melt-kneading.

[0098] The sheet-like curable composition can be obtained, for example, by blending the components of a substantially solvent-free curable composition, melt-kneading them with a roll or kneader to form a kneaded product into a sheet shape, and then cooling. Known kneading machines such as mixing rolls, pressure kneaders, and extruders can be used for melt-kneading. As the kneading conditions, the temperature is preferably not less than the softening point of each of the above components, for example, 30 to 150 °C, preferably 40 to 140 °C, and more preferably 60 to 120 °C in consideration of the thermosetting properties of epoxy resins. The time is, for example, 1 to 30 minutes, preferably 5 to 15 minutes. The kneading is preferably carried out under reduced pressure conditions. This allows for degassing and prevents the intrusion of gas into the kneaded product. The pressure under reduced pressure conditions is preferably 0.1 kg / cm 2 or less, more preferably 0.05 kg / cm 2 or less. The lower limit of the pressure under reduced pressure is not particularly limited, but for example, 1 × 10 -4 kg / cm 2 or more.

[0099] When the kneaded product is plastically processed to form a curable composition sheet, it is preferable to plastically process the kneaded product in a high-temperature state without cooling after melt-kneading. The plastic processing method is not particularly limited, and examples include a flat press method, a T-die extrusion method, a screw die extrusion method, a roll rolling method, a roll kneading method, an inflation extrusion method, a co-extrusion method, a calendar molding method, etc. Examples of molding machines include a T-die screw molding machine, a compression mold molding machine, and a calendar molding machine. The plastic processing temperature is preferably not less than the softening point of each of the above components, and in consideration of the thermosetting and formability of epoxy resins, it 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-like curable composition. Also, the sheet-like curable composition may be in the form of single sheets or a roll that can be wound up.

[0100] The thickness of the sheet-like curable composition can be adjusted as appropriate according to the application, but it is preferably 50 μm or more, and more preferably 70 μm or more. By setting the thickness to 50 μm or more, for example, when used to seal IC chips and their surrounding wiring layers and insulating layers together, it becomes easy to completely cover the object to be coated, and an excellent cured product can be obtained.

[0101] Furthermore, the obtained sheet-like curable composition may be pulverized to form a powder or granules. The powder or granules may also be compressed into tablets.

[0102] Powdered, granular, or tablet-formed curable compositions may be manufactured directly from a mixture by melt-kneading using rolls or a kneader, without going through a sheet. This method can be performed using, for example, a kneader, roll mill, super mixer, Henschel mixer, Shugi mixer, or vertical mixer. It can be manufactured using batch-type kneaders such as lanunators, high-speed mixers, fur matrices, ball mills, steel mills, sand mills, vibratory mills, attritors, and Banbury mixers; twin-screw extruders, single-screw extruders, rotor-type twin-screw kneaders, etc.

[0103] Specifically, examples include: a method in which a molten and kneaded curable composition is supplied to the inside of a rotor consisting of a cylindrical outer circumference having multiple small holes and a disc-shaped bottom surface, and the curable composition is passed through the small holes by centrifugal force obtained by rotating the rotor; a method in which each raw material component of the curable composition is pre-mixed in a mixer, then heated and kneaded in a kneader such as a roll, kneader, or extruder, followed by a cooling and pulverization process to obtain pulverized material, from which coarse particles and fine powder are removed using a sieve; and a method in which each raw material component of the curable composition is pre-mixed in a mixer, then heated and kneaded using an extruder equipped with a die having multiple small diameters at the tip of the screw, and the molten resin extruded in a strand-like manner from the small holes arranged in the die is cut by a cutter that slides and rotates substantially parallel to the die surface.

[0104] When the material is in granular form, a particle size of 70 to 500 μm is preferable. By setting the particle size to 70 to 500 μm, it becomes easier to adjust the thickness of the cured composition while suppressing contamination by powder particles. The particle size is measured by extracting and quantifying particles using image binarization by microscopic observation.

[0105] Alternatively, a varnish may be prepared by mixing each component with a solvent, or by dissolving or dispersing a curable composition obtained by kneading each raw material component in an organic solvent, and then applying and drying the varnish to obtain a sheet-like curable composition. Methods of application include coating using coating machines such as comma coaters and die coaters, and printing methods such as stencil printing and gravure printing.

