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

Abstract

To provide a curable composition from which a cured product having a high gas barrier function and excellent adhesiveness can be obtained, a cured product, a laminate, and a method for producing a cured product.SOLUTION: The curable composition contains a polyamide resin (A), a fluorene skeleton-containing polyol (B), at least one of a silica filler (C) and a thermally conductive filler (excluding a silica filler) (D), and a curing agent (E) in specific amounts. The polyamide resin (A) contains a dimer acid and / or a dimer diamine in an amount of 50-99 mass% in 100 mass% of monomers constituting the polyamide resin (A).SELECTED DRAWING: None

Description

[Technical Field]

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

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

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

[0004] [Patent Document 1] Japanese Patent Publication No. 2017-057313 [Patent Document 2] International Publication No. 2 016 / 136741 [Patent Document 3] Japanese Patent Publication No. 2019-119886 [Patent Document 4] International Publication No. 2016 / 001949 [Overview of the Initiative] [Problems that the invention aims to solve]

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

[0006] Electronic components and devices are widely used in automobiles, industrial machinery, ships, aircraft, and other applications. In these applications, moisture can accumulate at the interface between the chip and the molded resin, leading to concerns about package cracks, wire breakage, metal corrosion, and electrochemical migration due to water vapor expansion. Therefore, electronic components are inherently sensitive to oxidizing substances such as oxygen and water. This situation necessitates encapsulation materials with high gas barrier properties. Meanwhile, driven by the trend towards higher performance electronic components, resin compositions with high adhesive strength are required to enhance product stability. However, achieving both the rigidity required for gas barrier function and the flexibility of polymer chains required for adhesive strength is not easy.

[0007] This invention has been made in view of the above background, and aims to provide a curable composition, a cured product, a laminate, and a method for producing a cured product that yields a cured product with high gas barrier function and excellent adhesion. [Means for solving the problem]

[0008] After diligent research by the inventors, it was found that the problems of the present invention can be solved in the following embodiment. We discovered this and completed the present invention.

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

[0010] [1] A polyamide resin (A), a fluorene skeleton-containing polyol (B), at least one of a silica filler (C) and a thermally conductive filler (excluding silica filler) (D), and a curing agent (E), The polyamide resin (A) contains 50 to 99% by mass of dimer acid and / or dimer amine in 100% by mass of monomers, The amount of the polyamide resin (A) blended is 0.10 to 40% by mass relative to 100% by mass of the nonvolatile content of the curable composition. The amount of the fluorene skeleton-containing polyol (B) blended is 1 to 40% by mass relative to 100% by mass of the polyamide resin (A). A curable composition in which the total blending amount of the silica filler (C) and the thermal conductivity filler (D) is 40 to 95% by mass based on 100% by mass of the non-volatile content of the curable composition.

[0011] 〔2〕The curable composition according to 〔1〕, wherein the glass transition temperature of the polyamide resin (A) is 0 to 90°C.

[0012] 〔3〕The curable composition according to 〔1〕 or 〔2〕, wherein the curing agent (E) contains an epoxy resin.

[0013] 〔4〕The curable composition according to any one of 〔1〕 to 〔3〕, wherein the thermal conductivity filler (D) contains alumina.

[0014] 〔5〕A cured product formed from the curable composition according to any one of 〔1〕 to 〔4〕

[0015] 〔6〕A laminate comprising an adhesive layer formed from the curable composition according to any one of 〔1〕 to 〔4〕 and a substrate.

[0016] 〔7〕A curable composition comprising a polyamide resin (A), a fluorene skeleton-containing polyol (B), at least one of a silica filler (C) and a thermal conductivity filler (D), and a curing agent (E), containing 50 to 99% by mass of dimer acid and / or dimer diamine in 100% by mass of the monomers constituting the polyamide resin (A), wherein the blending amount of the polyamide resin (A) is 0.10 to 40% by mass based on 100% by mass of the non-volatile content of the curable composition, [[ID=3o]]wherein the blending amount of the fluorene skeleton-containing polyol (B) is 1 to 40% by mass based on 100% by mass of the polyamide resin (A), A curable composition in which the total blending amount of the silica filler (C) and the thermal conductivity filler (D) is 40 to 95% by mass based on 100% by mass of the non-volatile content of the curable composition, A method for producing a cured product, comprising a step of molding by hot melting and thermally curing.

Advantages of the Invention

[0017] The present invention provides a curable composition, cured product, laminate, and method for producing a cured product with good adhesive and gas barrier properties. [Modes for carrying out the invention]

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

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

[0020] The curable composition according to this embodiment is a solvent-free composition for melt molding that exhibits thermosetting properties, and comprises a specific polyamide resin (A), a fluorene skeleton-containing polyol (B), at least one of a silica filler (C) and a thermally conductive filler (D), and a curing agent (E). The polyamide resin (A) is such that the total charge of the dimer acid and dimer amine is 50 to 100% by mass of the total monomers used in the polymerization of the polyamide resin (A). The charge ratio of the monomers used in the polymerization of the polyamide resin (A) substantially equals the proportion of constituent components derived from the monomers of the polyamide resin (A).

[0021] In this embodiment, a curable composition containing a polyamide resin (A) having a specific amount of a dimer structure derived from at least one of a dimer acid and a dimer amine, an epoxy resin (B), at least one of a silica filler (C) and a thermally conductive filler (D), and a curing agent (E) provides the following effects. Specifically, when the cured product is used as a sealing resin for IC packages, for example, it enhances adhesion to the substrate and gas barrier properties against oxygen and hydrogen, thereby preventing the accumulation of moisture between the substrate and the resin. As a result, a cured product with abrasion resistance to package cracks, wire breakage, metal corrosion, and electrochemical migration can be provided. Further details will be explained below.

[0022] ≪Curable composition≫ [Polyamide resin (A)] Polyamide resins are polymers containing repeating structural units with amide groups, and among these, resins having a dimer structure derived from at least one of dimer acid and dimer amine are referred to as polyamide resin (A). Polyamide resin (A) is a polymer of a polybasic acid compound, a polyamine compound, and optionally other monomers, or a modified polymer obtained by modifying the polymer. Here, a modified polymer refers to a derivative obtained by changing a part of the molecular structure of the polymer (for example, by changing a functional group, substituting with another compound, or adding another compound). To introduce a dimer structure into a polyamide resin, a monomer having a dimer structure may be used, and dimer acid, which is a polybasic acid compound, and / or dimer amine, which is a polyamine compound, are preferably used as such monomers.

[0023] The polyamide resin (A) contains 50 to 99% by mass of dimer acid and / or dimer amine in 100% by mass of the monomers constituting the polyamide resin (A). That is, the total amount of dimer acid and dimer amine in 100% by mass of all monomers used in the polymerization of the polyamide resin (A) in this application is 50 to 99% by mass. Since the amount of monomers used in the polymerization of the polyamide resin (A) substantially matches the proportion of constituent components derived from the monomers of the polyamide resin (A), the effect of the dimer structure can be fully exhibited by setting the amount of monomers to 50 to 99% by mass. The total content of dimer acid and dimer amine is preferably 60 to 95% by mass, and more preferably 70 to 90% by mass. The content of the dimer structure can be determined in the case of a polymer from the content (mass%) of monomers having a dimer structure out of 100% by mass of all monomers used when synthesizing the polyamide resin (A). In the case of a modified product, it can be considered as a hypothetical monomer having the modified structure, and the unmodified monomer can be determined from the content (mass%) of monomers having a dimer structure out of 100% by mass of all monomers using the raw material monomers. The content of the hypothetical monomer having the modified structure can be determined by considering the reaction rate with respect to the polymer. For example, when modifying the side groups derived from monomer a after obtaining a polymer, the amount of monomer (mass) X, determined by "amount of monomer a charged (moles) × modification rate of the side groups / 100 × molecular weight of a hypothetical monomer having the structure after the side groups have been modified", and the amount of monomer (mass) Y, determined by "amount of monomer a charged (moles) × (1 - modification rate of the side groups / 100) × molecular weight of monomer a", can be used to determine the content of the dimer structure for other monomers in the same way as the polymer method described above.

[0024] The dimer structure, possessing hydrocarbon chains and ring structures, exhibits lower polarity compared to the epoxy resins used in its formulation, thereby suppressing moisture absorption from outside the system. Furthermore, strong hydrogen bonds exist, derived from the amide bonds of the polyamide resin (A). The high cohesiveness of these hydrogen bonds is expected to improve gas barrier properties, and the flexible skeleton enhances adhesive strength.

