Thermosetting resin composition, cured product, semiconductor sealing agent, semiconductor device, insulating material for printed wiring board, and printed wiring board

Abstract

The present disclosure addresses the problem of providing a thermosetting resin composition capable of achieving a low linear thermal expansion coefficient and a low elastic modulus. The present disclosure provides a thermosetting resin composition which contains a thermosetting resin (A), an acid anhydride (B), a compound (C), and at least one filler (D) selected from the group consisting of inorganic fine particles and fibers, and in which the compound (C) is one or more selected from the group consisting of terminal-blocked polyester oligomers, terminal-blocked polyether oligomers, and terminal-blocked polyether ester oligomers. The present disclosure also provides: a cured product of the thermosetting resin composition; and a semiconductor sealing agent, a semiconductor device, an insulating material for printed wiring board, and a printed wiring board, in all of which said thermosetting resin composition is contained.

Description

Thermosetting resin composition, cured product, semiconductor encapsulant, semiconductor device, insulating material for printed circuit board, and printed circuit board

[0001] This disclosure relates to thermosetting resin compositions, cured products, semiconductor encapsulants, semiconductor devices, insulating materials for printed circuit boards, and printed circuit boards.

[0002] Resin compositions containing thermosetting resins are used in a wide range of fields, including as encapsulating materials to protect semiconductor elements such as capacitors, diodes, transistors, and thyristors, integrated circuits such as ICs and LSIs, and insulating materials used in printed circuit boards. On the other hand, molded articles using the above-mentioned thermosetting resin compositions are composites with various dissimilar materials, and due to differences in the thermal expansion coefficients between the resin composition and each dissimilar material, warping may occur during the manufacturing of the composite, which can cause problems with the dimensional accuracy of the molded article. Furthermore, if the molded article is exposed to temperature changes in the usage environment, defects may occur in the molded article due to differences in the thermal expansion coefficients between the resin composition and each dissimilar material (see, for example, Patent Document 1).

[0003] Japanese Patent Publication No. 2003-82241 Japanese Patent Publication No. 2021-038356

[0004] The inventors have found that when a thermoplastic resin (modified resin) having at least one selected from the group consisting of hydroxyl groups and carboxyl groups is added to a thermosetting resin composition, the linear thermal expansion coefficient of the thermosetting resin composition decreases (see Patent Document 2). On the other hand, as a result of diligent research by the inventors, it has been found that in thermosetting resin compositions containing a specific curing agent, the effect of reducing the linear thermal expansion coefficient and the effect of reducing the elastic modulus are not sufficiently obtained even when a conventional modified resin is added.

[0005] The problem that this disclosure aims to solve is to provide a thermosetting resin composition capable of reducing the coefficient of linear thermal expansion and the modulus of elasticity.

[0006] As a result of further intensive research by the present inventors, they found that the above phenomenon occurs depending on the combination of the type of curing agent and the modified resin, and that by adding a specific modified resin to a thermosetting resin composition containing a specific curing agent, the above problem can be solved without impairing the function exhibited by the specific curing agent.

[0007] This disclosure includes the following embodiments: [1] A thermosetting resin composition comprising a thermosetting resin (A), an acid anhydride (B), a compound (C), and one or more fillers (D) selected from the group consisting of inorganic fine particles and fibers, wherein the compound (C) is one or more selected from the group consisting of end-encapsulated polyester oligomers, end-encapsulated polyether oligomers, and end-encapsulated polyether ester oligomers. [2] The thermosetting resin composition according to [1], wherein the compound (C) is a compound selected from the group of compounds represented by the following chemical formulas (I) to (III).

[0008] (In the above chemical formula (I), R1 and R2 are each independently any functional group consisting of one or more combinations selected from the group consisting of hydrocarbon groups, ether groups, ester groups, urethane groups, urea groups, amide groups, and amino groups having 1 to 30 carbon atoms, and at least one of R1 and R2 is a functional group containing an ether group and / or an ester group. n1 is a real number in the range of 1 to 6.)

[0009] (In the above chemical formula (II), R3 and R4 are each independently any functional group consisting of one or more combinations selected from the group consisting of hydrocarbon groups, ether groups, ester groups, urethane groups, urea groups, amide groups, and amino groups having 1 to 30 carbon atoms, and at least one of R3 and R4 is a functional group containing an ether group and / or an ester group. n2 is a real number in the range of 1 to 6.)

[0010] (In the above chemical formula (III), R5 is any functional group consisting of one or more combinations selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms, ether groups, ester groups, and sulfonyl groups, and R6 is any functional group consisting of one or more combinations selected from the group consisting of hydrocarbon groups having 1 to 30 carbon atoms, ether groups, ester groups, urethane groups, urea groups, amide groups, and amino groups, and at least one of R5 and R6 is a functional group containing an ether group and / or an ester group. n3 is a real number in the range of 1 to 6.) [3] The thermosetting resin composition according to [1] or [2] above, wherein the compound (C) is a reaction product of a monofunctional alcohol (I-A) and a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (I-B). [4] The thermosetting resin composition according to [1] or [2] above, wherein compound (C) is a reaction product of a monofunctional alcohol (I-A) and a polyester and / or polyether ester (I-C) having carboxyl groups at one or both ends. [5] The thermosetting resin composition according to [3] or [4] above, wherein the monofunctional alcohol (I-A) is one or more selected from the group consisting of monofunctional polyethylene glycol, monofunctional polypropylene glycol, and long-chain aliphatic alcohols. [6] The thermosetting resin composition according to [1] or [2] above, wherein compound (C) is a reaction product of a compound (II-A) having one or more hydroxyl groups and a monofunctional carboxylic acid (II-B). [7] The thermosetting resin composition according to [1] or [2] above, wherein compound (C) is a reaction product of a monofunctional or polyfunctional alcohol (III-A) and a monofunctional isocyanate (III-B). [8] A thermosetting resin composition according to any one of [1] to [7] above, wherein the hydroxyl value of compound (C) is 0 or more and 10 or less. [9] A thermosetting resin composition according to any one of [1] to [8] above, wherein the number average molecular weight of compound (C) is 500 to 50,000.

