CURABLE COMPOSITION, CURED PRODUCT, LAMINATE, AND METHOD FOR PRODUCING CURED PRODUCT

Abstract

Provided are a curable composition which gives a cured product which has excellent adhesive strength after long-term aging under high temperature and high humidity conditions and excellent adhesiveness at 25°C, a cured product, a laminate, and a method for producing the cured product. [Solution] A curable composition comprising a polyamide resin (A), a tetracarboxylic acid modified product (B), at least one of a silica filler (C) and a thermally conductive filler (D), and a curing agent (E), wherein, based on 100 mass% of the monomers constituting the polyamide resin (A), the total content of dimer acid and dimer diamine is 50 to 99 mass%, the tetracarboxylic acid modified product (B) is a reaction product of an aliphatic tetracarboxylic acid anhydride (b1) and a compound (b2) having one hydroxyl group at its terminal, and the curable composition contains, based on 100 mass% of the nonvolatile content of the curable composition, 0.1 to 40 mass% of the polyamide resin (A), 0.1 to 5 mass% of the tetracarboxylic acid modified product (B), and 40 to 95 mass% of the silica filler (C) and the thermally conductive filler (D).

Description

[Technical field]

[0001] The present invention relates to a curable 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 parts, such as microprocessors, transistors, and memories, and are mounted in various electronic devices such as computers, smartphones, and flat panel displays. Packages that incorporate ICs or mounting boards that incorporate ICs use insulating resins such as encapsulants, adhesives, underfill agents, and potting materials.

[0003] Patent Document 1 discloses a resin composition as a mold underfill material for WL-CS (wafer level chip size package), which contains a polymer resin having a number average molecular weight within a specific range and one or more structures selected from a polybutadiene structure, a polyisoprene structure, a polycarbonate structure, a (meth)acrylate structure, and a polysiloxane structure, an inorganic filler, an epoxy resin, and a curing accelerator. In addition, Patent Document 2 proposes a sealing film that contains 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, and contains a specific amount of the elastomer component. Furthermore, Patent Document 3 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, a phenolic hydroxyl group unit, and a hydroxyl group in a side chain, with a radically polymerizable epoxy, and also discloses a resin composition containing the radically polymerizable polyamide, a photopolymerization initiator, an epoxy resin, a phenolic resin, a silica filler, a solvent, etc. Patent Document 4 discloses a thermosetting resin composition containing a polyamide (A) having a dimer structure obtained by polymerizing a polybasic acid monomer and a polyamine monomer and having a phenolic hydroxyl group in a side chain, and a tri- or higher functional compound (B) capable of reacting with the phenolic hydroxyl group. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2017-057313 A [Patent Document 2] International Publication No. 2 016 / 136741 [Patent Document 3] JP 2019-119886 A [Patent Document 4] International Publication No. 2016 / 001949 Summary of the Invention [Problem to be solved by the invention]

[0005] In the manufacturing process of semiconductor packages, there are multiple heating steps to form a redistribution layer. For example, fan-out wafer-level packages (FO-WLPs) have been attracting attention as chip-sized packages that can increase the number of pins, and the manufacturing process of face-down WLPs, which are representative of FO-WLPs, includes a step in which a semiconductor chip is sealed on one side with a molding resin composition, and then repeatedly heated in the subsequent redistribution layer formation process. For this reason, there is a demand for resin compositions with high moisture and heat resistance that can suppress foaming and cracks during heating.

[0006] Electronic components and electronic devices are widely used in automobiles, industrial machines, ships, aircraft, etc. In such cases, there is concern that moisture may accumulate at the interface between the chip and the mold resin, causing package cracks, wire breakage, metal corrosion, and electrochemical migration due to water vapor expansion. For this reason, in recent years, there has been a demand for sealing materials that show high adhesion reliability in long-term aging tests under high temperature and high humidity. On the other hand, in response to the trend toward higher performance of electronic components, there is a demand for resin compositions with high adhesive strength at 25°C to increase the stability of products. However, it is not easy to achieve both the stability of adhesive strength, which requires the rigidity of the resin, and the adhesive strength, which requires the flexibility of the polymer chain.

[0007] The present invention has been made in view of the above-mentioned background, and an object of the present invention is to provide a curable composition, a cured product, a laminate, and a method for producing the cured product, which are capable of giving a cured product that has excellent adhesive strength after long-term aging under high temperature and high humidity conditions and excellent adhesiveness at 25°C. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have found that the problems of the present invention can be solved in the following manner. Based on this finding, the present invention has been completed.

[0009] [1] A composition comprising a polyamide resin (A), a tetracarboxylic acid modified product (B), at least one of a silica filler (C) and a thermally conductive filler (D), and a curing agent (E), The polyamide resin (A) contains 50 to 99 mass% of dimer acid and dimer diamine in total based on 100 mass% of monomers constituting the polyamide resin (A), The tetracarboxylic acid modified product (B) is a reaction product of an aliphatic tetracarboxylic acid anhydride (b1) and a compound (b2) having one terminal hydroxyl group, A curable composition comprising, relative to 100% by mass of nonvolatile content of the curable composition, 0.1 to 40% by mass of a polyamide resin (A), 0.1 to 5% by mass of a tetracarboxylic acid modified product (B), and 40 to 95% by mass in total of a silica filler (C) and a thermally conductive filler (D).

[0010] [2] The above curable composition, wherein the compound (b2) having one terminal hydroxyl group contains at least one of an ether bond and an ester bond in a part of its molecular structure and has a weight average molecular weight of 500 to 10,000.

[0011] [3] The above curable composition, wherein the polyamide resin (A) has a glass transition temperature of 0 to 90°C.

[0012] [4] The curable composition, wherein the curing agent (E) contains an epoxy-based curing agent.

[0013] [5] The curable composition, wherein the thermally conductive filler (D) contains alumina.

[0014] [6] A cured product formed from the curable composition.

[0015] [7] A laminate comprising an adhesive layer made of the cured product and a substrate.

[0016] [8] A method for producing a cured product, comprising the steps of: molding the curable composition by thermal melting; and thermally curing the composition. Effect of the Invention

[0017] The present invention can provide a curable composition, a cured product, a laminate, and a method for producing the cured product, which are excellent in adhesive strength after long-term aging under high temperature and high humidity conditions and in adhesiveness at 25°C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention will be described in detail below. Needless to say, other embodiments are also included in the scope of the present invention as long as they are consistent with the gist of the present invention. In addition, in this specification, a numerical range specified using "~" includes the numerical values ​​written before and after "~" as the range of the lower and upper limits. In addition, in this specification, "film" and "sheet" are not distinguished by thickness. In other words, in this specification, "sheet" includes a thin film-like material, and in this specification, "film" includes a thick sheet-like material. In addition, various components that appear in this specification may be used independently alone or in combination of two or more types, unless otherwise noted.

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

[0020] ≪Curable composition≫ The curable composition of the present invention contains a polyamide resin (A), a tetracarboxylic acid modified product (B), at least one of a silica filler (C) and a thermally conductive filler (D), and a curing agent (E). Each component is explained below.

[0021] [Polyamide resin (A)] A polyamide resin is a polymer containing a repeating structural unit containing an amide group, and is a polymer of a polybasic acid compound and a polyamine compound, and if necessary, other monomers, or a modified product obtained by modifying the polymer. Here, the modified product refers to a derivative obtained by modifying a part of the molecular structure of the polymer (for example, by modifying a functional group, substituting with another compound, or adding another compound). The introduction of a dimer structure into a polyamide resin can be achieved by using a monomer having a dimer structure, and the monomer preferably used is a dimer acid which is a polybasic acid compound and / or a dimer diamine which is a polyamine compound.