[0025] The polyamide resin (A) preferably has functional groups that can be crosslinked with a curing agent (E) by heat. Examples of functional groups include carboxyl groups, amino groups, and hydroxyl groups. These may be functional groups derived from the monomer of the polyamide resin (A), or they may be introduced as a modified product after obtaining the polymer. Functional groups can be located at the ends of the polymer, as well as on side groups and / or side chains. A preferred example is a polymer having functional groups such as carboxyl groups or amino groups at its ends. Another example is a polymer having at least one of functional groups such as carboxyl groups, amino groups, or hydroxyl groups on its side groups or side chains. Furthermore, if the functional group has a photopolymerizable group, the curable composition containing the polyamide resin may become over-crosslinked, resulting in reduced adhesion, or a thermal radical reaction may occur when the curable composition is heated and melted for molding, resulting in reduced moldability. Therefore, it is preferable that the functional group does not have a photopolymerizable group.

[0026] When the polyamide resin (A) has hydroxyl groups, phenolic hydroxyl groups are preferred. The presence of phenolic hydroxyl groups allows for the formation of a crosslinked structure with the curing agent (E), resulting in a cured product with excellent durability. Phenolic hydroxyl groups can be easily introduced by using polybasic acid compounds and / or polyamine compounds having phenolic hydroxyl groups. It is preferable that the aromatic ring of this phenolic hydroxyl group is included in the main chain skeleton of the polyamide resin (A). Furthermore, from the viewpoint of durability, it is preferable to use a polybasic acid compound having phenolic hydroxyl groups as the monomer of the polyamide resin (A).

[0027] The polyamide resin (A) may be a polyamide-imide having some imide groups, or a polyamide-ester having some ester groups, as long as it does not depart from the spirit of the present invention.

[0028] <Polybasic acid compounds> The polybasic acid compounds used as raw materials for polyamide resin (A) are dibasic or greater carboxylic acids. The polybasic acid compounds may also include acid anhydrides as part of their composition. Examples of polybasic acid compounds include dimer acids and other polybasic acid compounds.

[0029] When dimer acid is used in the polybasic acid compound, the content ratio of dimer acid in 100% by mass of the polybasic acid compound is preferably 60% by mass or more and 100% by mass or less, and more preferably 80% by mass or more. When the content ratio of dimer acid in 100% by mass of the polybasic acid compound is 60% by mass or more, the resistance to humid heat is enhanced, the stress relaxation effect due to the dimer structure is fully expressed, and superior adhesive strength can be achieved.

[0030] (Dimer acid) Dimer acids are polybasic acid compounds that have a dimer structure and are fatty acid dimers (hereinafter referred to as fatty acid dimers).

[0031] The fatty acid dimer is preferably a compound having 20 to 60 carbon atoms, more preferably a compound having 24 to 56 carbon atoms, even more preferably a compound having 28 to 48 carbon atoms, and particularly preferably a compound having 36 to 44 carbon atoms. The fatty acid dimer is preferably a dicarboxylic acid compound having a branched structure obtained by a Diels-Alder reaction of a fatty acid. The branched structure is preferably one that includes a fatty chain or a fatty chain and a ring structure, and more preferably one that includes a fatty chain and a ring structure. The ring structure is preferably one or more aromatic rings or alicyclic structures, and more preferably an alicyclic structure. The alicyclic structure may have one double bond in the ring, or it may not have a double bond, etc.

[0032] Examples of polybasic acid compounds having a dimer structure include the structures shown in the following chemical formulas (1) to (4). It goes without saying that polybasic acid compounds having a dimer structure are not limited to the structures shown below.

[0033] [ka] [ka] [ka] [ka]

[0034] The fatty acids are preferably unsaturated fatty acids having 10 to 30 carbon atoms, and more preferably unsaturated fatty acids having 10 to 24 carbon atoms. The unsaturated fatty acids have one or more carbon-carbon double bonds or carbon-carbon triple bonds. Examples of the fatty acids include natural fatty acids such as soybean oil fatty acids, tall oil fatty acids, and rapeseed oil fatty acids, as well as oleic acid, linoleic acid, linolenic acid, and erucic acid obtained by refining these. When synthesizing the aforementioned fatty acid dimers, in addition to fatty acid dimers, fatty acid trimers and, in some cases, tetramers are also produced. Therefore, the polybasic acid compound containing the dimer skeleton is a mixture that includes not only the main component fatty acid dimer, but also fatty acid trimers and, in some cases, the raw material fatty acid. The fatty acid dimer is preferably present in an amount of 70% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on 100% by mass of the dimer acid.

[0035] Because dimer acids use unsaturated fatty acids as raw materials, unsaturated bonds may remain. In such cases, hydrogenation (also called a hydrogenation reaction) can be performed to suppress the number of unsaturated bonds. This improves the reaction stability when synthesizing polyamide resin (A), and further improves the high-temperature resistance of the cured product of the curable composition containing polyamide resin (A). Dimer acids can be used alone or in combination of two or more types.

[0036] Commercially available dimer acids include, for example, "Prepol 1004," "Prepol 1006," "Prepol 1009," "Prepol 1013," "Prepol 1015," "Prepol 1017," "Prepol 1022," "Prepol 1025," and "Prepol 1040" from Croda Japan; and "Empole 1008," "Empole 1012," "Empole 1016," "Empole 1026," "Empole 1028," "Empole 1043," "Empole 1061," and "Empole 1062" from BASF Japan. Among these, using "Prepol 1009," which has 36 carbon atoms, makes it easier to obtain a polyamide resin (A) with superior thermal cycling properties while maintaining adhesion to metals. Alternatively, using "Prepol 1004," which has 44 carbon atoms, makes it easier to obtain a polyamide resin (A) with good flexibility.

[0037] (Other polybasic acid compounds) Other polybasic acid compounds are polybasic acid compounds other than dimer acids that are bifunctional or multifunctional compounds. Polybasic acid compounds can be used alone or in combination of two or more types.

[0038] 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, dodecanediic acid, hexadecanedionic 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.

[0039] Examples of polybasic acid compounds with three or more functions include trimellitic acid, hydrogenated trimellitic acid, pyromellitic acid, hydrogenated pyromellitic acid, trimesic acid, and 1,4,5,8-naphthalenetetracarboxylic acid. By using polybasic acid compounds with three or more functions, a branched structure can be introduced into the polyamide resin (A), thereby improving the cohesive strength of the cured product and enhancing its thermal cycling properties and dimensional stability.

[0040] Other suitable examples of polybasic acid compounds include polybasic acid compounds having a phenolic hydroxyl group. Polybasic acid compounds having a phenolic hydroxyl group are compounds that, like phenol, have a hydroxyl group (also called a phenolic hydroxyl group) directly bonded to an aromatic ring, and have two or more acidic functional groups. Examples of acidic functional groups include carboxyl groups. By using a polybasic acid compound having phenolic hydroxyl groups, the crosslinking structure of the polyamide resin (A) and the curing agent (E) can be easily adjusted during the curing process. As a result, a strong crosslinking structure can be formed, effectively improving the durability of the cured product.

[0041] 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 acid such as 2-hydroxyterephthalic acid; dihydroxyterephthalic acids such as 2,3-dihydroxyterephthalic acid and 2,6-dihydroxyterephthalic acid; hydroxyphthalic acids such as 3-hydroxyphthalic acid and 4-hydroxyphthalic acid; and dihydroxyphthalic acids such as 3,4-dihydroxyphthalic acid, 3,5-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, and 3,6-dihydroxyphthalic acid. Among these, 5-hydroxyisophthalic acid is preferred as a polybasic acid compound having a phenolic hydroxyl group, due to its copolymerizability and ease of availability. Note that the polybasic acid compound having a phenolic hydroxyl group may have a carboxyl group forming an acid anhydride group, or the carboxyl group may form an ester.

[0042] <Polyamine compounds> The polyamine compounds used as raw materials for polyamide resin (A) are compounds having two or more amino groups. Preferred examples of polyamine compounds include dimer amines and other polyamine compounds. When dimeramine is used in the polyamine compound, the content ratio of dimeramine in 100% by mass of the polyamine compound is preferably 50% by mass or more and 100% by mass or less, and more preferably 90% by mass or more. By setting the content ratio of dimeramine in 100% by mass of dimeramine to 50% by mass or more, the stress relaxation properties due to the dimer structure can be fully expressed, and superior thermal cycling properties can be achieved.