[10] A thermosetting resin composition according to any one of [1] to [9] above, wherein the content of compound (C) is 5 to 45% by mass of the nonvolatile content of the components excluding the filler (D).

[11] A cured product of the thermosetting resin composition according to any one of [1] to

[10] above.

[12] A semiconductor encapsulant comprising the thermosetting resin composition described in any of [1] to

[10] above.

[13] A semiconductor device comprising the semiconductor encapsulant described in

[12] above.

[14] An insulating material for printed circuit boards comprising the thermosetting resin composition described in any of [1] to

[10] above.

[15] A printed circuit board comprising the insulating material for printed circuit boards described in

[14] above.

[0011] According to the thermosetting resin composition of this disclosure, a low coefficient of linear thermal expansion and a low modulus of elasticity can be achieved by using a specific compound (C) in combination with a composition containing an acid anhydride (B).

[0012] [Thermosetting Resin Composition] The thermosetting resin composition of the present disclosure contains, as an essential component, a thermosetting resin (A), an acid anhydride (B), a compound (C), and one or more fillers (D) selected from the group consisting of inorganic fine particles and fibers, wherein the compound (C) is one or more selected from the group consisting of end-capped polyester oligomers, end-capped polyether oligomers, and end-capped polyether ester oligomers.

[0013] The components of the thermosetting resin composition of this disclosure will be described in detail below. In this specification, compound (C) may be referred to as the "specific modified resin."

[0014] [1] Thermosetting resin (A) As the thermosetting resin (A), for example, epoxy resin, benzoxazine structure-containing resin, maleimide resin, vinylbenzyl compound, acrylic compound, copolymer of styrene and maleic anhydride, etc., can be used. These resins may be used alone or two or more in combination. Among these, epoxy resin and / or maleimide resin are preferred, and epoxy resin is more preferred, because they readily form a phase separation structure with compound (C) described later and the effects of this disclosure are more easily obtained.

[0015] Examples of the epoxy resins mentioned above include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, diglycidyloxynaphthalene compounds (1,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, etc.), phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, and dicyclopentadiene-phenol addition reaction type epoxy resin. Epoxy resins such as silicic acid resins, phenol aralkyl epoxy resins, naphthol novolac epoxy resins, naphthol aralkyl epoxy resins, naphthol-phenol copolymer novolac epoxy resins, naphthol-cresol copolymer novolac epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type epoxy resins, biphenyl novolac epoxy resins, naphthalene skeleton-containing epoxy resins such as 1,1-bis(2,7-diglycidyloxy-1-naphthyl)alkanes, and phosphorus-modified epoxy resins obtained by introducing phosphorus atoms into these various epoxy resins can be used. Hydrogenated versions of these epoxy resins (hydrogenated epoxy resins) can also be used.

[0016] Among these, cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl novolac type epoxy resins, naphthol novolac type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol copolymer novolac type epoxy resins, naphthol-cresol copolymer novolac type epoxy resins, crystalline biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, xanthene type epoxy resins, alkoxy group-containing aromatic ring-modified novolac type epoxy resins (compounds in which a glycidyl group-containing aromatic ring and an alkoxy group-containing aromatic ring are linked with formaldehyde), and hydrogenated versions of these epoxy resins (hydrogenated epoxy resins) are particularly preferred because they yield cured products with excellent heat resistance.

[0017] As the maleimide resin mentioned above, for example, a resin represented by any of the following structural formulas can be used.

[0018]

[0019] [In formula (1), R 1 represents an a1-valent organic group, R 2 and R 3 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and a1 represents an integer of 1 or more.

[0020]

[0021] [In formula (2), R 4 , R 5 and R 6 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms, L 1 and L 2 Each of these independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms, an aromatic hydrocarbon group with 6 to 10 carbon atoms, or a group with 6 to 15 carbon atoms formed by combining a saturated hydrocarbon group and an aromatic hydrocarbon group. Each of a3, a4, and a5 independently represents an integer from 1 to 3, and n represents an integer from 0 to 10.

[0022] The total content of the epoxy resin and the maleimide resin in the thermosetting resin (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, with an upper limit of 100% by mass.

[0023] The content of the thermosetting resin (A) is preferably 3% by mass or more, more preferably 5% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, based on the nonvolatile content of the components of the thermosetting resin composition excluding the filler (D).

[0024] [2] Acid anhydride (B) The above acid anhydride (B) functions as a curing agent and can cure the thermosetting resin composition, and can make the thermosetting resin composition even more viscous. By using the acid anhydride, the pot life of the thermosetting resin composition is extended and the cured product has excellent electrical properties.

[0025] Examples of the above-mentioned acid anhydride (B) include compounds having one or more acid anhydride groups in one molecule. Among these, compounds having two or more acid anhydride groups in one molecule are preferred. In addition to acid anhydrides, examples of the above-mentioned acid anhydride (B) include acid anhydrides having substituents (preferably hydrocarbon groups), aqueous additives of acid anhydrides, and modified acid anhydrides. Specific examples of the above-mentioned acid anhydride (B) include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, glutaric anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, succinic anhydride, methylhymic anhydride, which may have substituents (preferably hydrocarbon groups, more preferably alkyl or alkenyl groups), and methylhymic anhydride. These compounds may be used individually or in combination of two or more.

[0026] Examples of commercially available acid anhydrides (B) include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA", etc. from Shin Nippon Rika Co., Ltd.; "YH-306", "YH-307", etc. from Mitsubishi Chemical Corporation; "HN-2200", "HN-5500", etc. from Resona Corporation; and "EF-30", "EF-40", "EF-60", "EF-80", etc. from Clay Valley Corporation.

[0027] The content of the acid anhydride (B) in the thermosetting resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less, based on the nonvolatile content of the components of the thermosetting resin composition excluding the filler (D).