[0022] The polyamide resin (A) contains 50 to 99% by mass of dimer acid and dimer diamine in total, based on 100% by mass of monomers constituting the polyamide resin (A). The charge rate of the monomers used in the polymerization of the polyamide resin (A) is substantially the same as the ratio of the components constituting the polyamide resin (A), so the charge rate of the dimer acid and dimer diamine in total, based on 100% by mass of all monomers used in the polymerization of the polyamide resin (A), may be 50 to 99% by mass. This allows the effect of the dimer structure to be fully exerted. The total content of the dimer acid and dimer diamine is preferably 60 to 95% by mass, more preferably 70 to 90% by mass. In the case of a modified product, the content of the dimer structure is a virtual monomer having a structure after modification, and in the case of a monomer that is not modified, it can be calculated from the content (mass%) of a monomer having a dimer structure in 100 mass% of all monomers using raw material monomers. The content of the virtual monomer having a structure after modification can be calculated taking into consideration the reaction rate 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 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 is 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" can be used, and the dimer structure content of other monomers can be calculated in the same manner as in the above-mentioned method for calculating the polymer.

[0023] The dimer structure has a hydrocarbon chain or ring structure, and is less polar than the epoxy resin or other hardening resins that are blended with it, so it can suppress moisture absorption from outside the system. In addition, there are strong hydrogen bonds derived from the amide bonds of the polyamide resin (A). Due to the high cohesiveness of the hydrogen bonds, good adhesive strength can be expected even after long periods of time under high temperature and high humidity, and the flexible skeleton can also improve adhesive strength at 25°C.

[0024] The polyamide resin (A) preferably has a functional group capable of crosslinking with the curing agent (E) by heat. Examples of the functional group include a carboxy group, an amino group, and a hydroxyl group. These may be functional groups derived from the monomers of the polyamide resin (A), or the functional group may be introduced as a modified product after the polymer is obtained. The functional group may be present at the end of the polymer, or may be present in 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 end of the polymer. Another example is a polymer having at least one of a functional group such as a carboxy group, an amino group, or a hydroxyl group in a side group or a side chain. Incidentally, if the functional group has a photopolymerizable group, the curable composition containing the polyamide resin may be over-crosslinked, resulting in a decrease in adhesiveness, or when the curable composition is thermally melted and molded, a thermal radical reaction may occur, resulting in a decrease in moldability. Therefore, it is preferable that the curable composition does not have a photopolymerizable group.

[0025] When the polyamide resin (A) has a hydroxyl group, a phenolic hydroxyl group is preferable. By having a phenolic hydroxyl group, a crosslinked structure with the curing agent (E) can be constructed, and a cured product with excellent barrier properties can be obtained. 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 included in the main chain skeleton of the polyamide resin (A). In addition, from the viewpoint of adhesive strength, it is preferable to use a polybasic acid compound having a phenolic hydroxyl group as a monomer of the polyamide resin (A).

[0026] The polyamide resin (A) 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 invention.

[0027] <Polybasic acid compounds> The polybasic acid compound used as the raw material of the polyamide resin (A) is a dibasic or higher carboxylic acid. The polybasic acid compound may be a part of an acid anhydride. Examples of the polybasic acid compound include dimer acid and other 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, 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 increased, the stress relaxation effect due to the dimer structure is fully exerted, and better adhesive strength at 25°C can be exerted.

[0028] (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).

[0029] The fatty acid dimer is preferably a compound having 20 to 60 carbon atoms, more preferably a compound having 24 to 56 carbon atoms, further 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 Diels-Alder reaction of a fatty acid. The branched structure is preferably one containing an aliphatic chain or an aliphatic chain and a ring structure, more preferably one containing an aliphatic chain and a ring structure. The ring structure is preferably one or more aromatic rings or an alicyclic structure, more preferably an alicyclic structure. The alicyclic structure may have one double bond in the ring, or may have no double bond. The above carbon number and branched structure allow for excellent adhesive strength at 25°C and maintenance of adhesive strength after long-term storage under high temperature and high humidity.

[0030] Examples of polybasic acid compounds having a dimer structure include structures represented by the following chemical formulas (1) to (4). It goes without saying that the polybasic acid compounds having a dimer structure are not limited to the following structures.

[0031] [ka] [ka] [ka] [ka]

[0032] 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 carbon-carbon triple bonds. Examples of the fatty acid include natural fatty acids such as soybean oil fatty acid, tall oil fatty acid, rapeseed oil fatty acid, and oleic acid, linoleic acid, linolenic acid, and erucic acid which are refined from these fatty acids. When the fatty acid dimer is synthesized, in addition to the fatty acid dimer, a fatty acid trimer and sometimes a tetramer are generated. Therefore, the polybasic acid compound containing a dimer skeleton is a mixture containing not only the fatty acid dimer as the main component, but also the fatty acid trimer and the like, and sometimes the fatty acid as the raw material. The fatty acid dimer is preferably 70% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more in 100% by mass of the dimer acid.

[0033] Since the dimer acid uses unsaturated fatty acids as raw materials, unsaturated bonds may remain. In such cases, hydrogenation (also called hydrogenation reaction) can be performed to suppress the number of unsaturated bonds. This improves the reaction stability when synthesizing the polyamide resin (A), and further improves the adhesive strength of the cured product of the curable composition containing the polyamide resin (A). The dimer acid can be used alone or in combination of two or more kinds.

[0034] 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 Co., Ltd.; and "Empol 1008", "Empol 1012", "Empol 1016", "Empol 1026", "Empol 1028", "Empol 1043", "Empol 1061", and "Empol 1062" manufactured by BASF Japan Co., Ltd. Among these, by using "Pripol 1009" having 36 carbon atoms, a polyamide resin (A) having better adhesion to the adherend is easily obtained. In addition, by using "Pripol 1004" having 44 carbon atoms, a polyamide resin (A) having good flexibility is easily obtained.

[0035] (Other polybasic acid compounds) The other polybasic acid compound is a polybasic acid compound other than dimer acid, which is a compound having two or more functional groups. The polybasic acid compounds can be used alone or in combination of two or more kinds.

[0036] 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.

[0037] Examples of trifunctional or higher polybasic acid compounds include trimellitic acid, hydrogenated trimellitic acid, pyromellitic acid, hydrogenated pyromellitic acid, trimesic acid, and 1,4,5,8-naphthalenetetracarboxylic acid. By using a trifunctional or higher polybasic acid compound, a branched structure can be introduced into the polyamide resin (A), improving the cohesive strength of the cured product and allowing the adhesive strength to be maintained after long-term storage under high temperature and high humidity.

[0038] Other suitable examples of polybasic acid compounds include polybasic acid compounds having phenolic hydroxyl groups. Polybasic acid compounds having phenolic hydroxyl groups are compounds having hydroxyl groups (also called phenolic hydroxyl groups) directly bonded to aromatic rings like phenol, and having two or more acidic functional groups. Examples of the acidic functional groups include carboxyl groups. By using a polybasic acid compound having a phenolic hydroxyl group, the crosslinking structure between the polyamide resin (A) and the curing agent (E) can be easily adjusted during the curing process. As a result, strong crosslinks can be formed, which effectively improves the adhesive strength after long-term storage under high temperature and high humidity conditions.

[0039] 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 the polybasic acid compound having a phenolic hydroxyl group in terms of copolymerizability, ease of availability, etc. In addition, in the polybasic acid compound having a phenolic hydroxyl group, the carboxy group of the compound exemplified in the upper row may form an acid anhydride group, or the carboxy group may form an ester.

[0040] <Polyamine compounds> The polyamine compound serving as the raw material of the polyamide resin (A) is a compound having two or more amino groups. Suitable examples of the polyamine compound include dimer diamine and other polyamine compounds other than dimer diamine. When a dimer diamine is used as the polyamine compound, the content of the 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 making the content of the dimer diamine in 100% by mass of the polyamine compound 50% by mass or more, the stress relaxation property due to the dimer structure can be sufficiently exhibited, and more excellent adhesive strength can be realized.

[0041] (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. For example, the conversion method includes amidating a carboxylic acid, converting it to an amine by the Hofmann rearrangement, and further distilling and purifying it. The dimer diamine is preferably a compound having 20 to 60 carbon atoms in terms of adhesive strength, more preferably a compound having 24 to 56 carbon atoms, even more preferably a compound having 28 to 48 carbon atoms, and from the viewpoint of availability, even more preferably a compound having 36 to 44 carbon atoms.

[0042] Commercially available dimer diamines include, for example, "Priamine 1071", "Priamine 1073", "Priamine 1074", and "Priamine 1075" manufactured by Croda Japan Ltd., and "Versamine 551" manufactured by BASF Japan Ltd. The dimer diamines can be used alone or in combination of two or more kinds.