[0043] (Dimer amine) Dimer amines are compounds having two amino groups with a dimer structure, and compounds obtained by converting the carboxyl group of the aforementioned dimer acid to an amino group can be used. Conversion methods include, for example, amidating a carboxylic acid, aminating it by Hoffmann rearrangement, and then distilling and purifying it. The dimer amine is preferably a compound having 20 to 60 carbon atoms, more preferably a compound having 24 to 56 carbon atoms, even more preferably a compound having 28 to 48 carbon atoms, and even more preferably a compound having 36 to 44 carbon atoms from the viewpoint of availability.

[0044] Commercially available dimer amines include, for example, "Priamine 1071," "Priamine 1073," "Priamine 1074," and "Priamine 1075" from Croda Japan, and "Versamin 551" from BASF Japan. Dimer amines can be used alone or in combination of two or more types.

[0045] (Other polyamine compounds) Other polyamine compounds include polyamine compounds other than dimer amines, such as diamine compounds and polyamine compounds with three or more functionalities.

[0046] Examples of diamine compounds 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, and 3,4'-diamine. Examples include aromatic diamines such as nodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diamino-1,2-diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 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.

[0047] Another example is a polyamine compound having a phenolic hydroxyl group. A polyamide resin (A) using a polyamine compound having a phenolic hydroxyl group is preferred in terms of durability. Using a polyamine compound having a phenolic hydroxyl group is preferable because it allows for the introduction of phenolic hydroxyl groups into the polyamide resin (A). By introducing phenolic hydroxyl groups, it becomes possible to obtain a tougher cured product by three-dimensional crosslinking with the curing agent (E) that is added. Polyamine compounds having phenolic hydroxyl groups have multiple amino groups and also possess phenolic hydroxyl groups. Examples of polyamine compounds having phenolic hydroxyl groups include the polyamine represented by the following general formula (1).

[0048] [ka]

[0049] R in the formula 1 This refers to a group that is directly bonded or contains carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen. Examples of such groups include divalent hydrocarbon groups having 1 to 30 carbon atoms or divalent hydrocarbon groups having 1 to 30 carbon atoms in which some or all of the hydrogen atoms are substituted by halogen atoms, -(C=O)-, -SO2-, -O-, -S-, -NH-(C=O)-, -(C=O)-O-, the group represented by the following general formula (2), and the group shown by the following general formula (3).

[0050] [ka]

[0051] [ka] In the formula, r and s each independently represent integers from 1 to 20, and R 2 represents a hydrogen atom or a methyl group.

[0052] Examples of polyamines represented by general formula (1) include 2,2-bis(3-amino-4-hydroxyphenyl)propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybisphenyl.

[0053] Examples of amines having three or more amino groups and lacking phenolic hydroxyl groups include 1,2,4-triaminobenzene and 3,4,4'-triaminodiphenyl ether.

[0054] Among these, isophorone diamine or norbornane diamine are preferred as other polyamine compounds because they enhance heat and moisture resistance and further improve adhesion and thermal cycling properties.

[0055] <Method for producing polyamide resin (A)> Polyamide resin (A) can be synthesized by, for example, melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, and solid-phase polymerization, as well as combinations thereof. Among these, solution polymerization is preferred. Polymerization of polyamide resin (A) can be carried out with or without a catalyst using the above-mentioned polybasic acid compound, polyamine compound, and other monomers as needed. For example, predetermined amounts of dimer acid, other acid monomers, dimer amine, other amine monomers, and deionized water are charged into a nitrogen-filled flask and heated and stirred at 20 to 100°C to uniformly dissolve or disperse. Then, the temperature is gradually raised to 230°C while removing the deionized water and water produced by the reaction, and once 230°C is reached, the pressure is reduced to about 15 mmHg and maintained at that state for about 1 hour to obtain polyamide resin (A). The heating temperature can be, for example, 150 to 300°C, and the heating time can be about 1 to 24 hours. To promote the synthesis reaction, it is preferable to carry out a dehydration or dealcoholization reaction, and to avoid discoloration and decomposition reactions at high temperatures, it is preferable to carry out the reaction under reduced pressure at 180 to 270°C.

[0056] In addition to polyamines, monoamines may also be used as other monomers. Monoamines act as reaction stoppers, making it easier to adjust the molecular weight of the polyamide resin (A). Furthermore, since some of the main chain ends of the polyamide resin (A) are not reactive functional groups, its stability over time is improved. Examples of monoamines include aniline, benzylamine, 4-aminophenol, and 2-ethylhexylamine.

[0057] <Physical properties of polyamide resin (A)> The glass transition temperature (Tg) of the polyamide resin (A) is preferably 0 to 90°C, and more preferably 0 to 70°C. Tg is the temperature at which the value obtained by dividing the viscosity term by the elastic term (tanδ), measured by a dynamic viscoelasticity analyzer, of the polyamide resin (A) shows a maximum. By setting the Tg of the polyamide resin (A) to 0-90°C, the compatibility with the curing agent (E), silica filler (C), and / or thermally conductive filler (D) in the process of forming the molten material of the curable composition is further improved, and the fillers are uniformly dispersed in the system, making it easier to obtain good barrier properties.

[0058] 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 Mw is 15,000 or more, an appropriate crosslinking density is obtained when the cured product is formed, and the adhesion to the semiconductor chip is further improved. When Mw is 100,000 or less, the wettability to the adherend is improved, and the adhesion is further improved.

[0059] The acid value of the polyamide resin (A) is preferably 2 to 30 mg KOH / g, more preferably 3 to 25 mg KOH / g, and even more preferably 4 to 20 mg KOH / g. By setting the acid value to 2 to 30 mg KOH / g, an appropriate crosslinking density is obtained when the cured product is formed, further improving the adhesion strength to semiconductor chips and gas barrier properties.

[0060] The amount of polyamide resin (A) is preferably 0.10 to 40% by mass, and more preferably 0.60 to 10%, based on 100% by mass of nonvolatile content. Within this range, good adhesive strength and barrier properties can be achieved.

[0061] [Fluorene skeleton-containing polyol (B)] Fluorene skeleton-containing polyol (B) is a compound having a fluorene skeleton and two or more hydroxyl groups. The bulky diol skeleton widens the spacing between hydrogen bonds in the polyamide, optimizing the strength of the hydrogen bonds, improving kneadability with fillers, and enhancing gas barrier properties.

[0062] The amount of fluorene skeleton-containing polyol (B) blended is preferably 1 to 40% by mass, and more preferably 10 to 30% by mass, relative to 100% by mass of polyamide resin (A). By using the above ratio, gas barrier properties can be enhanced and adhesive strength can be well-balanced.

[0063] The molecular weight of the fluorene skeleton-containing polyol (B) is preferably 300 to 600. A molecular weight of 300 to 600 improves compatibility with fillers and enhances gas barrier properties.

[0064] Examples of fluorene skeleton-containing polyols (B) include phenolic type and alcoholic type. Specific examples of phenolic types include 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and 9,9-bis(hydroxynaphthyl)fluorene. Examples of alcoholic forms include 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, and 9,9-bis[4-(2-hydroxypropoxy)-3-phenylphenyl]fluorene. Among these, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, which have good compatibility with polyamide resin (A), are preferred.

[0065] [Silica filler (C) and thermally conductive filler (D)] The curable composition of this embodiment comprises at least one of a silica filler (C) and a thermally conductive filler (D), except that the thermally conductive filler (D) is the silica filler. The barrier properties of the cured product are improved by at least one of the silica filler (C) and the thermally conductive filler (D). Furthermore, the gas barrier effect is enhanced by combining at least one of the silica filler (C) and the thermally conductive filler (D) with the aforementioned polyamide resin (A), fluorene skeleton-containing polyol (B), and curing agent (E).