[0028] [3] Compound (C) Compound (C) above is one or more selected from the group consisting of end-capped polyester oligomers, end-capped polyether oligomers, and end-capped polyether ester oligomers. End-capped polyester oligomers, end-capped polyether oligomers, and end-capped polyether ester oligomers are oligomers that substantially do not have acid groups such as hydroxyl groups or carboxyl groups at at least one end. In particular, oligomers that substantially do not have acid groups such as hydroxyl groups or carboxyl groups at both ends are preferred, and oligomers that substantially do not have acid groups such as hydroxyl groups or carboxyl groups in the molecule are more preferred. In this disclosure, "end" of each compound refers to the end in the length direction of the molecular main chain. Furthermore, substantially not having means that the hydroxyl value and acid value are within the range described later. Compound (C) contained in the thermosetting resin composition of this disclosure may be one type or two or more types.

[0029] The hydroxyl value of compound (C) is preferably 0 to 10, more preferably 0 to 5, even more preferably 0 to 2, and particularly preferably 0. The acid value of compound (C) is also preferably 0 to 10, more preferably 0 to 5, even more preferably 0 to 2, and particularly preferably 0. The hydroxyl value and acid value of compound (C) can be adjusted, respectively, by the type of raw material and reaction ratio (molar ratio) of compound (C).

[0030] Examples of the above compound (C) include compounds selected from the group consisting of compounds represented by the following chemical formulas (I) to (III). One or more of these can be used. In particular, for the end-capped polyester oligomer and the end-capped polyether ester oligomer, one or more compounds selected from the group consisting of compounds represented by the following chemical formulas (I) to (III) can be used. Furthermore, for the end-capped polyether oligomer, one or more compounds represented by the following chemical formula (III) can be used.

[0031]

[0032] (In the above chemical formula (I), R1 and R2 are each independently an arbitrary functional group composed of one or more combinations selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, an ether group, an ester group, a urethane group, a urea group, an amide group, and an amino group, and at least one of R1 and R2 is a functional group containing an ether group and / or an ester group. n1 is a real number in the range of 1 to 6.) Among them, n1 is preferably a real number in the range of 1 to 3, and more preferably a real number in the range of 1 to 2.

[0033]

[0034] (In the above chemical formula (II), R3 and R4 are each independently an arbitrary functional group composed of one or more combinations selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, an ether group, an ester group, a urethane group, a urea group, an amide group, and an amino group, and at least one of R3 and R4 is a functional group containing an ether group and / or an ester group. n2 is a real number in the range of 1 to 6.) Among them, n2 is preferably a real number in the range of 1 to 3, and more preferably a real number in the range of 1 to 2.

[0035]

[0036] (In the above chemical formula (III), R5 is an arbitrary functional group composed of one or more combinations selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, an ether group, an ester group, and a sulfonyl group, R6 is an arbitrary functional group composed of one or more combinations selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, an ether group, an ester group, a urethane group, a urea group, an amide group, and an amino group, and at least one of R5 and R6 is a functional group containing an ether group and / or an ester group. n3 is a real number in the range of 1 to 6.) Among them, n (should be n3) is preferably a real number in the range of 1 to 3, and more preferably a real number in the range of 1 to 2

[0037] It should be noted that there seems to be a small error in the original text where "n" in the last part of should probably be "n3" for consistency. This has been corrected in the translation.- The above compound (C) represented by the above chemical formula (I) - As the above compound (C) represented by the above chemical formula (I), for example, the reaction product of a monofunctional alcohol (I-A) and a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (I-B), the reaction product of a monofunctional alcohol (I-A) and a polyester and / or a polyether ester (I-C) having a carboxyl group at one end or both ends, etc. can be mentioned.

[0038] The monofunctional alcohol (I-A) that is a raw material for the compound represented by the above chemical formula (I) has one hydroxyl group in the compound. The monofunctional alcohol (I-A) preferably has no functional group that can react with a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (I-B), and a polyester and / or a polyether ester (I-C) having a carboxyl group at one end or both ends other than one hydroxyl group.

[0039] The monofunctional alcohol (I-A) only needs to have one hydroxyl group. For example, aliphatic alcohols, monofunctional polyethylene glycols, monofunctional polypropylene glycols, monofunctional polyoxybutylene, monofunctional polycaprolactone, monofunctional polyesters, etc. can be mentioned. These can be used alone or in combination of two or more. When the compound reacting with the monofunctional alcohol (I-A) is a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (I-B), the aliphatic alcohol used as the monofunctional alcohol (I-A) is preferably a long-chain aliphatic alcohol. When the compound reacting with the monofunctional alcohol (I-A) is a polyester and / or a polyether ester (I-C) having a carboxyl group at one end or both ends, the aliphatic alcohol used as the monofunctional alcohol (I-A) may be a long-chain aliphatic alcohol or a short-chain aliphatic alcohol. Among them, from the viewpoint of easily forming a phase-separated structure, the monofunctional alcohol (I-A) is preferably a compound selected from the group consisting of monofunctional polyethylene glycol, monofunctional polypropylene glycol, and long-chain aliphatic alcohols.

[0040] The long-chain aliphatic alcohols described above preferably have 5 to 25 carbon atoms, and more preferably 6 to 23 carbon atoms. Specific examples of such long-chain aliphatic alcohols include linear or branched long-chain aliphatic saturated alcohols such as pentyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, behenyl alcohol, 2-methyl-decane-1-ol, 2-ethyl-decane-1-ol, 2-hexyl-octan-1-ol, 2-octyldodecanol, 2-isoheptylisoundodecanol, and 2-decyltetradecanol, as well as linear or branched long-chain aliphatic unsaturated alcohols such as hexenol, 2-hexen-1-ol, 1-hexen-3-ol, pentenol, and 2-methyl-1-pentenol. These may be used individually or in combination of two or more. Among these, branched aliphatic saturated alcohols are preferred because they tend to become liquid and have reduced crystallinity.

[0041] Examples of monofunctional polyethylene glycols include polyethylene glycol monoalkyl ethers such as polyethylene glycol monobutyl ether and polyethylene glycol monododecyl ether, and polyethylene monoesters such as polyethylene monoacetate. These may be used individually or in combination of two or more.