[0043] (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.

[0044] 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'-diaminodiphenylether, 4,4'-diaminodiphenylether, 4,4'-diamino-1,2-diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl Examples of the diamines include aromatic diamines such as phenylsulfone, 3,3'-diaminobenzophenone, and 3,3'-diaminodiphenylsulfone; aliphatic diamines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,9-nonanediamine, 1,12-dodecamethylenediamine, and metaxylenediamine; and alicyclic diamines such as isophoronediamine, norbornanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, and piperazine.

[0045] Also, polyamine compounds having phenolic hydroxyl groups can be mentioned. A polyamide resin (A) using a polyamine compound having a phenolic hydroxyl group is preferable in terms of adhesive strength. A polyamine compound having a phenolic hydroxyl group is preferable because it can introduce a phenolic hydroxyl group into the polyamide resin (A). By introducing a phenolic hydroxyl group, it becomes possible to obtain a tougher cured product by three-dimensional crosslinking with the curing agent (E) to be blended. The polyamine compound having a phenolic hydroxyl group has a plurality of amino groups and a phenolic hydroxyl group. Examples of the polyamine compound having a phenolic hydroxyl group include polyamines represented by the following general formula (1).

[0046] [ka]

[0047] R in the formula 1 represents a direct bond or a group containing carbon, hydrogen, oxygen, nitrogen, sulfur, or a halogen. The above group is, for example, 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 (2) and a group represented by the following general formula (3).

[0048] [ka]

[0049] [ka] In the formula, r and s each independently represent an integer of 1 to 20; 2 represents a hydrogen atom or a methyl group.

[0050] Examples of polyamines represented by the general formula (1) include 2,2-bis(3-amino-4-hydroxyphenyl)propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 4,4'-diamino-3,3'-dihydroxybisphenyl.

[0051] 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.

[0052] Among these, the other polyamine compound is preferably isophoronediamine or norbornanediamine, in terms of improving the resistance to moist heat and the adhesive strength and the adhesive strength after long-term aging under high temperature and high humidity conditions.

[0053] <Method for producing polyamide resin (A)> The polyamide resin (A) can be produced, for example, by melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid-state polymerization, or a combination of these. Among these, solution polymerization is preferred. The solution polymerization can be carried out in the presence or absence of a catalyst using the above-mentioned polybasic acid compound, polyamine compound, and other monomers as necessary. For example, a predetermined amount of dimer acid, other acid monomers, dimer diamine, other amine monomers, and ion-exchanged water are charged into a flask filled with nitrogen, and uniformly dissolved or dispersed by heating and stirring at 20 to 100°C. Thereafter, the temperature is gradually raised to 230°C while removing the ion-exchanged water and water generated by the reaction, and when the temperature reaches 230°C, the pressure is reduced to about 15 mmHg, and the state is maintained for about 1 hour to obtain polyamide resin (A). The heating temperature is, for example, 150 to 300°C, and the heating time can be about 1 to 24 hours. In order to promote the synthesis reaction, it is preferable to carry out a dehydration or dealcoholization reaction, and in order 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.

[0054] When producing the polyamide resin (A), 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 (A). In addition, a part of the main chain end of the polyamide resin (A) is no longer a reactive functional group, improving stability over time. Examples of monoamines include aniline, benzylamine, 4-aminophenol, and 2-ethylhexylamine.

[0055] <Physical properties of polyamide resin (A)> The glass transition temperature (Tg) of the polyamide resin (A) is preferably 0 to 90° C., more preferably 0 to 70° C. Tg is the temperature at which the value (tan δ) obtained by dividing the viscosity term by the elasticity term measured for the polyamide resin (A) using a dynamic viscoelasticity measuring device shows a maximum. By setting the Tg of the polyamide resin (A) to 0 to 90°C, the compatibility with the curing agent (E), the silica filler (C) and / or the thermally conductive filler (D) is further improved in the step of forming a melt of the curable 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 conditions.

[0056] The weight average molecular weight (Mw) of the polyamide resin (A) is preferably 15,000 to 100,000, and more preferably 17,000 to 78,000. When the Mw is 15,000 or more, a suitable 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.

[0057] The acid value of the polyamide resin (A) is preferably 2 to 30 mgKOH / g, more preferably 3 to 25 mgKOH / g, and even more preferably 4 to 20 mgKOH / g. By setting the acid value to 2 to 30 mgKOH / g, the cured product can obtain an appropriate crosslink density, and the adhesive strength to the semiconductor chip at 25°C and the adhesive strength after long-term aging under high temperature and high humidity can be further improved.

[0058] The content of the polyamide resin (A) is 0.1 to 40 mass% and preferably 0.6 to 10 mass% based on 100 mass% of the nonvolatile content of the curable composition. By being within the above 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.

[0059] [Tetracarboxylic acid modified product (B)] The tetracarboxylic acid modified product (B) is a reaction product of an aliphatic tetracarboxylic acid anhydride (b1) and a compound (b2) having one hydroxyl group at the end. The bulky monool and carboxylic acid residues increase the spacing of the hydrogen bonds of the polyamide, optimizing the strength of the hydrogen bonds and improving the adhesive strength after long-term storage under high temperature and high humidity conditions.

[0060] The content of the tetracarboxylic acid modified product (B) is 0.1 to 5 mass %, preferably 0.5 to 3 mass %, based on 100 mass % of the nonvolatile content of the curable composition. By setting the content in the above range, the adhesive strength after long-term storage under high temperature and high humidity conditions and the adhesive strength at 25°C can be exhibited in a well-balanced manner.

[0061] <Aliphatic tetracarboxylic acid anhydride (b1)> The aliphatic tetracarboxylic acid anhydride (b1) may be a compound having a chain hydrocarbon structure or a compound having an alicyclic hydrocarbon structure. The "chain hydrocarbon structure" is a straight chain 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. The portion not adjacent to the acid anhydride may contain an aromatic group.

[0062] Specific examples of the aliphatic tetracarboxylic acid anhydride (b1) 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. 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]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]octane-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]octane-7-ene-2,3,5,6 -tetracarboxylic acids, cyclo-, bicyclo-, and tricyclotetracarboxylic acids such as 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, and 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-tetratonate; Containing tetracarboxylic acid; tetracarboxylic 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, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, etc. can be exemplified. Among them, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic 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 are preferred, as they have good compatibility with the polyamide resin (A). These compounds may be used alone or in combination of two or more.

[0063] <Compound (b2) having one hydroxyl group at the terminal> Examples of the compound (b2) having one hydroxyl group at the end include alcohol compounds having a long-chain alkyl group with an average carbon number of 25 to 50, monool derived from polyethylene glycol, monool derived from polypropylene glycol, polyester monool, etc. Among them, those containing at least one of an ether bond and an ester bond in a part of the molecular structure are preferred, specifically, polyethylene glycol and polyester monool are preferred. By using these, the strength of the hydrogen bond of the polyamide is optimized, and the adhesive strength can be well maintained even after long-term aging under high temperature and high humidity.

[0064] The weight average molecular weight of the compound (b2) having one hydroxyl group at its terminal is preferably 500 to 10,000, and more preferably 2,000 to 8,000. By being within the above range, the adhesive strength can be well maintained even after long-term storage under high temperature and high humidity conditions.

[0065] 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, and compounds obtained by purifying these natural fatty acids, and synthetic fatty acid-derived alcohols within the above ranges. Examples of commercially available synthetic fatty acid-derived alcohols include Unilin 350, Unilin 550, and Unilin 700, synthetic fatty acids manufactured by NuCeraSolutions.

[0066] Monools derived from polyethylene glycol and polypropylene glycol include, for example, those obtained by polymerization reaction of ethylene oxide (EO) or propylene oxide (PO) using alcohol as an initiator. Commercially available products as EO adducts of synthetic alcohols having an average carbon number of 20 to 50 include, for example, Unithox 450, Unithox 480, and Unithox 750 manufactured by NuCera Solutions.

[0067] Examples of the polyester monol include polyester monols 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, but good compatibility with the polyamide resin (A) can be obtained by using 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.