[0106] Furthermore, as described above, the sheet-like curable composition produced via varnish may be further pulverized into granules or powder. It may also be molded from the granules or powder into any desired shape, such as tablets (pellets). Additionally, the varnish can be spray-dried to form granules, powder, etc. The form of the curable composition can be appropriately selected depending on the application. For example, from the viewpoint of mold filling properties, granular or powdery forms are preferred, while from the viewpoint of productivity, sheet forms are preferred.

[0107] ≪Cured product and method for producing the same≫ A cured product is obtained by coating a substrate with the thermosetting curable composition of this embodiment, then drying and thermal polymerization, or by thermal melt molding and curing treatment. Thermal melt molding and curing treatment may be performed simultaneously, or the curing treatment may be performed after thermal melt molding. Here, "cured product" refers to a state in which the curing reaction does not substantially proceed even if further heating is performed. In the melt kneading process when manufacturing the curable composition, a portion of the material may undergo a curing reaction, but this state, which could be cured by further heating, is not included in the definition of a cured product. When using the curable composition to encapsulate, for example, an IC chip, stress relaxation occurs due to the tetracarboxylic acid polymer (A) during the process of softening and fluidizing the molded body when heat is applied. The stress is distributed in the planar and longitudinal directions of the encapsulated body, resulting in effects such as suppression of adhesion reduction and improvement of barrier properties. Pressure may be applied during melt molding.

[0108] The thermosetting temperature is preferably 150 to 230°C, and the heating time is preferably 30 to 180 minutes. The curing agent (D) forms three-dimensional crosslinks and becomes a cured product. When thermal melting, pressure may be applied in addition to heat. Applying heat and pressure makes softening and fluidization easier.

[0109] The glass transition temperature (Tg) of the cured product is preferably 100 to 200°C, and more preferably 140 to 180°C. Within this range, adhesive strength and barrier properties are improved.

[0110] If the curable composition of this embodiment is in sheet form, for example, this sheet can be placed on a semiconductor chip, melt-molded by thermocompression bonding, and then cured to obtain an IC package in which the semiconductor chip is coated with a cured material that functions as a sealing resin. Alternatively, if the curable composition of this embodiment is in tablet form, for example, this tablet can be injected into a mold in which a semiconductor chip is set while melting and flowing, and an IC package can be obtained in which the cured material of the curable composition serves as the sealing resin through a molding process and a curing process.

[0111] ≪Laminated structure≫ The laminate comprises an adhesive layer formed from the curable composition of the present invention and a substrate. The laminate can be obtained by sandwiching an adhesive or adhesive sheet made from the curable composition of the present invention between plastic films such as polyester or polyimide, metal foil, etc., and then heating and pressurizing it. The film thickness of the curable composition is preferably 5 to 500 μm, and more preferably 10 to 100 μm, in order to exhibit sufficient adhesion and gas barrier properties, and also in terms of ease of handling.

[0112] When using a plastic film as the base material, examples of plastic materials 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, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketones, and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0113] When using metal foil as the base material, examples of metal foil include copper foil and aluminum foil, with copper foil being preferred. As for copper foil, foil made of single-metal copper may be used, or foil made of an alloy of copper with another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0114] The method for applying the curable composition to the substrate is not particularly limited and includes, for example, comma coating, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure printing, flexographic printing, dip coating, spray coating, spin coating, etc. [Examples]

[0115] The present invention will be described in more detail below, but the following examples do not limit the scope of the present invention in any way. In the examples, "parts" refers to "parts by mass," "%" refers to "percentage by mass," and "RH" refers to "relative humidity." The amounts in the table are in parts by mass.

[0116] <Method for measuring weight-average molecular weight (Mw)> Mw was measured using a GPC (gel permeation chromatography) system "GPC-101" manufactured by Showa Denko. GPC is a liquid chromatography system that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on differences in their molecular size. In this invention, two "KF-805L" columns (Showa Denko: GPC column: 8mm ID × 300mm size) were connected in series, and the measurement was performed under the conditions of a sample concentration of 1% by mass, a flow rate of 1.0 mL / min, a pressure of 3.8 MPa, and a column temperature of 40°C. The weight-average molecular weight (Mw) was determined in polystyrene equivalent. For data analysis, calibration curves, molecular weights, and peak areas were calculated using the manufacturer's built-in software, and the weight-average molecular weight was determined for the analysis target range of retention times from 17.9 to 30.0 minutes.