[0066] Silica filler (C) can be any silica filler such as plate-shaped silica, rod-shaped silica, molten crushed silica, molten spherical silica, crystalline silica, or secondary aggregated silica. Plate-shaped silica is preferred because it has excellent gas barrier properties. The thermally conductive filler (D) is preferably high in thermal conductivity at 20°C, with a filler of 15 (W / m·K) or higher being preferred. Furthermore, a high volume resistivity is preferred, with a filler of 10⁶ (Ω·cm) or higher being preferred. Suitable examples of the thermally conductive filler (D) include alumina (aluminum oxide), aluminum nitride, silicon nitride, or boron nitride and silicon carbide. Among these, alumina (aluminum oxide) or boron nitride are preferred due to their availability. The type of boron nitride is not particularly limited. Examples include hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), and wurtzite-type boron nitride. Among these, hexagonal boron nitride (h-BN) is preferred from the viewpoint of thermal conductivity. The shape of the boron nitride is not limited, but a flaky shape is preferred, and it may be primary particles or secondary particles formed by the aggregation of primary particles. Examples of thermally conductive fillers (D) include plates, rods, molten crushed bodies, molten spherical bodies, crystalline bodies, and secondary aggregates. Among these, plate-shaped alumina is preferred due to its excellent gas barrier properties.

[0067] The silica filler (C) and the thermally conductive filler (D) preferably have an average particle diameter in the range of 1 to 50 μm, more preferably 1 to 30 μm, and even more preferably 2 to 10 μm. An average particle diameter of 1 μm or more further improves the flexibility and pliability of the cured product. An average particle diameter of 30 μm or less improves the barrier properties. Note that the average particle diameter is the average particle diameter D. 50 For example, a sample arbitrarily selected from the population is used, and the measurement is performed using a laser diffraction scattering particle size distribution analyzer.

[0068] The silica filler (C) and the thermally conductive filler (D) may each be treated (pretreated) independently with a silane coupling agent. Treatment with a silane coupling agent improves the affinity with other materials and further improves the dispersibility of the silica filler (C) and / or the thermally conductive filler (D). Silane coupling agents are compounds having a hydrolyzable group and a reactive functional group. Examples of hydrolyzable groups include alkoxy groups having 1 to 6 carbon atoms, such as methoxy and ethoxy groups; acetoxy groups; and 2-methoxyethoxy groups. Among these, methoxy groups are preferred because they easily remove volatile components such as alcohols produced by hydrolysis. Examples of the reactive functional groups include vinyl groups, epoxy groups, styryl groups, methacrylic groups, acrylic groups, amino groups, ureido groups, mercapto groups, sulfide groups, and isocyanate groups, but epoxy groups are preferred among them.

[0069] Silane coupling agents include, for example, vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy group-containing silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styryl group-containing silane coupling agents such as p-styryltrimethoxysilane; methacryl group-containing silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane; and N-2-(aminoethyl)-3- Examples of amino group-containing silane coupling agents include minopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; ureido group-containing silane coupling agents include 3-ureidopropyltriethoxysilane; mercapto group-containing silane coupling agents include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; sulfide group-containing silane coupling agents include bis(triethoxysilylpropyl)tetrasulfide; and isocyanate group-containing silane coupling agents include 3-isocyanatetopropyltriethoxysilane. From the viewpoint of exhibiting excellent adhesive strength and gas barrier properties, phenylaminosilane treatment and / or vinylsilane treatment are preferred.

[0070] Methods for treating silica filler (C) with a silane coupling agent include, for example, a wet method in which silica filler (C) and the silane coupling agent are mixed in a solvent, and a dry method in which silica filler (C) and the silane coupling agent are treated in the gas phase. Preferably, the amount of silane coupling agent used is about 0.1 to 1 part by mass of silane coupling agent per 100 parts by mass of untreated silica filler (C).

[0071] The method and amount of treatment for the thermally conductive filler (D) with a silane coupling agent are the same as those for the silica filler (C) described above.

[0072] The silica filler (C) and the thermal conductive filler (D) are preferably present in an amount of 40% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on 100% by mass of the nonvolatile content of the curable composition. Including 40% by mass or more further improves the barrier properties of the cured product. The preferred upper limit for the above content of silica filler (C) and thermal conductive filler (D) is 95% by mass. This curable composition may be configured to contain only one of silica filler (C) or thermal conductive filler (D), or to contain both.

[0073] Silica filler (C) and thermally conductive filler (D) may be used independently, as a single type or in combination of two or more types, but from the viewpoint of improving adhesive strength, it is preferable to include two or more types. Embodiments containing two or more types of silica filler (C) include those in combination of any two or more types selected from plate-shaped silica, rod-shaped silica, molten crushed silica, molten spherical silica, crystalline silica, and secondary aggregated silica. Examples also include embodiments in which two or more types with different average particle sizes are used in combination, and embodiments in which two or more silica fillers with different surface treatments are used in combination. Embodiments containing two or more types of thermally conductive fillers (D) include embodiments in which any two or more types from plate-shaped, rod-shaped, molten crushed, molten spherical, crystalline, and secondary aggregates are used in combination. Examples also include embodiments in which two or more types with different average particle sizes are used in combination, and embodiments in which two or more types of thermally conductive fillers (D) with different surface treatments are used in combination. By using silica filler (C) and thermally conductive filler (D) in combination, the different types of fillers with different charges become more compatible with the polyamide resin (A), allowing for better adhesion and gas barrier properties.

[0074] [Hardening agent (E)] The curable composition of the present invention comprises a curing agent (E). The curing agent (E) is preferably one or more selected from epoxy resins, acid anhydride group-containing compounds, isocyanate compounds, aziridine compounds, amine compounds, phenol compounds, and metal chelate compounds. Compound (E) may be a high molecular weight compound or a low molecular weight compound.

[0075] Epoxy resins are compounds containing two or more epoxy groups, acid anhydride group-containing compounds are compounds having two or more acid anhydride groups, isocyanate compounds are compounds containing two or more isocyanate groups, aziridine compounds are compounds having two or more aziridine groups, amine compounds are compounds having two or more amino groups, and phenol compounds are compounds having two or more structures in which a hydroxyl group is directly attached to an aromatic group (aromatic ring). Metal chelate compounds are complexes formed when a polydentate ligand (chelate ligand) coordinates to a metal ion. Among the above compounds, epoxy resins are most suitable for improving adhesion and gas barrier properties.

[0076] Epoxy resins are thermosetting resins that can be heat-cured due to the presence of epoxy groups. Epoxy resins can form a crosslinked structure on their own if they contain reactive functional groups such as hydroxyl groups. In addition to, or instead of, single crosslinking, it is also preferable to thermally crosslink a polyamide resin (A) with an epoxy resin. The three-dimensional crosslinked structure formed by thermal crosslinking of the polyamide resin (A) and the epoxy resin provides excellent adhesion and even better barrier properties. Furthermore, one or more types of curing agents may be used in combination.

[0077] The mass ratio of polyamide resin (A) to curing agent (E) is preferably (A):(E) = 5:95 to 50:50, and more preferably (A):(E) = 10:90 to 30:70. This ratio allows for a good balance of adhesive strength and gas barrier properties.

[0078] The epoxy resin preferably has repeating units containing aromatic rings. Furthermore, it is preferable that at least a portion of the aromatic rings in the repeating units contain organic groups including epoxy groups as substituents. The epoxy equivalent of the epoxy resin is preferably 100 to 300 g / eq., and is preferably 200 g / eq. or more from the viewpoint of increasing rigidity, effectively promoting microphase separation of the resin components during melt molding, suppressing foaming when cured, and further improving crack resistance and heat and moisture resistance. More preferably it is 220 to 320 g / eq., and even more preferably 250 to 300 g / eq.

[0079] From the viewpoint of improving compatibility with polyamide resin (A) during kneading, monocyclic aromatic hydrocarbons having a single ring, such as a benzene ring, are preferred over polycyclic aromatic hydrocarbons such as naphthalene. Polycyclic epoxy resins having multiple monocyclic aromatic hydrocarbons are also preferred. Furthermore, from the viewpoint of effectively forming a phase separation structure between polyamide resin (A) and epoxy resin during melt molding, epoxy resins containing repeating unit structures are preferred. Examples of epoxy resins include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin; novolac-type epoxy resins such as o-cresol novolac-type epoxy resin; biphenyl-type epoxy resin, naphthalene-type epoxy resin, naphthalene-containing novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, phenol aralkyl-type epoxy resin, trisphenolmethane-type epoxy resin, and phenol-modified xylene resin-type epoxy resin. Examples of liquid epoxy compounds include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, biphenyl-type epoxy resin, novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, polyfunctional phenol-based epoxy resin, naphthalene-type epoxy resin, phenol aralkyl-modified epoxy resin, glycidyl ethers such as alicyclic and alcohol-based, glycidylamine-based epoxy resins such as alicyclic and alcohol-based, and glycidyl ester-based epoxy resins such as alicyclic and alcohol-based.