[0068] 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-hydroxyindan and 1-phenyl-1-propanol. Of these, benzyl alcohol and phenoxyethanol are preferred from the viewpoint of good compatibility with the polyamide resin (A).

[0069] Examples of monoalcohols having a molecular weight of 300 or less containing alkyleneoxy units 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, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, 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-Examples of the alkylene glycol monoalkyl ether include ethylhexyl ether, tetrapropylene glycol monomethyl ether, 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. Of these, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether are preferred from the viewpoint of good compatibility with the polyamide resin (A).

[0070] 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 good compatibility with the polyamide resin (A).

[0071] Examples of the alkyleneoxy unit-containing monoamine 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 good compatibility with the polyamide resin (A).

[0072] The initiator used for producing the polyester monool is preferably a monoalcohol. The monoalcohol and monoamine may be used alone or in combination of two or more kinds.

[0073] Examples of cyclic compounds that can be used in the production of polyester monool include alkylene oxides, lactones, lactides, dicarboxylic acid anhydrides, and epoxides. The cyclic compounds can be used alone or in combination of two or more kinds.

[0074] The alkylene oxide may be, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, or a combination 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.

[0075] 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 to the hydroxyl group of a monoalcohol are commercially available, such as the UNIOX series manufactured by NOF Corporation and the BLEMMER series manufactured by NOF Corporation, and can be used as the polymer (PeOH) in the production method of the present invention. 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.

[0076] Examples of lactones include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, alkyl-substituted ε-caprolactone, etc. Among these, it is preferable to use δ-valerolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone in terms of ring-opening polymerizability.

[0077] The lactones that can be used are not limited to those exemplified above, and may be used alone or in combination of two or more kinds.

[0078] As the lactide, one represented by the following general formula (4) is preferred (including glycolide).

[0079] [ka] [In general formula (4), R 31 and R 32 are each independently a hydrogen atom or a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms; R 33 and R 34 are each independently a hydrogen atom, a halogen atom, or a saturated or unsaturated, straight-chain or branched lower alkyl group having 1 to 9 carbon atoms.] In the present specification, lactide refers to lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) and glycolide (1,4-dioxane-2,5-dione). Of the above lactones and lactides, lactones are preferred.

[0080] 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 monoalcohol having a low boiling point 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.

[0081] The number of moles of lactone and / or lactide polymerized per mole of the initiator is preferably in the range of 1 to 60 moles, more preferably 2 to 20 moles, and most preferably 3 to 15 moles.

[0082] 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, and benzyltrimethylammonium iodide; Examples of the catalyst include quaternary phosphonium salts such as trimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodide, 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, organic tin compounds, organic aluminum compounds, organic titanate compounds, and zinc compounds such as zinc chloride. The amount of the 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 satisfied, a polymer without coloring is easily obtained at a polymerization rate suitable for production.

[0083] 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. If the range is satisfied, a polymer with fewer by-products can be easily obtained at a polymerization rate suitable for production.

[0084] Examples of dicarboxylic acid anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, itaconic anhydride, glutaric anhydride, dodecenylsuccinic anhydride, and chlorendec anhydride.

[0085] 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.

[0086] The method for producing the polyester monool is not particularly limited, but for example, an alkylene oxide may be polymerized with the initiator in the first stage, a lactone may be polymerized in the second stage, and a dicarboxylic anhydride and an epoxide may be polymerized alternately in the third stage. In this example, the initiator for polymerizing the lactone in the second stage is the alkylene oxide polymer having a hydroxyl group at one end polymerized in the first stage. In addition, the initiator for polymerizing the dicarboxylic anhydride and the epoxide alternately 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.

[0087] 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 anhydride and epoxide in the third step, and the combination of alkylene oxide, lactone (and / or lactide), and dicarboxylic anhydride and epoxide can be carried out in any order, one or more times. Alternatively, for the combinations of alkylene oxide, lactone (and / or lactide), and dicarboxylic anhydride and epoxide, ring-opening polymerization can be carried out by selecting any cyclic compound from them without carrying out ring-opening polymerization for all of them.

[0088] 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 the carboxyl group to generate a hydroxyl group. Furthermore, the acid anhydride group of the dicarboxylic anhydride reacts with the hydroxyl group, and the same reactions as above can be carried out in sequence. The polymerization mole numbers of the dicarboxylic anhydride and the epoxide per mole of the initiator are preferably 0 to 30 moles. In addition, the reaction ratio ([D] / [E]) of the dicarboxylic anhydride and the epoxide is preferably 0.8≦[D] / [E]≦1.0 ([D] is the number of moles of the dicarboxylic anhydride, and [E] is the number of moles of the epoxide). 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.

[0089] The alternating polymerization of dicarboxylic anhydride and epoxide is preferably carried out in the range of 50° C. to 180° C., more preferably 60° C. to 150° C. If the reaction temperature is less than 50° C. or exceeds 180° C., the reaction rate is extremely slow.

[0090] In terms of the simplicity of the production process, ease of molecular weight control, and high reaction rate, it is preferable to use lactone or lactide as the cyclic compound for the polyester monool.

[0091] 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 can be removed by an operation such as distillation, or can be used as it is as a part of the dispersant product.

[0092] <Method for producing tetracarboxylic acid modified product (B)> The tetracarboxylic acid modified product (B) can be obtained by reacting an aliphatic tetracarboxylic acid anhydride (b1) with a compound (b2) having one terminal hydroxyl group. The number of moles of aliphatic tetracarboxylic acid anhydride (b1) <h>and the number of moles of compound (b2) having one terminal hydroxyl group <n>When 1< <n> / <h><2.4 is preferable, and 1.4< is more preferable. <n> / <h><2.2, most preferably <n> / <h>= 2. <n> / <h>When the reaction is carried out with a molar ratio of less than 1, the remaining acid anhydride may be hydrolyzed with a required amount of water before use.

[0093] A catalyst may be used in the above reaction. For example, a tertiary amine compound such as triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc. can be used as the catalyst.

[0094] The above process may be carried out without a solvent or with a suitable dehydrated organic solvent. After completion of the reaction, the solvent used in the reaction may be removed by an operation such as distillation, or may be used as it is as part of the dispersant product.

[0095] The reaction temperature in the above step is preferably in the range of 80° C. to 180° C., more preferably 90° C. to 160° C. If the reaction temperature is less than 80° C., the reaction rate is slow, and if the reaction temperature exceeds 180° C., the acid anhydride that has reacted and opened the ring may again produce a cyclic anhydride, making it difficult to complete the reaction.

[0096] The weight average molecular weight of the tetracarboxylic acid modified product (B) is preferably from 1000 to 20,000, and more preferably from 4,000 to 16,000. By being within the above range, the adhesive strength after aging under high temperature and high humidity conditions is improved.

[0097] [Silica filler (C) and thermally conductive filler (D)] The curable composition of the present embodiment contains at least one of a silica filler (C) and a thermally conductive filler (D). By containing the silica filler (C) and / or the thermally conductive filler (D), the adhesive strength of the cured product after aging under high temperature and high humidity is improved. Furthermore, by combining at least one of the silica filler (C) and the thermally conductive filler (D) with the above-mentioned polyamide resin (A), tetracarboxylic acid modified product (B), and curing agent (E), the adhesive strength after aging under high temperature and high humidity is increased.

[0098] Examples of the silica filler (C) include plate-like silica, rod-like silica, fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, etc. Plate-like silica is preferred in terms of excellent gas barrier properties. The thermally conductive filler (D) preferably has a high thermal conductivity at 20°C, and is preferably 15 (W / m·K) or more. In addition, the volume resistivity is preferably high, and a filler having a volume resistivity of 10 to the power of 6 (Ω·cm) or more is preferable. Suitable examples of the thermally conductive filler (D) include alumina (aluminum oxide), aluminum nitride, silicon nitride, boron nitride, and silicon carbide. Among these, alumina (aluminum oxide) or boron nitride is preferable from the viewpoint of availability, and alumina is most preferable. The type of boron nitride is not particularly limited. For example, hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), wurtzite boron nitride, etc. can be exemplified. Among these, hexagonal boron nitride (h-BN) is preferable from the viewpoint of thermal conductivity. The shape of boron nitride is not limited, but a scaly shape is preferable, and it may be a primary particle or a secondary particle formed by agglomeration of primary particles. Examples of the thermally conductive filler (D) include plate-like, rod-like, molten crushed bodies, molten spheres, crystals, secondary aggregates, etc. Among these, plate-like alumina is preferred because it has excellent adhesive strength after aging under high temperature and high humidity conditions.