[0117] <Average particle diameter D 50 Measurement method > The average particle size was measured dry using a Shimadzu Corporation SALD-2300 laser diffraction particle size distribution analyzer. The refractive indices of silica filler (B) and insulating thermal conductive filler (C) were taken as literature values ​​for silica filler (B) and insulating thermal conductive filler (C). For example, for aluminum oxide, the refractive index parameter was set to 1.70-0.10i for the analysis. From the measurement results, the particle size (median diameter) at 50% of the cumulative mass percentage was calculated, and the average particle size D of the powder was determined. 50 That's what I decided.

[0118] Synthesis of <tetracarboxylic acid modified product (A)> [Tetracarboxylic acid modified product (A-1)] In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 31 parts of 2-(benzyloxy)ethaneamine, 177.6 parts of ε-caprolactone, and 0.1 part of monobutyltin(IV) oxide as a catalyst were charged. After purging with nitrogen gas, the mixture was heated and stirred at 120°C for 4 hours. Non-volatile content measurement confirmed that 98% had reacted, yielding compound (a2-1) with one hydroxyl group at the end. Next, 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 reacted at 100°C for 5 hours to obtain tetracarboxylic acid modified product (A-1). The weight-average molecular weights of (a2-1) and (A-1) were measured and the results are shown in Table 1.

[0119] [Tetracarboxylic acid modified products (A-2)~(A-7), (A'-1)] The synthesis was carried out in the same manner as in (A-1) according to the composition and mass of the components in Table 1 to obtain tetracarboxylic acid modified products (A-2) to (A-7) and (A'-1).

[0120] [Compounds having one hydroxyl group at the terminal end (a2-9)] The compound (a2-9), having one hydroxyl group at its terminus, was synthesized in the same manner as (a2-1) according to the composition and mass of the components in Table 1.

[0121] [Tetracarboxylic acid modified product (A-8)] In a four-necked flask equipped with a stirrer, a reflux condenser with a Dean-Stark apparatus, a nitrogen inlet tube, and a thermometer, 100 parts of UNILIN350 and 33 parts of MCTC (5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride) were charged. The mixture was heated to 120°C while stirring, and the temperature was maintained at that temperature for 6 hours to complete the reaction and obtain the tetracarboxylic acid modified product (A-8).

[0122] [Tetracarboxylic acid modified product (A-15)] In a four-necked flask equipped with a stirrer, a reflux condenser with a Dean-Stark apparatus, a nitrogen inlet tube, and a thermometer, 50 parts of UNITHOX480, 50 parts of the compound (a2-9) having one hydroxyl group at the end prepared above, and 5.1 parts of MCTC (5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride) were charged. The mixture was heated to 120°C while stirring, and the temperature was maintained at that temperature for 6 hours to complete the reaction, yielding the tetracarboxylic acid modified product (A-15).

[0123] [(A-9)~(A-14), (A-16)] The synthesis was carried out in the same manner as in (A-8) according to the composition and mass of the components in Table 2 to obtain tetracarboxylic acid modified products (A-9) to (A-14) and (A-16).

[0124] [Table 1]

[0125] [Table 2]

[0126] The meanings of the abbreviations in Tables 3-5 are shown below. BTA: 1,2,3,4-butanetetracarboxylic dianhydride MCTC: 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid 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 Uniox M2000: Weight-average molecular weight 2,600, polyoxyethylene monomethyl ether UNITHOX480: Weight average molecular weight 3,000, ethoxylated alcohol, EO content 80% by mass UNITHOX420: Weight average molecular weight 800, ethoxylated alcohol, EO content 20% by mass UNITHOX450: Weight average molecular weight 1,200, ethoxylated alcohol, EO content 50% by mass UNITHOX750: Weight average molecular weight 1800, ethoxylated alcohol, EO content 50% by mass

[0127] [Example 1] 0.6 parts of tetracarboxylic acid modified product (A-1), 69.9 parts of plate-like silica (B-1), 10 parts of molten spherical silica (B-2), and 14.3 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 are blended and kneaded in a kneader at 80°C under reduced pressure (0.01 kg / cm²). 2 The mixture was prepared by melt-kneading using the method described below, and its kneadability was evaluated. Next, the obtained mixture was formed by a plate press method to obtain a sheet-like curable composition with a thickness of 300 μm.

[0128] [Examples 2-35], [Comparative Examples 1-6] The compounds were prepared in the same manner as in Example 1 as shown in Tables 3-5, and a sheet-like curable composition was obtained in the same manner as in Example 1. The results of the kneadability evaluation are also shown in Tables 3-5.