[0042] Examples of monofunctional polypropylene glycols include compounds in which one end of a polypropylene glycol is encapsulated, such as polypropylene monoalkyl ethers like polypropylene glycol monobutyl ether; polyoxypropylene glycol monoalkyl ethers such as polyoxypropylene methyl ether, polyoxypropylene ethyl ether, polyoxypropylene butyl ether, polyoxypropylene-2-ethylhexyl ether, polyoxypropylene oleyl ether, and polyoxypropylene-2-octyldodeca ether; and polypropylene glycol monoesters such as polypropylene glycol monoacetate and polypropylene glycol monoacetate. These may be used individually or in combination of two or more.

[0043] In addition to the compounds exemplified above, other examples of monofunctional alcohols (I-A) include compounds classified as monofunctional alcohols having one hydroxyl group among the compounds exemplified as polyols used as raw materials for polyesters and / or polyether esters (I-C), (I-C-1), and (I-C-2) having carboxyl groups at one or both ends, as described later; compounds classified as monofunctional alcohols having one hydroxyl group among the compounds exemplified as compounds (II-A) having one or more hydroxyl groups, used as raw materials for compounds represented by chemical formula (II) described later; and so on. These may be used individually or in combination of two or more.

[0044] The molecular weight of the monofunctional alcohol (I-A) is preferably in the range of 100 to 20,000, and more preferably in the range of 150 to 10,000. The above molecular weights are values ​​calculated based on the hydroxyl value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0045] The monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (I-B) used as a raw material for the compound represented by the above chemical formula (I) is not particularly limited, but dicarboxylic acids such as aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids, and / or their acid anhydrides are preferred.

[0046] The above aliphatic dicarboxylic acids and their acid anhydrides preferably have a carboxyl group at least at one end, and more preferably have carboxyl groups at both ends. Examples include malonic acid, adipic acid, succinic acid, azelaic acid, suberic acid, sebacic acid, glutaric acid, dodecanedioic acid, eicosanedioic acid, maleic acid, fumaric acid, maleic anhydride, and itaconic anhydride. The above alicyclic dicarboxylic acids and their acid anhydrides preferably have a carboxyl group at least at one end, and more preferably have carboxyl groups at both ends. Examples include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, and 1,4-cyclohexanedicarboxylic acid. Examples of the above-mentioned aromatic dicarboxylic acids and / or their acid anhydrides include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, pyromellitic acid, and the like. These compounds may be used individually or in combination of two.

[0047] Furthermore, as monofunctional or polyfunctional carboxylic acids and / or their acid anhydrides (I-B), examples include compounds classified as monofunctional or polyfunctional carboxylic acids and / or their acid anhydrides among the compounds exemplified as polybasic acids used as raw materials for polyesters and / or polyether esters (I-C), (I-C-1), and (I-C-2) having carboxyl groups at one or both ends, as described later; compounds exemplified as monofunctional carboxylic acids (II-B) used as raw materials for compounds represented by compound (II) described later, and / or their acid anhydrides; and so on. These may be used individually or in combination of two or more.

[0048] The above monofunctional or polyfunctional carboxylic acids and / or their acid anhydrides (I-B) are more preferably linear aliphatic dicarboxylic acids due to their low viscosity and tendency to form phase separation, and among these, compounds selected from the group consisting of adipic acid, azelaic acid, sebacic acid, and dodecanediic acid are preferred.

[0049] The molecular weight of the above monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (I-B) is preferably in the range of 110 to 400, and more preferably in the range of 140 to 350. The above molecular weight is the value calculated based on the acid value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0050] In the compound represented by the above chemical formula (I), the reaction between a monofunctional alcohol (I-A) and a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (I-B) is carried out in a molar equivalent ratio (hydroxyl group / carboxyl group) of 0.5 to 2, more preferably in the range of 0.7 to 1.4, and even more preferably in the range of 0.9 to 1.1. By setting the molar equivalent ratio within the above range, the carboxyl groups of the monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (I-B) can be encapsulated by the monofunctional alcohol (I-A).

[0051] The polyester and / or polyether ester (I-C) having carboxyl groups at one or both ends, which serves as a raw material for the compound represented by the above chemical formula (I), can be, for example, a reaction product of a polyether polyol and a polybasic acid. These polyols may be used alone or in combination of two or more.

[0052] Examples of the polyether polyols used include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Among these, polypropylene glycol is preferred because it is easier to obtain the effects of compound (C).

[0053] As the polybasic acid mentioned above, one or more types can be used, for example, aliphatic polycarboxylic acids such as malonic acid, adipic acid, succinic acid, azelaic acid, suberic acid, sebacic acid, glutaric acid, dodecanedioic acid, eicosanedioic acid, maleic acid, fumaric acid, maleic anhydride, and itaconic anhydride; alicyclic polycarboxylic acids such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, and 1,4-cyclohexanedicarboxylic acid; and aromatic polycarbonates such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid.

[0054] Furthermore, examples of polyesters and / or polyether esters (I-C) having carboxyl groups at one or both ends, which can be used as raw materials for the compound represented by the above chemical formula (I), include polyesters (I-C-1) or polyether esters (I-C-2) obtained by reacting a polyol with a polycarboxylic acid (polybasic acid); and polyesters obtained by copolymerizing the above polyesters (I-C-1) or polyether esters (I-C-2) with a polyester obtained by a ring-opening polymerization reaction of a cyclic ester compound.

[0055] One or more polyols can be used as raw materials for the above polyester (I-C-1). For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-pro Examples include aliphatic polyols such as pandiol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,4-diethyl-1,5-pentanediol, trimethylolethane, trimethylolpropane, and pentaerythritol; polyols having an alicyclic structure such as cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, and alkylene oxide adducts thereof; polyols having an aromatic structure such as bisphenol A and bisphenol F; and polyols obtained by alkylene oxide modification of the above aromatic polyols.

[0056] The molecular weight of the polyol, which is the raw material for the above polyester (I-C-1), is preferably 50 or more, preferably 1,500 or less, more preferably 1,000 or less, and even more preferably 700 or less. The above molecular weight is the value calculated based on the hydroxyl value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0057] Furthermore, as the polyol used as a raw material for the above-mentioned polyether ester (I-C-2), for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., can be used. One or more of these can be used.