[0099] The silica filler (C) and the thermally conductive filler (D) each preferably have an average particle size 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 30 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.

[0100] The silica filler (C) and the thermally conductive filler (D) may 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 (C) and / or the thermally conductive filler (D). 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, the methoxy group is preferred in terms of ease of removing volatile components such as alcohol generated by hydrolysis. Examples of the reactive functional group include a vinyl group, an epoxy group, a styryl group, a methacryl group, an acryl group, an amino group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group. Among these, an epoxy group is preferable.

[0101] 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-a 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 achieving excellent adhesive strength and gas barrier properties, a phenylaminosilane treatment and / or a vinylsilane treatment is preferred.

[0102] The method of treating the silica filler (C) with a silane coupling agent includes, for example, a wet method of mixing the silica filler (C) with a silane coupling agent in a solvent, and a dry method of treating the silica filler (C) with a silane coupling agent 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 (C).

[0103] The method for treating the thermally conductive filler (D) with the silane coupling agent and the amount of the silane coupling agent to be treated are the same as those for the silica filler (C) described above.

[0104] The total content of the silica filler (C) and the thermally conductive filler (D) is 40 to 95% by mass in 100% by mass of the non-volatile content of the curable composition. It is preferably 60% by mass or more, and more preferably 70% by mass or more. If it contains 40% by mass or more, the barrier property of the cured product is further improved. The curable composition may contain only one of the silica filler (C) and the thermally conductive filler (D), or may contain both.

[0105] The silica filler (C) and the thermally conductive filler (D) may each independently be of a single type or of a combination of two or more types, but from the viewpoint of improving adhesive strength, it is preferable to contain two or more types. The embodiment containing two or more kinds of silica fillers (C) includes an embodiment in which any two or more kinds are combined from among plate-like silica, rod-like silica, fused crushed silica, fused spherical silica, crystalline silica, and secondary aggregated silica. In addition, an embodiment in which two or more kinds with different average particle sizes are combined, and an embodiment in which two or more kinds of silica fillers with different surface treatments are combined can be exemplified. The embodiment containing two or more kinds of thermally conductive fillers (D) may be a combination of any two or more kinds selected from plate-shaped, rod-shaped, molten crushed, molten spheres, crystals, and secondary aggregates. In addition, examples of the embodiment include a combination of two or more kinds of thermally conductive fillers (D) having different average particle sizes, and a combination of two or more kinds of thermally conductive fillers (D) having different surface treatments. By using the silica filler (C) and the thermally conductive filler (D) in combination, different fillers with different charges become more compatible with the polyamide resin (A), and the adhesive strength can be more suitably exhibited after long-term storage at high temperature and high humidity, in addition to the adhesiveness at 25°C.

[0106] [Hardening agent (E)] The curable composition of the present invention contains a curing agent (E). The curing agent (E) is preferably at least one 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 them, it is preferable to contain an epoxy-based curing agent, and in particular, it is preferable to use an epoxy-based curing agent and a phenol-based curing agent in combination from the viewpoint of achieving both adhesive strength at 25°C and adhesive strength after long-term aging under high temperature and high humidity. The curing agent (E) may be a polymeric compound or a low molecular weight compound.

[0107] The epoxy-based curing agent is a compound containing two or more epoxy groups, the acid anhydride group-containing compound is a compound having two or more acid anhydride groups, the isocyanate-based curing agent is a compound containing two or more isocyanate groups, the aziridine-based curing agent is a compound having two or more aziridine groups, the amine-based curing agent is a compound having two or more amino groups, and the phenol-based curing agent is a compound having two or more structures in which a hydroxyl group is directly bonded to an aromatic group (aromatic ring). The metal chelate-based curing agent is a complex formed by coordination of a multidentate ligand (chelate ligand) with a metal ion. Among the above, the epoxy-based curing agent is most suitable for improving the adhesive strength at 25°C and the adhesive strength after long-term aging under high temperature and high humidity.

[0108] The epoxy-based curing agent is a thermosetting resin that can be thermally cured by having an epoxy group. If the epoxy resin itself has a reactive functional group such as a hydroxyl group, the epoxy curing agent can form a crosslinked structure by itself. In addition to or instead of the single crosslinking, a preferred embodiment is to thermally crosslink the polyamide resin (A) and the epoxy curing agent. The three-dimensional crosslinked structure formed by thermal crosslinking the polyamide resin (A) and the epoxy curing agent provides adhesive strength at 25°C and adhesive strength after long-term aging under high temperature and high humidity. The types of these curing agents may be used alone or in combination of two or more.

[0109] The content mass ratio of the polyamide resin (A) to the curing agent (E) is preferably (A):(E)=5:95 to 50:50, and more preferably (A):(E)=10:90 to 30:70. By setting the ratio in the above range, it is possible to exhibit a good balance between the adhesive strength at 25°C and the adhesive strength after long-term storage under high temperature and high humidity conditions.

[0110] The epoxy-based curing agent preferably has a repeating unit containing an aromatic ring. In addition, it is preferable that at least a part of the aromatic ring in the repeating unit contains 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 when the cured product is obtained, and further improving crack resistance and moist heat resistance. It is more preferably 220 to 320 g / eq., and even more preferably 250 to 300 g / eq.

[0111] From the viewpoint of increasing the compatibility of the epoxy-based curing agent with the polyamide resin (A) during kneading, monocyclic aromatic hydrocarbons having one ring such as a benzene ring are preferred over polycyclic aromatic hydrocarbons such as naphthalene. Polyaromatic ring epoxy resins having multiple monocyclic aromatic hydrocarbons are also suitable. Furthermore, from the viewpoint of effectively forming a phase separation structure of the polyamide resin (A) and the epoxy-based curing agent during melt molding, epoxy-based curing agents containing a repeating unit structure are suitable. 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 type epoxy resins, naphthalene type epoxy resins, phenol aralkyl modified epoxy resins, alicyclic and alcohol type glycidyl ethers, alicyclic and alcohol type glycidyl amine type epoxy resins, and alicyclic and alcohol type glycidyl ester type epoxy resins.

[0112] Among these, from the viewpoints of enhancing the moist heat resistance and further improving the barrier properties, 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.

[0113] Suitable examples include epoxy curing agents represented by the following chemical formulas (5) to (10): In the formula, n is an integer of 1 or more, and preferably 1 to 10, for example. [ka] [ka] [ka] [ka] [ka] [ka]

[0114] Two or more types of epoxy curing agents may be used in combination. By using two or more types in combination, it is easy 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 trisphenol methane type epoxy resin. Among them, 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 trisphenol methane type epoxy resin in a mass ratio of 2:8 to 8:2, since it has appropriate compatibility with the polyamide resin (A) and improves the adhesive strength at 25°C and the adhesive strength after long-term aging under high temperature and high humidity.

[0115] 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 the 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 2,3:3',4'-dianhydride, and dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride. In addition, examples of the acid dianhydrides include copolymers such as styrene-maleic anhydride copolymers and ethylene-maleic anhydride copolymers, and modified products such as acid anhydride-modified polypropylene. Examples of 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 TAFMAR (registered trademark, manufactured by Mitsui Chemicals, Inc.).

[0116] The isocyanate-based 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] Further examples include trimethylolpropane adducts of diisocyanates, biuret forms reacted with water, and trimers having an isocyanurate ring.

[0121] 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, when used in this embodiment, hexamethylene diisocyanate trimer having an isocyanurate ring and blocked with MEK oxime or pyrazole is very preferable because it has excellent storage stability, as well as 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.

[0122] Examples of the aziridine-based curing agent include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxite), N,N'-toluene-2,4-bis(1-aziridinecarboxite), bisisophthaloyl-1-(2-methylaziridine), tri-1-aziridinylphosphine oxide, N,N'-hexamethylene-1,6-bis(1-aziridinecarboxite), 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 has both adhesive strength and barrier properties.