[0080] Among these, biphenyl-type epoxy resins, o-cresol novolac-type epoxy resins, trisphenolmethane-type epoxy resins, dicyclopentadiene-type epoxy resins, naphthalene-containing novolac-type epoxy resins, phenol aralkyl-type epoxy resins, and phenol-modified xylene resin-type epoxy resins are preferred from the viewpoint of improving heat and humidity resistance and further enhancing thermal cycling properties.

[0081] As preferred examples, epoxy resins of the following chemical formulas (5) to (10) can be cited. In the formulas, n is an integer, for example, 1 to 10 is preferred. [ka] [ka] [ka] [ka] [ka] [ka]

[0082] Two or more types of epoxy resins may be used in combination. Using two or more types makes it easier to adjust the adhesive strength and thermal cycling properties. For example, it is preferable to include a phenol aralkyl type epoxy resin and a phenol-modified xylene resin type epoxy resin, or a phenol aralkyl type epoxy resin and a trisphenolmethane type epoxy resin. In particular, it is preferable to use a combination of a phenol aralkyl type epoxy resin and a phenol-modified xylene resin type epoxy resin, or a phenol aralkyl type epoxy resin and a trisphenolmethane type epoxy resin, in a mass ratio of 2:8 to 8:2, as this provides appropriate compatibility with the polyamide resin (A) and improves adhesive strength and gas barrier properties.

[0083] Examples of acid anhydride group-containing compounds include 1,2,4,5-benzenetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-di Examples of acid dianhydrides include ethylene glycol bis-anhydrotrimellitate, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4-bis(3,4-dicarboxyphenol)benzenedioanhydride, p-phenylenebis(trimellitate anhydride)4,4'-oxydiphthalic anhydride, 1,1'-biphenyl-2,3,3',4'-tetracarboxylic acid 2,3:3',4'-dianhydride, and dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride. Copolymers such as styrene-maleic anhydride copolymer and ethylene-maleic anhydride copolymer, and modified products such as acid anhydride-modified polypropylene can also be mentioned. Examples of commercially available products include Ricacid (registered trademark, manufactured by Shin-Nippon Rika Co., Ltd.), Zybond (registered trademark, manufactured by Polyscope Polymers Corporation), SMA (registered trademark) resin (manufactured by Claybury USA), and Tuffmer (registered trademark, manufactured by Mitsui Chemicals, Inc.).

[0084] The isocyanate compound is not particularly limited, but examples include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Furthermore, multiple types of isocyanate group-containing compounds may be used in combination.

[0085] Examples of aromatic polyisocyanates include 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 2,4-tolylenediisocyanate (TDI), 2,6-tolylenediisocyanate, 4,4'-diphenylmethanediisocyanate (MDI), 2,4-diphenylmethanediisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylenediisocyanate, 4,4',4''-triphenylmethanetriisocyanate, m-isocyanatophenylsulfonyl isocyanate, and p-isocyanatophenylsulfonyl isocyanate.

[0086] 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.

[0087] 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.

[0088] Other examples include the trimethylolpropane adduct of diisocyanate, the biuret compound obtained by reaction with water, and trimers having an isocyanurate ring.

[0089] The blocked isocyanate compound is not particularly limited and can be any blocked isocyanate group-containing compound in which the isocyanate group in the isocyanate group-containing compound is protected with ε-caprolactam, MEK oxime, or the like. Specifically, examples include those in which the isocyanate group of the isocyanate group-containing compound is blocked with ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol, or the like. In particular, hexamethylene diisocyanate trimers having an isocyanurate ring and blocked with MEK oxime or pyrazole are very preferred when used in this embodiment because they have excellent storage stability, as well as excellent adhesive strength to bonding materials such as polyimide and copper, and excellent solder heat resistance.

[0090] Examples of aziridine compounds include N,N'-diphenylmethane-4,4'-bis(1-aziridinyl carboxite), N,N'-toluene-2,4-bis(1-aziridinyl carboxite), bisisophthaloyl-1-(2-methylaziridine), tri-1-aziridinylphosphine oxide, N,N'-hexamethylene-1,6-bis(1-aziridinyl carboxite), trimethylolpropane-tri-β-aziridinyl propionate, tetramethylolmethane-tri-β-aziridinyl propionate, tris-2,4,6-(1-aziridinyl)-1,3,5-triazine, trimethylolpropane-tris[3-(1-aziridinyl)propionate], and trimethylolpropane. Examples include lis[3-(1-aziridinyl)butyrate], trimethylolpropanetris[3-(1-(2-methyl)aziridinyl)propionate], trimethylolpropanetris[3-(1-aziridinyl)-2-methylpropionate], 2,2'-bishydroxymethylbutanoltris[3-(1-aziridinyl)propionate], pentaerythritoltetra[3-(1-aziridinyl)propionate], diphenylmethane-4,4-bis-N,N'-ethyleneurea, 1,6-hexamethylenebis-N,N'-ethyleneurea, 2,4,6-(triethyleneimino)-Syn-triazine, and bis[1-(2-ethyl)aziridinyl]benzene-1,3-carboxylic acid amide. In particular, 2,2'-bishydroxymethylbutanoltris[3-(1-aziridinyl)propionate] is preferred because it can achieve both adhesive strength and barrier properties.

[0091] Examples of amine compounds include polyamines having a dimer structure, as exemplified by the monomer of polyamide resin (A), and other polyamines that do not have a dimer structure.

[0092] The type of phenol compound is not particularly limited, but phenolic resins having two or more phenolic hydroxyl groups in one molecule are preferred. Examples of such phenolic resins include bisphenol A type phenolic resin, bisphenol F type phenolic resin, phenol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, triphenylmethane type phenolic resin, novolac type phenolic resin, dicyclopentadiene type phenolic resin, xylylene type phenolic resin, and biphenyl type phenolic resin.

[0093] Specific examples of metal chelates include aluminum chelate compounds, titanium chelate compounds, and zirconium chelate compounds. The central metal can be various metals such as iron, cobalt, and indium.

[0094] [Curing catalyst (F)] When an epoxy resin is used as the curing agent (E), a curing catalyst can be used in combination with the epoxy resin. Examples of curing catalysts used in combination with epoxy resins include urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Among these, imidazole-based curing accelerators are preferred from the viewpoint of improving crosslinkability. Other curing accelerators may be used individually or in combination of two or more. When a curing catalyst (F) is used, its content is, for example, 0.05 to 0.5% by mass, preferably 0.1 to 0.3% by mass, of 100% by mass of the total solid content of the curable composition.

[0095] Examples of urea-based curing accelerators include aliphatic dimethylureas such as 1,1-dimethylurea, 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, and 3-(2-methylphenyl)-1,1-dimethylurea. Examples include 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, and 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea.

[0096] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 1-methylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0097] Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-methylimidazole. Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, Examples include imidazole compounds such as 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins.

[0098] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0099] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0100] [Release agent (G)] The curable composition of the present invention may further contain a release agent (G). The addition of a release agent (G) is particularly preferable when molding using a mold. The use of a release agent (G) improves the release properties from the mold of the thermoforming apparatus. Examples of release agents (G) include natural waxes, synthetic waxes such as montanic acid esters, higher fatty acids or their metal salts, paraffin, and polyethylene oxide. Examples of natural waxes include carnauba wax and candelilla wax. Examples of synthetic waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and polyethylene wax. When using a release agent (G), only one type may be used, or two or more types may be used in combination. When a release agent (G) is used, its content is, for example, 0.1 to 0.5% by mass, preferably 0.2 to 0.3% by mass, of 100% by mass of the total solid content of the curable composition.

[0101] [Other fillers (H)] The curable composition of the present invention may contain other fillers (H) other than silica filler (C) and thermal conductive filler (D). Examples of other fillers (H) include flame retardant fillers and electromagnetic shielding fillers. Examples of other fillers (H) include quartz glass, talc, aluminum hydroxide, magnesium hydroxide, and ferrite. Preferred average particle size D of other fillers (H) 50 The surface treatment method is the same as that for silica filler (C) described above. From the viewpoint of exhibiting other properties such as electromagnetic shielding, the content ratio (mass ratio) of silica filler (C), thermal conductive filler (D), and other fillers (H) is preferably ((C)+(D)):(H)=50:50 to 90:10. However, it is preferable that the total of silica filler (C), thermal conductive filler (D), and other fillers does not exceed 95% by mass relative to 100% by mass of the curable composition.