[0058] The molecular weight of the polyol, which is the raw material for the above polyether ester (I-C-2), is preferably 400 or more, preferably 700 or more, and the upper molecular weight is preferably 4,000 or less, and more preferably 2,000 or less. The above molecular weights are values ​​calculated based on the hydroxyl value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0059] As the polycarboxylic acid (polybasic acid) used as a raw material for the polyester and / or polyether ester (I-C) mentioned above, one or more types can be used. For example, aliphatic polycarboxylic acids such as malonic acid, adipic acid, succinic acid, azelaic acid, suberic acid, sebacic acid, glutaric acid, dodecanedioic acid, eicosanedioic acid, maleic acid, fumaric acid, maleic anhydride, and itaconic anhydride; alicyclic polycarboxylic acids such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, and 1,4-cyclohexanedicarboxylic acid; and aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid can be used.

[0060] Furthermore, as the polycarboxylic acid (polybasic acid) used as a raw material for polyester and / or polyether ester (I-C), other examples include compounds classified as polycarboxylic acids (polybasic acids) among the compounds exemplified above as monofunctional or polyfunctional carboxylic acids and / or their acid anhydrides (I-B); and so on. These may be used individually or in combination of two or more.

[0061] Polyesters and / or polyether esters (I-C) having carboxyl groups at one or both ends can be obtained, for example, by reacting the above-mentioned polyol with a polycarboxylic acid under conditions in which the equivalent amount of carboxyl groups in the reaction materials is greater than the equivalent amount of hydroxyl groups.

[0062] The number-average molecular weight of the polyester and / or polyether ester (I-C) having carboxyl groups at one or both ends is preferably in the range of 140 to 40,000, and more preferably in the range of 140 to 20,000. The above molecular weight is the value calculated based on the acid value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0063] The monofunctional alcohol (I-A) reacted with the polyester and / or polyether ester (I-C) having carboxyl groups at one or both ends is the same as the monofunctional alcohol (I-A) described above. Furthermore, the monofunctional alcohol (I-A) reacted with the polyester and / or polyether ester (I-C) having carboxyl groups at one or both ends includes compounds classified as monofunctional alcohols having one hydroxyl group among the compounds exemplified as polyols used as raw materials for polyester and / or polyether esters (I-C), (I-C-1), and (I-C-2) having carboxyl groups at one or both ends; compounds classified as monofunctional alcohols having one hydroxyl group among the compounds exemplified as compounds (II-A) having one or more hydroxyl groups used as raw materials for the compound represented by chemical formula (II) described later; and so on. These may be used individually or in combination of two or more.

[0064] In the compound represented by the above chemical formula (I), the reaction between a monofunctional alcohol (I-A) and a polyester and / or polyether ester (I-C) having carboxyl groups at one or both ends is preferably carried out in a molar equivalent ratio (hydroxyl groups / carboxyl groups) of 0.5 to 2, more preferably in the range of 0.7 to 1.4, and even more preferably in the range of 0.9 to 1.1. By setting the equivalent ratio within the above range, the carboxyl groups of the polyester and / or polyether ester (I-C) having carboxyl groups at one or both ends can be encapsulated by the monofunctional alcohol (I-A).

[0065] Compound (C), which is a reaction product of a monofunctional alcohol (I-A) and a polyester and / or polyether ester (I-C) having carboxyl groups at one or both ends, may be obtained by reacting a polyol and a polycarboxylic acid (polybasic acid), which are raw materials for polyester and / or polyether ester (I-C) having carboxyl groups at one or both ends (in other words, raw materials for polyester (I-C-1) or polyether ester (I-C-2)), with the monofunctional alcohol (I-A), or by simultaneously reacting a polyol and a polycarboxylic acid (polybasic acid), which are raw materials for polyester and / or polyether ester (I-C) having carboxyl groups at one or both ends (in other words, raw materials for polyester (I-C-1) or polyether ester (I-C-2)), with the monofunctional alcohol (I-A).

[0066] - Compound (C) represented by the above chemical formula (II) - Examples of the above compound (C) represented by the above chemical formula (II) include the reaction product of a compound (II-A) having one or more hydroxyl groups and a monofunctional carboxylic acid (II-B).

[0067] Compounds (II-A) having one or more hydroxyl groups that can be used as raw materials for the compound represented by the above chemical formula (II) include monofunctional alcohols and polyfunctional alcohols (low molecular weight polyols, high molecular weight polyols). Polyfunctional alcohols preferably have a hydroxyl group at least at one end, and more preferably at both ends. In this disclosure, a polyfunctional alcohol only needs to have one or more hydroxyl groups, and preferably two or more. Furthermore, there is no upper limit to the number of hydroxyl groups, but five or fewer is preferred.

[0068] Specific examples of monofunctional alcohols can be the same as those exemplified by monofunctional alcohol (I-A) used as a raw material for the compound represented by chemical formula (I) above.

[0069] Furthermore, specific examples of monofunctional alcohols include compounds classified as monofunctional alcohols among those exemplified as polyols used as raw materials for polyesters and / or polyether esters (I-C), (I-C-1), and (I-C-2) having carboxyl groups at one or both ends, which are used as raw materials for the compound represented by the above-mentioned chemical formula (I); and so on. These may be used alone or in combination of two or more.

[0070] Examples of low molecular weight polyols among the polyfunctional alcohols mentioned above include polyols with a molecular weight of less than 300. Examples of the low molecular weight polyols mentioned above include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide and propylene oxide adducts of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, and other low molecular weight diols; trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, dipentaerythritol, sorbitol, and other low molecular weight polyols with three or more functions.

[0071] Examples of high molecular weight polyols among the polyfunctional alcohols mentioned above include polyols with a molecular weight of 300 or more (preferably 500 or more). Examples of high molecular weight polyols include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyolefin polyol, polybutadiene polyol, polyester polyol, polyether polyol, polyether ester polyol, polycarbonate polyol, ethylene oxide or propylene oxide adducts of bisphenol A, and hydroxyl group-containing urethane resins made from one or more of these polyols as raw materials. These may be used individually or in combination of two or more.