[0123] Examples of the amine-based curing agent include polyamines having a dimer structure exemplified as the monomers of the polyamide resin (A) and other polyamines not having a dimer structure.

[0124] The type of phenol-based curing agent is not particularly limited, but a phenol resin having two or more phenolic hydroxyl groups in one molecule is suitable. Examples of such phenol resins include bisphenol A type phenol resin, bisphenol F type phenol resin, phenol aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin, novolac type phenol resin, dicyclopentadiene type phenol resin, xylylene type phenol resin, and biphenyl type phenol resin.

[0125] Specific examples of metal chelate-based 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.

[0126] [Curing catalyst (F)] When an epoxy-based curing agent is used as the curing agent (E), a curing catalyst can be used in combination with the epoxy-based curing agent. Examples of the curing catalyst 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 them, imidazole-based curing accelerators are preferred from the viewpoint of improving crosslinking properties. The other curing accelerators may be used alone or in combination of two or more. When the curing catalyst (F) is used, the content thereof is, for example, 0.05 to 0.5 mass %, and preferably 0.1 to 0.3 mass %, relative to 100 mass % of the total nonvolatile content of the curable composition.

[0127] Examples of the urea-based curing accelerator 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. Examples of the dimethylurea 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.

[0128] Examples of the guanidine curing accelerator 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.

[0129] Examples of the imidazole-based 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-furan. 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-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 of the imidazole compound include 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 and epoxy resins.

[0130] Examples of the metal-based curing accelerator 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 octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0131] Examples of the amine 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.

[0132] [Release agent (G)] The curable composition of the present invention may further contain a release agent (G). In particular, the addition of the release agent (G) is preferred when molding using a mold. By using the release agent (G), the releasability from the mold of the thermoforming device is improved. Examples of the release agent (G) include natural wax and synthetic wax. Examples of the natural wax include carnauba wax and candelilla wax. Examples of the synthetic wax include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and polyethylene wax. When using the release agent (G), only one type may be used, or two or more types may be used in combination. When the release agent (G) is used, the content thereof is, for example, 0.1 to 0.5 mass %, and preferably 0.2 to 0.3 mass %, relative to 100 mass % of the total nonvolatile content of the curable composition.

[0133] [Other fillers (H)] The curable composition of the present invention may contain other fillers (H) other than the silica filler (C) and the thermally conductive filler (D). Examples of the other fillers (H) include flame-retardant fillers and electromagnetic shielding fillers. Examples of the other fillers (H) include quartz glass, talc, aluminum hydroxide, magnesium hydroxide, and ferrite. The preferred average particle diameter D of the other fillers (H) is 100 to 2000 nm. 50 The surface treatment method is the same as that for the silica filler (C) described above. From the viewpoint of achieving other properties such as electromagnetic shielding, the content ratio (mass ratio) of the silica filler (C) and the thermally conductive filler (D) to the other fillers (H) is preferably ((C)+(D)):(H)=50:50 to 90:10. However, it is preferable that the total content of the silica filler (C), the thermally conductive filler (D) and the other fillers does not exceed 95% by mass relative to 100% by mass of the curable composition.

[0134] Other components that can be used include thermoplastic resins (elastomers), dyes, pigments (e.g., carbon black), flame retardants, antioxidants, polymerization inhibitors, defoamers, leveling agents, ion collectors, moisturizers, viscosity adjusters, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbing agents, infrared absorbing agents, and electromagnetic wave shielding agents.

[0135] [Method of producing curable composition] The curable composition is obtained by kneading each blended component. For example, after mixing each blended component, the components are melt-kneaded in a state substantially free of solvent to obtain a solvent-free curable composition. At this time, the composition may be formed into a desired shape such as a sheet, granule, pellet, powder, tablet, etc. Alternatively, the blended composition may be melt-kneaded to obtain an amorphous solid.

[0136] The sheet-shaped curable composition can be obtained, for example, by blending the components of the substantially solvent-free curable composition, melt-kneading the mixture with a roll or kneader, forming the kneaded mixture into a sheet, and then cooling it. For melt-kneading, a known kneader such as a mixing roll, a pressure kneader, or an extruder can be used. As 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, and considering the thermosetting property of the epoxy resin, preferably 40 to 140°C, and more preferably 60 to 120°C. The time is, for example, 1 to 30 minutes, preferably 5 to 15 minutes. The kneading is preferably carried out under reduced pressure conditions, which allows degassing and prevents the intrusion of gas into the kneaded product. The pressure under reduced pressure conditions is preferably 0.1 kg / cm. 2 Less than 0.05 kg / cm, 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.

[0137] When the kneaded material is plastically processed to form a curable composition sheet, it is preferable to plastically process 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 point of each of the above-mentioned components, and is, for example, 40 to 150°C, preferably 50 to 140°C, and more preferably 70 to 130°C, taking into consideration the thermosetting and moldability of the epoxy resin. A protective film may be laminated on the surface of the sheet-shaped curable composition. The sheet-shaped curable composition may be in the form of a sheet or a roll that can be wound up.

[0138] The thickness of the sheet in the sheet-like 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, for example, when used for sealing 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.

[0139] The obtained sheet-like curable composition may be pulverized into powder or granules, and the powder or granules may be compressed into tablets.

[0140] The curable composition in the form of powder, granules, or tablets may be produced directly from the kneaded product by melt-kneading it with 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 grating mixer, or a mixer. The composition can be produced using a batch mixer such as a ranulator, a high-speed mixer, a fur matrix, a ball mill, a steel mill, a sand mill, a vibration mill, an attritor, or a Banbury mixer; a twin-screw extruder, a single-screw extruder, or a rotor-type twin-screw kneader.

[0141] Specifically, examples of such a method 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 surface, and the curable composition is passed through the small holes by centrifugal force obtained by rotating the rotor to obtain a curable composition; a method in which each raw material component of the curable composition is premixed in a mixer, then heated and kneaded with a kneading machine such as a roll, kneader or extruder, and then cooled and crushed to obtain a pulverized product, and coarse particles and fine powder are removed using a sieve to obtain a curable composition; and a method in which each raw material component of the curable composition is 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 from the small holes arranged in the die is cut with a cutter that rotates and slides approximately parallel to the die surface to obtain a curable composition.

[0142] 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 easy 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.

[0143] Alternatively, each compounding component may be mixed with a solvent to prepare a varnish, or each raw material component may be kneaded to obtain a curable composition, and the varnish may be dissolved or dispersed in an organic solvent to prepare a varnish, which may then be coated and dried to obtain a sheet-shaped curable composition. Examples of the coating method include a coating method using a coater such as a comma coater or a die coater, and a printing method such as stencil printing or gravure printing.

[0144] Similarly to the 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 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, and from the viewpoint of productivity, a sheet form is preferred.

[0145] <Cured product and manufacturing method thereof> The curable composition exhibiting thermosetting properties according to the present embodiment is applied to a substrate, and then dried, thermally polymerized, or thermally melt molded, followed by curing to obtain a cured product. The thermal melt molding and curing may be performed simultaneously, or the curing may be performed after the thermal melt molding. The cured product referred to here refers to a state in which the composition is cured to such an extent that the curing reaction does not proceed substantially even if the composition is further heated. In the melt kneading step for producing the curable composition, a part of the composition may undergo a curing reaction, but the cured product referred to here does not include a state in which the composition may be cured by further heating. When the curable composition is used to seal, for example, an IC chip, the dimer structure contained in the polyamide resin (A) causes stress relaxation during the process of applying heat to soften and flow the molded product, but the stress is distributed in the planar and vertical directions of the sealed product, resulting in effects such as suppressing the decrease in adhesive strength, suppressing foaming, and suppressing cracking. Pressure may be applied during melt molding.

[0146] The heat curing temperature is preferably 150 to 230°C, and the heating time is preferably 30 to 180 minutes. The curing agent (E) forms three-dimensional crosslinks to become a cured product. When the resin is melted by heat, pressure may be applied in addition to heat. By applying heat and pressure, softening and fluidization can be more easily achieved. In addition, stress relaxation due to the dimer structure contained in the polyamide resin (A) can be promoted.