[0102] In addition, thermoplastic resins (elastomers) can be used as other components. Other examples include dyes, pigments (e.g., carbon black), flame retardants, antioxidants, polymerization inhibitors, defoamers, leveling agents, ion capture agents, humectants, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, and electromagnetic shielding agents.

[0103] [Method for producing a curable composition] A curable composition is obtained by kneading each component. For example, a solvent-free curable composition can be obtained by melt-kneading the mixed components in a substantially solvent-free state. In this case, it may be in the desired shape such as a sheet, granules, pellets, powder, or tablet. Alternatively, the compounded composition may be a solid of any shape obtained by melt-kneading.

[0104] A sheet-like curable composition can be obtained, for example, by blending components of a substantially solvent-free curable composition, melt-kneading them with rolls or a kneader to form a sheet, and then cooling it. For melt-kneading, known kneaders such as mixing rolls, pressure kneaders, and extruders can be used. As for the kneading conditions, the temperature is preferably above the softening point of each of the above-mentioned components, for example, 30 to 150°C, preferably 40 to 140°C, and more preferably 60 to 120°C, considering the thermosetting properties of epoxy resins. The time is, for example, 1 to 30 minutes, preferably 5 to 15 minutes. Mixing is preferably carried out under reduced pressure, which allows for degassing and prevents gas from entering the mixture. The pressure under reduced pressure is preferably 0.1 kg / cm². 2 More preferably, 0.05 kg / cm³ 2 The following applies: The lower limit of pressure under reduced pressure is not particularly limited, but for example, 1 × 10⁻⁶ -4 kg / cm 2 That's all.

[0105] When forming a curable composition sheet by plastic deformation of a compound, it is preferable to perform plastic deformation on the compound while it remains at a high temperature without cooling after melt-kneading. The plastic deformation method is not particularly limited and includes methods such as plate pressing, T-die extrusion, screw die extrusion, roll rolling, roll kneading, inflation extrusion, co-extrusion, and calendering. Examples of molding machines include T-die screw molding machines, compression molding machines, and calendering machines. The plastic deformation temperature is preferably above the softening point of each component mentioned above, and considering the thermosetting and moldability of the epoxy resin, it is, for example, 40 to 150°C, preferably 50 to 140°C, and more preferably 70 to 130°C. A protective film may be laminated on the surface of the sheet-like curable composition. The sheet-like curable composition may be in the form of a single leaf or a roll that can be wound up.

[0106] The thickness of the sheet-like curable composition can be adjusted as appropriate according to the application, but it is preferably 50 μm or more, and more preferably 70 μm or more. By setting the thickness to 50 μm or more, for example, when used to seal IC chips and their surrounding wiring layers and insulating layers together, it becomes easy to completely cover the object to be coated, and an excellent cured product can be obtained.

[0107] Furthermore, the obtained sheet-like curable composition may be crushed into a powder or granules. The powder or granules may also be compressed into tablets.

[0108] Powdered, granular, or tablet-formed curable compositions may be manufactured directly from a mixture by melt-kneading using rolls or a kneader, without going through a sheet. This method can be performed using, for example, a kneader, roll mill, super mixer, Henschel mixer, Shugi mixer, or vertical mixer. It can be manufactured using batch-type kneaders such as lanunators, high-speed mixers, fur matrices, ball mills, steel mills, sand mills, vibratory mills, attritors, and Banbury mixers; twin-screw extruders, single-screw extruders, rotor-type twin-screw kneaders, etc.

[0109] Specifically, examples include: a method in which a molten and kneaded curable composition is supplied to the inside of a rotor consisting of a cylindrical outer circumference having multiple small holes and a disc-shaped bottom surface, and the curable composition is passed through the small holes by centrifugal force obtained by rotating the rotor; a method in which each raw material component of the curable composition is pre-mixed in a mixer, then heated and kneaded in a kneader such as a roll, kneader, or extruder, followed by a cooling and pulverization process to obtain pulverized material, from which coarse particles and fine powder are removed using a sieve; and a method in which each raw material component of the curable composition is pre-mixed in a mixer, then heated and kneaded using an extruder equipped with a die having multiple small diameters at the tip of the screw, and the molten resin extruded in a strand-like manner from the small holes arranged in the die is cut by a cutter that slides and rotates substantially parallel to the die surface.

[0110] When the material is in granular form, a particle size of 70 to 500 μm is preferable. By setting the particle size to 70 to 500 μm, it becomes easier to adjust the thickness of the cured composition while suppressing contamination by powder particles. The particle size is measured by extracting and quantifying particles using image binarization by microscopic observation.

[0111] Alternatively, a varnish may be prepared by mixing each component with a solvent, or by dissolving or dispersing a curable composition obtained by kneading each raw material component in an organic solvent, and then applying and drying the varnish to obtain a sheet-like curable composition. Methods of application include coating using coating machines such as comma coaters and die coaters, and printing methods such as stencil printing and gravure printing.

[0112] Furthermore, as described above, the sheet-like curable composition produced via varnish may be further pulverized into granules or powder. It may also be molded from the granules or powder into any desired shape, such as tablets (pellets). Additionally, the varnish can be spray-dried to form granules, powder, etc. The form of the curable composition can be appropriately selected depending on the application. For example, from the viewpoint of mold filling properties, granular or powdery forms are preferred, while from the viewpoint of productivity, sheet forms are preferred.

[0113] ≪Cured product and method for producing the same≫ The thermosetting curable composition of this embodiment is applied to a substrate, then dried and thermally polymerized. Alternatively, a cured product is obtained by thermal melt molding and curing treatment. Thermal melt molding and curing treatment may be performed simultaneously, or the curing treatment may be performed after thermal melt molding. Here, "cured product" refers to a state in which the curing reaction does not substantially proceed even if further heating is performed. In the melt kneading process when manufacturing the curable composition, a portion of the material may undergo a curing reaction, but this state, which could be cured by further heating, is not included in the definition of a cured product. When using the curable composition to encapsulate, for example, an IC chip, stress relaxation occurs due to the dimer structure contained in the polyamide resin (A) during the process of softening and fluidizing the molded body when heat is applied. The stress is distributed in the planar and longitudinal directions of the encapsulated body, resulting in effects such as suppression of adhesion reduction, suppression of foaming, and suppression of cracking. Pressure may be applied during melt molding.

[0114] The thermosetting 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 and becomes a cured product. When thermal melting, pressure may be applied in addition to heat. Applying heat and pressure makes softening and fluidization easier. Furthermore, stress relaxation due to the dimer structure contained in the polyamide resin (A) can be promoted.

[0115] The glass transition temperature (Tg) of the cured product is preferably 100 to 200°C, and more preferably 120 to 180°C. Setting the temperature within this range improves the gas barrier properties.

[0116] If the curable composition of this embodiment is in sheet form, for example, this sheet can be placed on a semiconductor chip, melt-molded by thermocompression bonding, and then cured to obtain an IC package in which the semiconductor chip is coated with a cured material that functions as a sealing resin. Alternatively, if the curable composition of this embodiment is in tablet form, for example, this tablet can be injected into a mold in which a semiconductor chip is set while melting and flowing, and an IC package can be obtained in which the cured material of the curable composition serves as the sealing resin through a molding process and a curing process.

[0117] ≪Laminated structure≫ The laminate comprises an adhesive layer formed from the curable composition of the present invention and a substrate. The laminate can be obtained by sandwiching an adhesive or adhesive sheet made from the curable composition of the present invention between plastic films such as polyester or polyimide, metal foil, etc., and then heating and pressurizing it. The film thickness of the curable composition is preferably 5 to 500 μm, and more preferably 10 to 100 μm, in order to exhibit sufficient adhesion and gas barrier properties, and also for ease of handling.