[0072] Furthermore, examples of polyfunctional alcohols include those compounds classified as polyfunctional alcohols among the compounds exemplified as polyols used as raw materials for polyesters and / or polyether esters (I-C), (I-C-1), and (I-C-2) having carboxyl groups at one or both ends, which are used as raw materials for the compound represented by the chemical formula (I) described above; and so on. These may be used individually or in combination of two or more.

[0073] Among these, the compound (II-A) having one or more hydroxyl groups is preferably a high molecular weight polyol, and preferably polyester polyols, polyether polyols, polyether ester polyols, and hydroxyl group-containing urethane resins made from these polyols are preferred. These may be used individually or in combination of two or more. These preferably have a hydroxyl group at least at one end, and more preferably have a hydroxyl group at both ends.

[0074] The molecular weight of the compound (II-A) having one or more hydroxyl groups is preferably in the range of 100 to 20,000. Among these, the molecular weight of the high molecular weight polyol is preferably in the range of 300 to 20,000, more preferably in the range of 600 to 10,000, and even more preferably in the range of 800 to 5,000. The above molecular weights are values ​​calculated based on the hydroxyl value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0075] Examples of monofunctional carboxylic acids (II-B) that serve as raw materials for the compound represented by the above chemical formula (II) include aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids. These may be used individually or in combination of two. Among these, aliphatic monocarboxylic acids are preferred due to their ease of phase separation and esterification. Aliphatic monocarboxylic acids preferably have 5 to 20 carbon atoms.

[0076] Aliphatic monocarboxylic acids may be linear or branched.

[0077] Furthermore, the aliphatic monocarboxylic acid may be a saturated aliphatic monocarboxylic acid or an unsaturated aliphatic monocarboxylic acid, but a saturated aliphatic monocarboxylic acid is preferred for reasons of storage stability.

[0078] Examples of aliphatic monocarboxylic acids include caproic acid, 2-ethylhexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, and arachidic acid. These may be used individually or in combination of two or more.

[0079] Furthermore, as the monofunctional carboxylic acid (II-B) mentioned above, other examples include compounds classified as monofunctional or polyfunctional carboxylic acids and / or acid anhydrides (I-B) used as raw materials for the compound represented by chemical formula (I) as described above, and which are classified as monofunctional carboxylic acids and / or acid anhydrides. These may be used individually or in combination of two or more.

[0080] The number-average molecular weight of the monofunctional carboxylic acid (II-B) is preferably in the range of 100 to 400, and more preferably in the range of 120 to 350. The above molecular weights are values ​​calculated based on the acid value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0081] In the compound represented by the above chemical formula (II), the reaction between a compound (II-A) having one or more hydroxyl groups and a monofunctional carboxylic acid (II-B) is carried out in a molar equivalent ratio (hydroxyl groups / carboxyl groups) of 0.5 to 2, more preferably in the range of 0.7 to 1.4, and even more preferably in the range of 0.9 to 1.1. By setting the equivalent ratio within the above range, the hydroxyl groups of the compound (II-A) having one or more hydroxyl groups can be encapsulated by the monofunctional carboxylic acid (II-B).

[0082] - Compound (C) represented by the above chemical formula (III) - Examples of compound (C) represented by the above chemical formula (III) include the reaction product of a monofunctional or polyfunctional alcohol (III-A) and a monofunctional isocyanate (III-B).

[0083] Examples of monofunctional or polyfunctional alcohols (III-A) used as raw materials for the compound represented by the above chemical formula (III) include the compound exemplified as a monofunctional alcohol (I-A) used as a raw material for the compound represented by the above chemical formula (I); the compound exemplified as a polyol used as a raw material for polyesters and / or polyether esters (I-C) having carboxyl groups at one or both ends; and the compound exemplified as a compound (II-A) having one or more hydroxyl groups used as a raw material for the compound represented by the above chemical formula (II). These may be used individually or in combination of two or more. The above monofunctional or polyfunctional alcohol (III-A) has one or more hydroxyl groups, and it is preferable that it has a hydroxyl group at least at one end, and preferably has a hydroxyl group at both ends. Among these, high molecular weight polyols are preferred as monofunctional or polyfunctional alcohols (III-A), and polyester polyols, polyether polyols, polyether ester polyols, and hydroxyl group-containing urethane resins made from these polyols are preferred. These may be used individually or in combination of two or more. Preferably, they have a hydroxyl group at at least one end, and more preferably, they have hydroxyl groups at both ends.

[0084] The preferred ranges for the molecular weight of the monofunctional or polyfunctional alcohol (III-A) and the molecular weight of the high molecular weight polyol can be the same as the preferred ranges for the molecular weight of the monofunctional or polyfunctional alcohol and the molecular weight of the high molecular weight polyol exemplified in the compound (II-A) having one or more hydroxyl groups, which is a raw material for the compound represented by the chemical formula (II).

[0085] Examples of monofunctional isocyanates (III-B) that serve as raw materials for the compound represented by the above chemical formula (III) include aliphatic isocyanates such as ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, and octadecyl isocyanate; alicyclic isocyanates such as cyclohexyl isocyanate; and aromatic isocyanates such as phenyl isocyanate, benzyl isocyanate, and p-toluenesulfonyl isocyanate.

[0086] The number-average molecular weight of the monofunctional isocyanate (III-B) is preferably in the range of 70 to 500, and more preferably in the range of 90 to 300. The above molecular weights are those calculated by the n-dibutylamine method in accordance with the potentiometric titration method of JIS K-1603-1:2007.

[0087] In the compound represented by the above chemical formula (III), the reaction between a monofunctional or polyfunctional alcohol (III-A) and a monofunctional isocyanate (III-B) is carried out in a molar equivalent ratio (OH / NCO) of the molar equivalents of hydroxyl groups (OH) in the monofunctional or polyfunctional alcohol (III-A) to the molar equivalents of isocyanate groups (NCO) in the monofunctional isocyanate (III-B), preferably in the range of 2 to 0.8, more preferably in the range of 1.5 to 0.9, and even more preferably in the range of 1.1 to 1. By setting the equivalent ratio (OH / NCO) within the above range, the hydroxyl groups of the monofunctional or polyfunctional alcohol (III-A) can be encapsulated by the monofunctional isocyanate (III-B).