[0129] <Evaluation of kneadability> Mixed in a kneader at 80°C under reduced pressure (0.01 kg / cm²). 2 The mixture was melted and kneaded, the resin-insoluble components were visually inspected, the time required to adjust the kneaded mixture until the insoluble components were eliminated was measured, and the mixture was evaluated according to the following evaluation criteria. 3. Mixing time is less than 10 minutes. 2. The mixing time is 10 minutes or more but less than 20 minutes. 1: After a 20-minute preparation time for the mixture, the composition is uneven and cannot be mixed.

[0130] Details of the materials used in the examples and comparative examples are shown below.

[0131] • Silica filler (B) B-1: Plate-shaped silica (manufactured by AGC, Sunlovely, average particle size D 50 5μm) B-2: Fused spherical silica (Admatex Co., Ltd., SO-25R, average particle size D 50 (0.5 μm)

[0132] • Insulating thermal conductive filler (C) C-1: Plate-shaped alumina (manufactured by Kinsei Matec, Seraph 02025, average particle size D 50 2μm) C-2: Plate-shaped alumina (manufactured by Kinsei Matec, Seraph 05070, average particle size D) 50 5μm) C-3: Boron nitride (manufactured by Tomoe Chemical Co., Ltd., PT120, average particle size D 50 12μm)

[0133] • Hardener (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: Phenolic-modified xylene 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 phenolic resin, manufactured by Meiwa Kasei Co., Ltd., MEH-7500, OH equivalent = 97 g / eq. D-10: Tris(2,3-epoxypropyl) isocyanurate

[0134] Curing catalyst (E) E-1: Imidazole compound (2PHZ-PW, manufactured by Shikoku Chemicals Co., Ltd.)

[0135] For the cured products of the curable compositions in each example and comparative example, the glass transition temperature was measured, and the water vapor permeability, oxygen permeability, and adhesiveness were evaluated. The measurement methods and evaluation criteria are as follows.

[0136] <Method for measuring the glass transition temperature (Tg) of a cured product> Each of the prepared 300 μm sheet-like curable compositions was heat-cured on a heat-resistant release film at 180°C for 60 minutes to prepare samples for glass transition temperature measurement. Tanδ was measured using a dynamic viscoelasticity analyzer 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: 10Hz Grip length: 15mm Width: 5mm

[0137] <Preparation of samples and test pieces for adhesive strength testing> Each sheet of curable composition prepared was cut to 50 mm x 50 mm, and nine 5 mm x 5 mm x 300 μm Au-plated silicon chips were placed on top of it in three vertical and three horizontal rows at equal intervals. However, the sheet of curable composition was positioned so that it was in contact with the silicon surface of the silicon chips. To ensure close adhesion between the sheet of curable composition and the silicon chips, a 38 μm polyethylene terephthalate sheet treated with silicone release agent was placed opposite and heat-laminated using a heat lamination test apparatus (temperature 80°C, cylinder pressure 0.3 MPa). After heat lamination, cuts were made around the silicon chips with a utility knife to create samples for adhesion strength testing, with the sheet of curable composition temporarily adhered to one side of the silicon chip. A gold-plated copper frame substrate was prepared as the adherend, and a silicon chip with a sheet-like curable composition temporarily bonded to it was placed on top of it. The substrate was then hot-pressed (150°C × 1 MPa × 1 min), followed by post-baking (170°C × 2 hours) to prepare the test specimen.

[0138] <Evaluation of adhesive strength> Each test specimen prepared as described above was evaluated using a bond tester (Nordson Advanced Technologies, product name: Dage4000-PXY). The measurement conditions were a measurement speed of 100 μm / s and a measurement height of 100 μm. The arithmetic mean of the adhesive strength measured at three points was calculated. A higher value indicates better adhesion of the cured material to the silicone chip and the substrate. The evaluation criteria are as follows. 5: Excellent (arithmetic mean of adhesive strength is 7 N / mm or higher). 4: Superior (arithmetic mean of adhesive strength is 5 N / mm or greater, but less than 7 N / mm). 3: Excellent (arithmetic mean of adhesive strength is 3 N / mm or more, and less than 5 N / mm). 2: Practical (arithmetic mean of adhesive strength is 1 N / mm or more, and less than 3 N / mm). 1: Impractical (arithmetic mean of adhesive strength is less than 1 N / mm).