[0118] When using a plastic film as the base material, examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketones, and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0119] When using metal foil as the base material, examples of metal foil include copper foil and aluminum foil, with copper foil being preferred. As for copper foil, foil made of single-metal copper may be used, or foil made of an alloy of copper with another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0120] The method for applying the curable composition to the substrate is not particularly limited and includes, for example, comma coating, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure printing, flexographic printing, dip coating, spray coating, spin coating, etc. [Examples]

[0121] The present invention will be described in more detail below, but the following examples do not limit the scope of the present invention in any way. In the examples, "parts" refers to "parts by mass," and "%" refers to "percentage by mass." The amounts in the table are in parts by mass.

[0122] <Measurement of Acid Value> Precisely weigh approximately 1 g of the sample into a stoppered Erlenmeyer flask and dissolve it in 100 mL of cyclohexanone solvent. Add phenolphthalein reagent as an indicator and hold for 30 seconds. Then, titrate with 0.1 N alcoholic potassium hydroxide solution until the solution turns pale pink. The acid value was determined by the following formula (unit: mgKOH / g). Acid value (mgKOH / g)=(5.611×a×F) / S however, S: Sample volume (g) a: Consumption volume (mL) of 0.1N alcoholic potassium hydroxide solution F: Titer of 0.1N alcoholic potassium hydroxide solution

[0123] <Method for measuring weight-average molecular weight (Mw)> Mw was measured using a GPC (gel permeation chromatography) system "GPC-101" manufactured by Showa Denko. GPC is a liquid chromatography system that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on differences in their molecular size. In this invention, two "KF-805L" columns (Showa Denko: GPC column: 8mm ID × 300mm size) were connected in series, and the measurement was performed under the conditions of a sample concentration of 1% by mass, a flow rate of 1.0 mL / min, a pressure of 3.8 MPa, and a column temperature of 40°C. The weight-average molecular weight (Mw) was determined in polystyrene equivalent. For data analysis, calibration curves, molecular weights, and peak areas were calculated using the manufacturer's built-in software, and the weight-average molecular weight was determined for the analysis target range of retention times from 17.9 to 30.0 minutes.

[0124] <Method for measuring the glass transition temperature (Tg) of polyamide resin (A)> A polyamide resin varnish was prepared by dissolving polyamide resin in cyclohexanone to a non-volatile content of 35%. This varnish was applied to a heat-resistant release film using a 10 mil doctor blade and dried at 130°C for 10 minutes to obtain a 25 μm thick polyamide resin film, which was used as a sample for glass transition temperature measurement. The glass transition temperature (Tg) was determined by measuring Tanδ in the temperature range of -50 to 200°C using a dynamic viscoelasticity analyzer. Dynamic viscoelasticity measuring device: DVA-200 (manufactured by IT Measurement & Control Co., Ltd.) Heating rate: 10℃ / min Measurement frequency: 10Hz Grip length: 15mm Width: 5mm

[0125] <Synthesis of polyamide resin> [Polyamide resin (A'-1)] In a four-necked flask equipped with a stirrer, a reflux condenser with a Dean-Stark apparatus, a nitrogen inlet tube, and a thermometer, 481.0 g (0.901 mol) of priamine 1075 as a C36 dimeramine, 187.5 g (0.938 mol) of 3,4'-diaminodiphenyl ether as another diamine, 139.1 g (0.952 mol) of adipic acid and 192.4 g (0.952 mol) of sebacic acid as polybasic acids were charged and stirred. Once the exothermic reaction subsided, the mixture was gradually heated to allow the reaction to proceed. While removing the water generated during the reaction, the internal temperature was raised to 230°C and maintained at that temperature for 4 hours. Then, the reaction was completed by maintaining the temperature under reduced pressure of approximately 2 kPa for 2 hours. A polyamide resin (A'-1) with a weight-average molecular weight of 30,000, an acid value of 11.4 mg KOH / g, and a Tg of 28°C was obtained. The total content of dimer amine and dimer acid constituting the polyamide resin (A) is 48.1% by mass.

[0126] [Polyamide resin (A-1~A-12, A-14~A-16)] Polyamide resin was synthesized using the same method as for polyamide resin (A'-1), according to the composition and mass shown in Table 1, to obtain a polyamide resin. Its characteristic values ​​are shown in Table 1.

[0127] [Polyamide resin (A-13)] In a four-necked flask equipped with a stirrer, a reflux condenser with a Dean-Stark apparatus, a nitrogen inlet tube, and a thermometer, 672.6 g (1.26 mol) of priamine 1075 as a C36 dimeramine, 59.1 g (0.295 mol) of 3,4'-diaminodiphenyl ether as another diamine, 194.5 g (1.33 mol) of adipic acid and 59.1 g (0.292 mol) of sebacic acid as polybasic acids were charged and stirred. Once the exothermic reaction subsided, the mixture was gradually heated to allow the reaction to proceed. While removing the water generated during the reaction, the internal temperature was raised to 230°C and maintained at that temperature for 4 hours. Subsequently, the reaction was allowed to proceed under reduced pressure of approximately 2 kPa and maintained at the same temperature for 2 hours. Subsequently, the internal temperature was lowered to 180°C, 14.7 g (0.137 mol) of benzylamine was added, and the temperature was gradually raised to 240°C to complete the reaction. A polyamide resin (A-13) with a weight-average molecular weight of 30,000, an acid value of 0.5 mg KOH / g, and a Tg of 26°C was obtained.

[0128] [Table 1]

[0129] The meanings of the abbreviations in Table 1 are shown below. Dacid: A 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 "Prepol 1009" manufactured by Croda Japan Co., Ltd.) AdA: Adipic acid SeA: Sebacinic acid 5-HIP: 5-hydroxyisophthalic acid IPA: Isophthalic Acid DA: A dimer amine with 36 carbon atoms and a 6-carbon ring structure (dimer structure ratio: 95% or higher, "Priamine 1075" manufactured by Croda Japan Co., Ltd.) DAPE: 3,4'-diaminodiphenyl ether BzA: Benzylamine

[0130] [Example 1] 2.4 parts of polyamide resin (A-1), 0.6 parts of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (B-1), 79.9 parts of plate-like silica (C-1), and as a curing agent, 12 parts of biphenyl type epoxy resin (E-5) and 5 parts of triphenylmethane type phenolic resin (E-9). Further, 0.1 part of an imidazole compound (F-1) was blended as a curing catalyst, and melt-kneaded at 100 °C for 10 minutes under reduced pressure (0.01 kg / cm 2 ), to prepare a kneaded product. Next, the obtained kneaded product was formed into a sheet-like curable composition with a thickness of 300 μm by the flat plate press method.

[0131] [Examples 2 to 36], [Comparative Examples 1 to 4] Formulated as shown in Tables 2 to 4 in the same manner as in Example 1, and a sheet-like curable composition was obtained in the same manner as in Example 1.

[0132] Details of the materials used in the examples and comparative examples are shown below.

[0133] · Polyol (B) containing fluorene skeleton B-1: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene B-2: 9,9-bis(4-hydroxyphenyl)fluorene B-3: 9,9-bis(4-hydroxy-3-methylphenyl)fluorene

[0134] · Silica filler (C) C-1: Plate-like silica (manufactured by AGC, Sunbree, average particle size 5 μm) C-2: Fused spherical silica (manufactured by Admatechs, SO-25R, average particle size d50: 0.5 μm)

[0135] · Thermal conductivity filler (D) D-1: Plate-like alumina (manufactured by Kinsai Matech, Seraph 02025, average particle size 2 μm) D-2: Plate-like alumina (manufactured by Kinsai Matech, Seraph 05070, average particle size 5 μm) D-3: Boron nitride (manufactured by Tomoe Chemical Co., Ltd., PT120, average particle size 12 μm)

[0136] • Hardener (E) E-1: Trisphenolmethane type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., EPPN-501H, epoxy equivalent (EPW) = 167 E-2: Phenol aralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., NC-3000, EPW=275 E-3: Phenolic-modified xylene resin type epoxy resin, manufactured by Mitsubishi Chemical Corporation, YX7700, EPW=270 E-4: Dicyclopentadiene type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., XD-1000, EPW=253 E-5: Biphenyl-type epoxy resin, manufactured by Mitsubishi Chemical Corporation, YX4000HK, EPW=185 E-6: Tetrakisphenolethane type epoxy resin, manufactured by Mitsubishi Chemical Corporation, jER1031S, EPW=200 E-7: Naphthalene-type epoxy resin, manufactured by DIC Corporation, HP-6000, EPW=250 E-8: Naphthalene-containing novolac-type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., NC-7000L, EPW=231 E-9: Triphenylmethane-type phenolic resin, manufactured by Meiwa Kasei Co., Ltd., MEH-7500, OH equivalent = 97 g / eq. E-10: Xylylene-type phenolic resin, manufactured by Meiwa Kasei Co., Ltd., MEHC-7800-SS, OH equivalent = 173 g / eq. E-11: Hexamethylene diisocyanurate, manufactured by Sumika Bayer, Desmodule N3300

[0137] Curing catalyst (F) F-1: Imidazole compound (2P4MZ, manufactured by Shikoku Chemicals Co., Ltd.)