[0088] A end-capped polyester oligomer, compound (C) represented by any of the above chemical formulas (I) to (III), is, for example, a compound in which the hydroxyl groups at one or both ends of a polyester polyol are capped. In other words, this compound can be called an end-capped polyester polyol. A end-capped polyether oligomer, compound (C) represented by any of the above chemical formulas (I) to (III), is, for example, a compound in which the hydroxyl groups at one or both ends of a polyether polyol are capped. In other words, this compound can be called an end-capped polyether polyol. A end-capped polyether ester oligomer, compound (C) represented by any of the above chemical formulas (I) to (III), is, for example, a compound in which the hydroxyl groups at one or both ends of a polyether ester polyol are capped. In other words, this compound can be called an end-capped polyether ester polyol. Note that compound (C) substantially does not have isocyanate groups at one or both ends.

[0089] The number-average molecular weight of compound (C) is preferably 500 to 50,000, and more preferably 1,000 to 30,000. The number-average molecular weight of compound (C) is shown as the value measured by gel permeation chromatography (GPC) under the following conditions.

[0090] Measurement device: High-speed GPC instrument (HLC-8220GPC manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used in series: "TSKgel G5000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G3000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G2000" (7.8 mm I.D. × 30 cm) × 1 Detector: RI (differential refractometer) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard samples: Calibration curves were prepared using the following standard polystyrene.

[0091] (Standard Polystyrene) TSKgel Standard Polystyrene A-500 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene A-1000 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene A-2500 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene A-5000 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-1 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-2 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-4 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-10 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-20 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-40 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-80 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-128 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-288 (manufactured by Tosoh Corporation) TSKgel Standard Polystyrene F-550 (manufactured by Tosoh Corporation)

[0092] The above compound (C) may or may not have an ether group in its molecule. When the above compound (C) has an ether group, the thermosetting resin composition of this disclosure is more likely to achieve lower viscosity and a lower coefficient of thermal expansion in addition to lower elasticity. Therefore, the ether concentration of the above compound (C) is preferably 11.5 to 23 mol / kg, and more preferably 13 to 20 mol / kg. When using one type of above compound (C), the ether concentration of the above compound (C) indicates the concentration of the ether group relative to the total mass of the raw materials. When using two or more types of above compound (C), it indicates the concentration of the ether group of the compound with the highest ether concentration.

[0093] The total content of the above compound (C) is preferably 5% by mass or more, more preferably 8% by mass or more, preferably 40% by mass or less, and more preferably 35% by mass or less, in the nonvolatile content of the components of the above thermosetting resin composition excluding the filler (D).

[0094] [4] Filler (D) One or more fillers (D) selected from the group consisting of inorganic fine particles and fibers are essential components for reducing the thermal expansion of the insulating layer to a predetermined basic level. Examples of the inorganic fine particles include silica (fused silica, crystalline silica, etc.), silicon nitride, alumina, clay minerals (talc, clay, etc.), mica powder, aluminum hydroxide, magnesium hydroxide, magnesium oxide, aluminum titanate, barium titanate, calcium titanate, titanium oxide, etc. Silica is preferred, and fused silica is more preferred. The shape of the silica may be either crushed or spherical, but from the viewpoint of suppressing the melt viscosity of the thermosetting resin composition while increasing the amount of silica added, it is preferred to be spherical.

[0095] The volume-average particle diameter of the above inorganic fine particles is, for example, 0.01 μm or more, more preferably 0.03 μm or more, preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 μm or less. The volume-average particle diameter of the above inorganic fine particles can be measured by laser diffraction.

[0096] Examples of the above fibers include inorganic fibers such as glass fibers and carbon fibers, and organic fibers may also be used. The inorganic fibers may be long fibers or short fibers. The carbon fibers may be polyacrylonitrile-based or pitch-based. The diameter of the inorganic fibers is, for example, 1 μm or more, preferably 3 μm or more, for example 30 μm or less, preferably 20 μm or less, and even more preferably 15 μm or less.

[0097] Furthermore, the fibers may be dispersed in a thermosetting resin composition, arranged in a single direction, or formed into a woven or nonwoven fabric. The thickness of the woven or nonwoven fabric is preferably 100 μm or less, preferably 2 μm or more, and more preferably 5 μm or more.

[0098] The content of the above-mentioned filler (D) is 40% by mass or more, preferably 60% by mass or more, preferably 99% by mass or less, and more preferably 95% by mass or less, based on the nonvolatile content of the thermosetting composition.

[0099] [5] Thermosetting resin composition The thermosetting resin composition of this disclosure contains the above components (A) to (D) as essential components, but may contain any components as needed.

[0100] The thermosetting resin composition of this disclosure may contain a curing accelerator (E). Examples of the curing accelerator (E) include phosphorus compounds, tertiary amines, imidazole compounds, organic acid metal salts, Lewis acids, amine complex salts, etc. When using the curing accelerator (E), the content is preferably 0.005% by mass or more and 5% by mass or less of the nonvolatile content of the components of the thermosetting resin composition excluding the filler (D).

[0101] The thermosetting resin composition of this disclosure may contain one or more curing agents (F) other than acid anhydride (B). The curing agent (F) other than acid anhydride (B) can be any agent capable of curing the thermosetting resin composition, such as amine compounds, amide compounds, activated ester resins, phenol resins, cyanate ester resins, etc. When a curing agent (F) other than acid anhydride (B) is included, the content of the curing agent (F) is preferably 0% by mass or more and 30% by mass or less of the nonvolatile content of the components of the thermosetting resin composition excluding the filler (D).

[0102] The thermosetting resin composition of this disclosure may contain a resin (G) other than compound (C) that can form a phase-separated structure with the thermosetting resin, but it is preferable that it does not contain such a resin. Examples of the resin (G) other than compound (C) that can form a phase-separated structure with the thermosetting resin include polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polyolefin polyol, polybutadiene polyol, polyester polyol, polyether polyol, polyether ester polyol, and polycarbonate polyol, or hydroxyl group-containing urethane resins, acrylic resins, styrene-butadiene copolymers, etc., made from one or more of these polyols. The content of the above resin (G) is preferably 0% by mass or more and 50% by mass or less, more preferably 30% by mass or less, and even more preferably substantially 0% by mass, in the non-volatile content of the components of the thermosetting resin composition excluding the filler (D).