[0139] <Evaluation of water vapor transmission rate> Each of the obtained sheet-like curable compositions was cut into 50 mm x 50 mm sections and post-baked (170°C x 2 hours) to prepare samples for water vapor transmission rate measurement. Water vapor transmission rate was measured using a cup method moisture meter. The measurement method was carried out in accordance with JIS Z0208, and the measurement conditions were 40°C and 90% relative humidity. 5: Excellent (Water vapor transmission rate of 3.0 g / m³) 2 ·day or less). 4: Superior (water vapor transmission rate of 3.0 g / m³) 2 • Over 5.0 g / m² per day 2 ·day or less). 3: Excellent (Water vapor transmission rate of 5.0 g / m³) 2 • Over 10.0 g / m³ 2 ·day or less). 2: Practical (water vapor transmission rate of 10.0 g / m³) 2 • 30.0 g / m³ over a day 2 (Less than 1 day) 1: Impossible to use (water vapor transmission rate of 30.0 g / m³) 2 (more than one day).

[0140] <Evaluation of oxygen permeability> Each of the obtained sheet-like curable compositions was cut into 50 mm x 50 mm sections and post-baked (170°C x 2 hours) to prepare samples for measurement. Oxygen permeability was measured under conditions of 23°C and 80% RH relative humidity and evaluated according to the following criteria. Oxygen permeability was measured using the isobaric method in accordance with JIS K 7126, using a MOCON OX-TRAN2 / 21 oxygen permeability analyzer. 5: Excellent (oxygen permeability of 3.0 cc / m³) 2 ·day · atm or less). 4: Superior (oxygen permeability of 3.0 cc / m³) 2 • day • atm exceeding 5.0 cc / m 2 ·day · atm or less). 3: Excellent (oxygen permeability of 5.0 cc / m³) 2 • day • atm exceeding 10.0 cc / m 2 ·day · atm or less). 2: It is practical (oxygen permeability of 10.0 cc / m³) 2 • day • atm exceeding 30.0 cc / m 2 (Less than 1 / day ATM) 1: Impossible to use (oxygen permeability of 30.0 cc / m³) 2 ·day · atm or more).

[0141] As shown in the examples, it was confirmed that the cured product obtained from the curable composition according to this example exhibits superior adhesion and gas barrier properties compared to Comparative Examples 1 to 5.

[0142] [Table 3]

[0143] [Table 4]

[0144] [Table 5]

[0145] [Industrial applicability] The curable composition according to this embodiment exhibits excellent kneadability, adhesion, and gas barrier properties, making it suitable for use as an insulating resin material, including encapsulants, adhesives, underfills, and potting materials for semiconductor chips. Furthermore, it can be applied to fields with high barrier properties, such as organic thin-film solar cells and organic devices like display elements, and is expected to be useful in a wide range of fields.< / h> < / n> < / h> < / n> < / h> < / n> < / h> < / n> < / n> < / h>

Claims

1. The material comprises a tetracarboxylic acid modified product (A), at least one of a silica filler (B) and an insulating thermal conductive filler (C), and a curing agent (D). The tetracarboxylic acid modified product (A) is a reaction product of an aliphatic tetracarboxylic anhydride (a1) and a compound (a2) having one hydroxyl group at its terminal end. A curable composition containing 0.01 to 5% by mass of a tetracarboxylic acid modified product (A) and a total of 40 to 95% by mass of silica filler (B) and insulating thermal conductive filler (C) in 100% by mass of the nonvolatile content of the curable composition.

2. The curable composition according to claim 1, wherein the compound (a2) having one hydroxyl group at its terminus 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 curing agent (D) comprises an epoxy curing agent.

4. The curable composition according to claim 1, wherein the insulating thermal conductive filler (C) contains alumina.

5. A cured product formed from the curable composition according to any one of claims 1 to 4.

6. A laminate comprising an adhesive layer made of the cured product described in claim 5, and a substrate.

7. The material comprises a tetracarboxylic acid modified product (A), at least one of a silica filler (B) and an insulating thermal conductive filler (C), and a curing agent (D). The tetracarboxylic acid modified product (A) is a reaction product of an aliphatic tetracarboxylic anhydride (a1) and a compound (a2) having one hydroxyl group at its terminal end. A method for producing a cured product comprising the steps of forming a curable composition by thermal melting and then thermally curing it, wherein the curable composition contains 0.1 to 5% by mass of a tetracarboxylic acid modified product (A), and a total of 40 to 95% by mass of silica filler (B) and insulating thermal conductive filler (C) in 100% by mass of the nonvolatile content of the curable composition.

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