[0147] The glass transition temperature (Tg) of the cured product is preferably from 100 to 200° C., and more preferably from 120 to 180° C. By setting it within the above range, the adhesive strength after long-term aging under high temperature and high humidity conditions is improved.

[0148] When the curable composition of the present embodiment is in the form of a sheet, for example, this 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 a sealing resin. When the curable composition of the present embodiment is in the form of a tablet, for example, this tablet is injected while being melted and flowed into a mold in which a semiconductor chip is set, and an IC package in which the cured product of the curable composition is used as the sealing resin can be obtained through a molding step and a curing step.

[0149] <Laminate> 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 of the curable composition of the present invention between plastic films such as polyester or polyimide, metal foil, etc., and applying heat and pressure. The thickness of the curable composition is preferably 5 to 500 μm, more preferably 10 to 100 μm, in order to exhibit sufficient adhesiveness and gas barrier properties and in terms of ease of handling.

[0150] 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, and inexpensive polyethylene terephthalate is particularly preferred.

[0151] When a metal foil is used as the substrate, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is 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.

[0152] 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. EXAMPLES

[0153] The present invention will be described in more detail, but the following examples do not limit the scope of the present invention. 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.

[0154] <Acid value measurement> Approximately 1 g of sample was precisely weighed and placed in a stoppered Erlenmeyer flask, and 100 mL of cyclohexanone solvent was added to dissolve it. Phenolphthalein test solution was added as an indicator and the solution was held for 30 seconds. Then, the solution was titrated with 0.1N alcoholic potassium hydroxide solution until it turned a pale pink color. The acid value was calculated using the following formula (unit: mgKOH / g). Acid value (mgKOH / g)=(5.611×a×F) / S however, S: Amount of sample collected (g) a: Consumption of 0.1N alcoholic potassium hydroxide solution (mL) F: Potency of 0.1N alcoholic potassium hydroxide solution

[0155] <Method of measuring weight average molecular weight (Mw)> The measurement of Mw was performed 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 the difference in their molecular size. The measurement in the present invention was performed using two "KF-805L" (GPC column: 8 mm ID x 300 mm size manufactured by Showa Denko K.K.) columns connected in series under the 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 equivalent. The data was analyzed 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 by analyzing the range of retention times from 17.9 to 30.0 minutes.

[0156] <Method for measuring glass transition temperature (Tg) of polyamide resin (A)> Polyamide resin was dissolved in cyclohexanone to a non-volatile content of 35%, to prepare a polyamide resin varnish. This varnish was applied to a heat-resistant release film with a doctor blade of 10 mil, and dried at 130°C for 10 minutes to obtain a polyamide resin film with a thickness of 25 μm, which was used as a sample for measuring the glass transition temperature. Tan δ was measured in the temperature range of -50 to 200°C using a dynamic viscoelasticity measuring device to determine the glass transition temperature (Tg). Dynamic viscoelasticity measuring device: DVA-200 (manufactured by IT Measurement and Control Co., Ltd.) Heating rate: 10℃ / min Measurement frequency: 10Hz Grip length: 15mm Width: 5mm

[0157] <Average particle diameter D 50 Measurement method> The average particle size was measured in a dry state using a laser diffraction particle size distribution analyzer SALD-2300 manufactured by Shimadzu Corporation. The refractive index of the thermally conductive inorganic particles (A) was taken as the literature value for the refractive index of thermally conductive inorganic particles (A). For example, for aluminum oxide, the analysis was performed with a refractive index parameter of 1.70-0.10i. From the measurement results, the particle size (median diameter) at a cumulative value of 50% was calculated as the cumulative (accumulated) mass percentage, and the average particle size D of the powder was calculated. 50 It was decided.

[0158] <Synthesis of polyamide resin> [Polyamide resin (A'-1)] 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, 481 g (0.901 mol) of DA (Priamine 1075) as a dimer diamine having a carbon number of 36, 187.5 g (0.938 mol) of DAPE (3,4'-diaminodiphenyl ether) as other diamines, 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) were charged and stirred. When 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 (A'-1) was obtained having a weight average molecular weight of 30,000, an acid value of 11.4 mgKOH / g, and a Tg of 28° C. The total content of dimer diamine and dimer acid in 100% by mass of the monomers constituting the polyamide resin (A) was 48.1% by mass.

[0159] [Polyamide resins (A-1 to A-11, A-13 to A-15)] Polyamide resins were obtained by synthesis in the same manner as for polyamide resin (A'-1) according to the compositions and parts by weight of ingredients shown in Tables 1 and 2. The properties of the resulting polyamide resins are shown in Tables 1 and 2.

[0160] [Polyamide resin (A-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 a carbon number of 36, 59.1 parts of DAPE (3,4'-diaminodiphenyl ether) as other diamines, 194.5 parts of AdA (adipic acid) as a polybasic acid, and 59.1 parts of sebacic acid were charged and stirred. When the heat generation subsided, the reaction was allowed to proceed by gradually heating. While removing water generated with the progress of the reaction from the system, the internal temperature was raised to 230°C, and the temperature was maintained at that temperature for 4 hours. Next, the reaction was allowed to proceed at the same temperature for 2 hours under a reduced pressure of about 2 kPa. Thereafter, the internal temperature was lowered to 180°C, 14.7 parts of BzA (benzylamine) were added, and the temperature was gradually raised to 240°C to complete the reaction. A polyamide resin (A-12) was obtained having a weight average molecular weight of 30,000, an acid value of 0.5 mgKOH / g, and a Tg of 26° C. In addition, the total content of dimer diamine and dimer acid in 100% by mass of the monomers constituting the polyamide resin (A) was 67.4% by mass.

[0161] [Table 1]

[0162] [Table 2]

[0163] The abbreviations in Tables 1 and 2 are as follows: Dacid: Dimer acid with 36 carbon atoms and a ring structure with 6 carbon atoms (dimer structure ratio: 95% or more, acid value: 197 mg KOH / g, "Pripol 1009" manufactured by Croda Japan) AdA: Adipic acid SeA: Sebacic acid 5-HIP: 5-hydroxyisophthalic acid IPA: Isophthalic acid DA: Dimer diamine with 36 carbon atoms and a ring structure with 6 carbon atoms (dimer structure ratio: 95% or more, "Priamine 1075" manufactured by Croda Japan) DAPE: 3,4'-diaminodiphenyl ether BzA: benzylamine

[0164] Synthesis of <Tetracarboxylic acid modified product (B)> [Tetracarboxylic acid modified product (B-1)] In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 31 parts of 2-(benzyloxy)ethanamine, 177.6 parts of ε-caprolactone, and 0.1 parts of monobutyltin(IV) oxide as a catalyst were charged, and after replacing with nitrogen gas, the mixture was heated and stirred at 120°C for 4 hours. After confirming that 98% had reacted by measuring the non-volatile content, 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 a tetracarboxylic acid modified product (B-1).

[0165] [Tetracarboxylic acid modified products (B-2) to (B-7), (B'-1)] Synthesis was carried out in the same manner as for (B-1) according to the compositions and charged mass parts in Table 3, to obtain tetracarboxylic acid modified products (B-2) to (B-7) and (B'-1).

[0166] [Table 3]

[0167] [Tetracarboxylic acid modified product (B-8)] A four-neck 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 UNILIN350 and 33 parts of MCTC (5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride), and the temperature was raised to 120°C with stirring. The temperature was maintained for 6 hours to complete the reaction, and a tetracarboxylic acid modified product (B-8) was obtained.

[0168] [(B-9)~(B-13)] Synthesis was carried out in the same manner as for (B-8) according to the compositions and charged mass parts in Table 4, to obtain tetracarboxylic acid modified products (B-9) to (B-13).