[0138] For each example and comparative example, the cured product of the curable composition was subjected to Tg measurement, and its water vapor permeability, oxygen permeability, and adhesiveness were evaluated. The measurement methods and evaluation criteria are as follows.

[0139] <Method for measuring the glass transition temperature (Tg) of a cured product> Each of the prepared 300 μm sheet-like curable compositions was heat-cured on a heat-resistant release film at 180°C for 60 minutes to prepare samples for glass transition temperature measurement. Tanδ was measured using a dynamic viscoelasticity analyzer in the temperature range of -50 to 200°C to determine the glass transition temperature (Tg). Dynamic viscoelasticity measuring device: DVA-200 (manufactured by IT Measurement & Control Co., Ltd.) Heating rate: 10℃ / min Measurement frequency: 10Hz Grip length: 15mm Width: 5mm

[0140] <Preparation of samples and test pieces for adhesive strength testing> Each sheet of curable composition prepared was cut to 50 mm x 50 mm, and nine 5 mm x 5 mm x 300 μm Au-plated silicon chips were placed on top of it in three vertical and three horizontal rows at equal intervals. However, the sheet of curable composition was positioned so that it was in contact with the silicon surface of the silicon chips. To ensure close adhesion between the sheet of curable composition and the silicon chips, a 38 μm polyethylene terephthalate sheet treated with silicone release agent was placed opposite and heat-laminated using a heat lamination test apparatus (temperature 80°C, cylinder pressure 0.3 MPa). After heat lamination, cuts were made around the silicon chips with a utility knife to create samples for adhesion strength testing, with the sheet of curable composition temporarily adhered to one side of the silicon chip. A gold-plated copper frame substrate was prepared as the adherend, and a silicon chip with a sheet-like curable composition temporarily bonded to it was placed on top of it. The substrate was then hot-pressed (150°C × 1 MPa × 1 min), followed by post-baking (170°C × 2 hours) to prepare the test specimen.

[0141] <Evaluation of adhesive strength> Each test specimen prepared as described above was evaluated using a bond tester (Nordson Advanced Technologies, product name: Dage4000-PXY). The measurement conditions were a measurement speed of 100 μm / s and a measurement height of 100 μm. The arithmetic mean of the adhesive strength measured at three points was calculated. A higher value indicates better adhesion of the cured material to the silicone chip and the substrate. The evaluation criteria are as follows. 5: Excellent (arithmetic mean of adhesive strength is 10 N / mm or higher). 4: Superior (arithmetic mean of adhesive strength is 7 N / mm or higher, but less than 10 N / mm). 3: Excellent (arithmetic mean of adhesive strength is 5 N / mm or higher, but less than 7 N / mm). 2: Practical (arithmetic mean of adhesive strength is 3 N / mm or more, but less than 5 N / mm). 1: Impractical (arithmetic mean of adhesive strength is less than 3 N / mm).

[0142] <Evaluation of water vapor transmission rate> Each of the obtained sheet-like curable compositions was cut into 50 mm x 50 mm sections and post-baked (170°C x 2 hours) to prepare samples for water vapor transmission rate measurement. Water vapor transmission rate was measured using a cup method moisture meter. The measurement method was carried out in accordance with JIS Z0208, and the measurement conditions were 40°C and 90% relative humidity. 5: Excellent (Water vapor transmission rate of 3.0 g / m³) 2 ·day or less). 4: Superior (water vapor transmission rate of 3.0 g / m³) 2 • Over 5.0 g / m² per day 2 ·day or less). 3: Excellent (Water vapor transmission rate of 5.0 g / m³) 2 • Over 10.0 g / m³ 2 ·day or less). 2: Practical (water vapor transmission rate of 10.0 g / m³) 2 • 30.0 g / m³ over a day 2 (Less than 1 day) 1: Impossible to use (water vapor transmission rate of 30.0 g / m³) 2(more than one day).

[0143] <Evaluation of oxygen permeability> Each of the obtained sheet-like curable compositions was cut into 50 mm x 50 mm sections and post-baked (170°C x 2 hours) to prepare samples for measurement. Oxygen permeability was measured under conditions of 23°C and 80% RH relative humidity and evaluated according to the following criteria. Oxygen permeability was measured using the isobaric method in accordance with JIS K 7126, using a MOCON OX-TRAN2 / 21 oxygen permeability analyzer. 5: Excellent (oxygen permeability of 3.0 cc / m³) 2 ·day · atm or less). 4: Superior (oxygen permeability of 3.0 cc / m³) 2 • day • atm exceeding 5.0 cc / m 2 ·day · atm or less). 3: Excellent (oxygen permeability of 5.0 cc / m³) 2 • day • atm exceeding 10.0 cc / m 2 ·day · atm or less). 2: It is practical (oxygen permeability of 10.0 cc / m³) 2 • day • atm exceeding 30.0 cc / m 2 (Less than 1 / day ATM) 1: Impossible to use (oxygen permeability of 30.0 cc / m³) 2 ·day · atm or more).

[0144] [Table 2]

[0145] [Table 3]

[0146] [Table 4]

[0147] As shown in the examples, it was confirmed that the cured product obtained from the curable composition according to this example exhibits superior adhesion and gas barrier properties compared to Comparative Examples 1-4.

[0148] [Industrial applicability] The curable composition according to this embodiment exhibits excellent adhesion and gas barrier properties, making it suitable for use as an insulating resin material, including encapsulants, adhesives, underfills, and potting materials for semiconductor chips. Furthermore, it can be applied to fields requiring high barrier properties, such as organic thin-film solar cells and display elements, and is expected to be useful in a wide range of fields.

Claims

1. The material comprises a polyamide resin (A), a fluorene skeleton-containing polyol (B), at least one of a silica filler (C) and a thermally conductive filler (excluding silica filler) (D), and a curing agent (E). The aforementioned thermally conductive filler (D) is a filler with a thermal conductivity of 15 (W / m·K) or more at 20°C. The polyamide resin (A) contains 50 to 99% by mass of dimer acid and / or dimer amine in 100% by mass of monomers, The amount of the polyamide resin (A) blended is 0.10 to 40% by mass relative to 100% by mass of the nonvolatile content of the curable composition. The amount of the fluorene skeleton-containing polyol (B) blended is 1 to 40% by mass relative to 100% by mass of the polyamide resin (A). A curable composition in which the total amount of the silica filler (C) and the thermally conductive filler (D) is 40 to 95% by mass relative to 100% by mass of the non-volatile content of the curable composition.

2. The curable composition according to claim 1, wherein the glass transition temperature of the polyamide resin (A) is 0 to 90°C.

3. The curable composition according to claim 1, wherein the curing agent (E) comprises an epoxy resin.

4. The curable composition according to claim 1, wherein the thermally conductive filler (D) contains alumina.

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

6. A laminate comprising an adhesive layer formed from a curable composition according to any one of claims 1 to 4, and a substrate.

7. The material comprises a polyamide resin (A), a fluorene skeleton-containing polyol (B), at least one of a silica filler (C) and a thermally conductive filler (excluding silica filler) (D), and a curing agent (E). The aforementioned thermally conductive filler (D) is a filler with a thermal conductivity of 15 (W / m·K) or more at 20°C. The polyamide resin (A) contains 50 to 99% by mass of dimer acid and / or dimer amine in 100% by mass of monomers, The amount of the polyamide resin (A) blended is 0.10 to 40% by mass relative to 100% by mass of the nonvolatile content of the curable composition. The amount of the fluorene skeleton-containing polyol (B) blended is 1 to 40% by mass relative to 100% by mass of the polyamide resin (A). A curable composition in which the total amount of silica filler (C) and thermal conductive filler (D) is 40 to 95% by mass relative to 100% by mass of the nonvolatile content of the curable composition, A method for manufacturing a cured product, comprising a process of molding by thermal melting and then thermal curing.

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