[0169] [Table 4]

[0170] The abbreviations in Tables 3 and 4 are as follows: 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: Ethoxylated alcohol with number average molecular weight 2,300, EO content 80% by mass UNITHOX420: Number average molecular weight 575 ethoxylated alcohol, EO content 20% by mass UNITHOX450: Ethoxylated alcohol with number average molecular weight 920, EO content 50% by mass

[0171] [Example 1] 2.4 parts of polyamide resin (A-1), 0.6 parts of tetracarboxylic acid modified product (B-12), 79.9 parts of plate-like silica (C-1), 12 parts of biphenyl type epoxy resin (E-5) and 5 parts of triphenylmethane type phenolic resin (E-9) as hardeners, and 0.1 parts of imidazole compound (F-1) as a hardening catalyst were mixed and mixed in a kneader at 100°C for 10 minutes under reduced pressure (0.01 kg / cm 2 The mixture was then molded by a plate press method to obtain a sheet-like curable composition having a thickness of 300 μm.

[0172] [Examples 2 to 44], [Comparative Examples 1 to 5] The ingredients were blended as shown in Tables 5 to 8 in the same manner as in Example 1 to obtain a kneaded mixture, and then a sheet-shaped curable composition was obtained in the same manner as in Example 1.

[0173] Details of the materials used in the examples and comparative examples are given below. ·Silica filler (C) C-1: Plate-shaped silica (AGC, Sunlovely, average particle size D 50 : 5μm) C-2: Fused spherical silica (Admatechs, SO-25R, average particle size D 50 :0.5μm)

[0174] Thermally conductive filler (D) D-1: Plate-shaped alumina (Kinsei Matec Co., Ltd., Seraph 02025, average particle size D 50 : 2μm) D-2: Plate-shaped alumina (Kinsei Matec Co., Ltd., Seraph 05070, average particle size D 50 : 5μm) D-3: Boron nitride (Tomoe Chemical Co., Ltd., PT120, average particle size D 50 :12μm)

[0175] Hardener (E) E-1: Trisphenolmethane type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., EPPN-501H, epoxy equivalent (hereinafter EPW) = 167g / eq. E-2: Phenol aralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., NC-3000, EPW=275g / eq. E-3: Phenol-modified xylene resin type epoxy resin, Mitsubishi Chemical Corporation, YX7700, EPW=270g / eq. E-4: Dicyclopentadiene type epoxy resin, Nippon Kayaku Co., Ltd., XD-1000, EPW=253g / eq. E-5: Biphenyl type epoxy resin, Mitsubishi Chemical Corporation, YX4000HK, EPW=185g / eq. E-6: Tetrakisphenolethane type epoxy resin, Mitsubishi Chemical Corporation, jER1031S, EPW=200g / eq. E-7: Naphthalene type epoxy resin, DIC, HP-6000, EPW=250g / eq. E-8: Naphthalene-containing novolac type epoxy resin, Nippon Kayaku Co., Ltd., NC-7000L, EPW=231g / eq. E-9: Triphenylmethane type phenolic resin, Meiwa Kasei Co., Ltd., MEH-7500, hydroxyl equivalent = 97g / eq. E-10: 2,2'-bishydroxymethylbutanol tris[3-(1-aziridinyl)propionate]

[0176] Curing catalyst (F) F-1: Imidazole compound (2P4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.)

[0177] The cured products of the curable compositions of the Examples and Comparative Examples were subjected to measurement of the glass transition temperature, and evaluation of the adhesive strength at 25° C. and the adhesive strength after aging under high temperature and high humidity conditions. The measurement methods and evaluation criteria were as follows.

[0178] <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 obtain a sample for measuring the glass transition temperature. Tan δ was measured in the temperature range of −50 to 200° C. using a dynamic viscoelasticity measuring device to determine the glass transition temperature (Tg). Dynamic viscoelasticity measuring device: DVA-200 (manufactured by IT Measurement and Control Co., Ltd.) Heating rate: 10℃ / min Measurement frequency: 10Hz Grip length: 15mm Width: 5mm

[0179] <Preparation of samples and test pieces for adhesive strength evaluation> Each of the prepared 300 μm thick sheet-like curable compositions was cut into 50 mm×50 mm, and 5 mm×5 mm×300 μm gold-plated silicon chips were arranged on the silicon chips in three vertical rows and three horizontal rows, a total of nine pieces, at equal intervals. At this time, the sheet-like curable composition was arranged so as to be in contact with the silicon surface of the silicon chip. In order to adhere the sheet-like curable composition in contact with the silicon chip, a 38 μm polyethylene terephthalate treated with silicone release was placed opposite the silicon chip, and thermally laminated (temperature 80° C., cylinder pressure 0.3 MPa) using a thermal lamination tester. After thermal lamination, a cut was made around the silicon chip with a cutter knife, and a sample for evaluating adhesion strength was prepared in which the sheet-like curable composition was temporarily attached to one side of the silicon chip. A gold-plated copper frame substrate was prepared as an adherend, and a silicon chip with a sheet-shaped 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), followed by post-baking (170°C x 2 hours) to prepare a test specimen.

[0180] <25℃ adhesive strength> Each test piece prepared above was evaluated using a bond tester (Nordson Advanced Technology, product name: Dage4000-PXY). The measurement conditions were a measurement speed of 100 μm / sec, 25°C, 60% RH, and a measurement height of 100 μm. The adhesive strength was measured for three test pieces, and the arithmetic mean adhesive strength (X) 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 10N / mm or more: Excellent 4: (X) is 7N / mm or more and less than 10N / mm: Better 3: (X) is 5N / mm or more and less than 7N / mm: Excellent 2: (X) is 3N / mm or more and less than 5N / mm: Practical 1: (X) is less than 3N / mm: Impractical

[0181] <Adhesive strength after aging at 135℃ and 85% RH> A pressure cooker bias test (PCBT) was carried out on each of the test pieces prepared above under the following conditions. [PCBT test conditions] Temperature: 135℃ Relative humidity: 85% RH Bias voltage: 25V Test time: 500 hours The adhesive 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, and a measurement height of 100 μm under conditions of 25°C and 60% RH. The adhesive strength was measured on three test pieces, and the arithmetic mean value (Y) of the adhesive strength was calculated. The adhesive strength after aging under 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 adhesive strength at 25°C. The larger the value, the higher the adhesiveness of the cured product to the silicon chip and the adherend after aging under high temperature and high humidity. The evaluation criteria are as follows. 5: (Y) / (X) is 0.9 or more: Excellent 4: (Y) / (X) is 0.7 or more but 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: Practical 1: (Y) / (X) is less than 0.3: Impractical

[0182] As shown in the examples, it was confirmed that the cured product obtained from the curable composition of this example had excellent adhesion at 25°C and good adhesion even after a time-dependent test under high temperature and high humidity conditions, compared to Comparative Examples 1 to 5.

[0183] [Table 5]

[0184] [Table 6]

[0185] [Table 7]

[0186] [Table 8]

[0187] [Industrial Applicability] The curable composition according to the present embodiment has excellent adhesive properties and adhesive strength after aging at high temperature and high humidity, and can therefore be suitably used as an insulating resin material, including a semiconductor chip encapsulant, adhesive, underfill material, potting material, etc. In addition, the composition can be applied to fields where resistance to moisture and heat is highly required, such as organic thin-film solar cells and organic devices such as 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 present invention comprises a polyamide resin (A), a tetracarboxylic acid modified product (B), at least one of a silica filler (C) and a thermally conductive filler (D), and a curing agent (E), The polyamide resin (A) contains 50 to 99% by mass of dimer acid and dimer diamine in total based on 100% by mass of monomers constituting the polyamide resin (A), The tetracarboxylic acid modified product (B) is a reaction product of an aliphatic tetracarboxylic acid anhydride (b1) and a compound (b2) having one terminal hydroxyl group, The curable composition contains, relative to 100% by mass of nonvolatile matter of the curable composition, 0.1 to 40% by mass of a polyamide resin (A), 0.1 to 5% by mass of a tetracarboxylic acid modified product (B), and 40 to 95% by mass in total of a silica filler (C) and a thermally conductive filler (D).

2. The curable composition according to claim 1, wherein the compound (b2) having one hydroxyl group at its terminal contains at least one of an ether bond and an ester bond in a 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 polyamide resin (A) has a glass transition temperature of 0 to 90°C.

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

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

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

7. A laminate comprising an adhesive layer made of the cured product according to claim 6 and a substrate.

8. A method for producing a cured product, comprising the steps of: molding the curable composition according to any one of claims 1 to 5 by thermal melting; and thermally curing the composition.

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