[0103] The thermosetting resin composition of this disclosure may also contain other additives (H). Examples of other additives (H) include flame retardants, organic solvents, conductive particles, rubber, fillers, silane coupling agents, mold release agents, pigments, emulsifiers, and the like.

[0104] [Cured products, semiconductor encapsulants, semiconductor devices, insulating materials for printed circuit boards, printed circuit boards] The thermosetting resin composition of this disclosure can be obtained by mixing the above components and can be cured by thermosetting. Examples of the shape of the cured product include laminates, cast products, adhesive layers, coatings, films, etc.

[0105] Applications of the thermosetting resin composition disclosed herein include semiconductor encapsulation materials, printed circuit board materials, resin casting materials, adhesives, interlayer insulating materials for build-up substrates, and build-up adhesive films. Among these applications, the insulating materials for printed circuit boards and electronic circuit boards, and the build-up adhesive films, can be used as insulating materials for so-called electronic component embedded substrates, in which passive components such as capacitors and active components such as IC chips are embedded within the substrate. Among these, its properties such as high heat resistance, low thermal expansion, low viscosity, low elastic modulus, and solvent solubility make it preferable to use as a printed circuit board material or a build-up adhesive film.

[0106] A method for preparing a semiconductor encapsulating material from the thermosetting composition of this disclosure is to thoroughly melt and mix the thermosetting resin composition until it becomes uniform, for example, using an extruder, kneader, roll, etc.

[0107] When the thermosetting resin composition of this disclosure is used as a semiconductor encapsulation material, a semiconductor package can be formed. Specifically, the composition can be molded using a casting, transfer molding machine, injection molding machine, etc., and then heated at 50 to 200°C for 2 to 10 hours to obtain a molded semiconductor device.

[0108] Furthermore, a method for manufacturing a printed circuit board using the thermosetting resin composition of this disclosure involves impregnating a reinforcing substrate with the thermosetting resin composition, layering copper foil on top, and then heating and pressing the substrates together. Examples of the reinforcing substrates include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. More specifically, first, the thermosetting resin composition can be heated (preferably to 50 to 170°C depending on the type of organic solvent) to obtain a cured prepreg. The resin content in the prepreg is preferably 20% by mass or more and 60% by mass or less. Next, the prepregs are laminated, copper foil is layered on top, and the substrates are heated and pressed together at 170 to 300°C under pressure of 1 to 10 MPa for 10 minutes to 3 hours to obtain the desired printed circuit board.

[0109] When the thermosetting resin composition of this disclosure is used as a conductive paste, examples include dispersing conductive particles (fine conductive particles) in the thermosetting resin composition to create a composition for an anisotropic conductive film, or creating a paste resin composition for circuit connection or an anisotropic conductive adhesive that is liquid at room temperature.

[0110] A method for obtaining an interlayer insulating material for a build-up substrate from the thermosetting resin composition of this disclosure involves, for example, applying the thermosetting resin composition to a wiring board with a circuit formed on it using a spray coating method, a curtain coating method, or the like, and then curing it. After that, if necessary, holes such as predetermined through-holes are drilled, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, and then plated with a metal such as copper. Electroless plating and electrolytic plating are preferred as the plating method, and examples of roughening agents include oxidizing agents, alkalis, and organic solvents. By sequentially repeating these operations as desired, a build-up substrate can be obtained by alternately building up a resin insulating layer and a conductor layer of a predetermined circuit pattern. However, drilling the through-holes is performed after the formation of the outermost resin insulating layer. Alternatively, a resin-coated copper foil, with the thermosetting resin composition partially cured on copper foil, can be heated and pressed onto a wiring board with a circuit formed on it at 170 to 300°C to form a roughened surface, thus omitting the plating process and producing a build-up substrate.

[0111] A method for producing a build-up film from the thermosetting resin composition of this disclosure includes, for example, a method of applying the thermosetting resin composition of this disclosure onto a support film to form a resin composition layer and thereby producing a build-up film for a multilayer printed circuit board.

[0112] When the thermosetting resin composition of this disclosure is used in a build-up film, it is essential that the film softens under the lamination temperature conditions in the vacuum lamination method (usually 70°C to 140°C) and exhibits fluidity (resin flow) that allows for simultaneous lamination of the circuit board and resin filling of via holes or through holes present in the circuit board. It is preferable to blend the above-mentioned components in such a way as to exhibit these characteristics.

[0113] Here, the diameter of the through-holes in a multilayer printed circuit board is typically 0.1 to 0.5 mm, and the depth is typically 0.1 to 1.2 mm. It is generally preferable to be able to fill the holes with resin within this range. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes.

[0114] The adhesive film described above can be manufactured by first preparing a varnish-like thermosetting resin composition of the present disclosure, then applying this varnish-like composition to the surface of a support film (Y), and finally drying the organic solvent by heating or blowing hot air to form a layer (X) of the thermosetting composition.

[0115] The thickness of the formed layer (X) is usually greater than or equal to the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 μm, it is preferable that the thickness of the resin composition layer be 10 to 100 μm.

[0116] The layer (X) in this disclosure may be protected by a protective film as described later. Protecting it with a protective film prevents dirt and other debris from adhering to the surface of the resin composition layer and prevents scratches.

[0117] The support film and protective film mentioned above can be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and also release paper and metal foils such as copper foil and aluminum foil. In addition, the support film and protective film may be treated with a mat treatment, corona treatment, or release treatment.

[0118] The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0119] The above-mentioned support film (Y) is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after heat curing the adhesive film, it is possible to prevent the adhesion of dust or the like during the curing process. When peeling off after curing, usually, the support film is previously subjected to a release treatment.

[0120] Next, a method for manufacturing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (X) is protected by a protective film, after peeling these, the layer (X) is directly contacted with the circuit board, and it is laminated on one side or both sides of the circuit board by, for example, a vacuum lamination method. The lamination method may be a batch type or a continuous type using a roll. Also, before performing lamination, the adhesive film and the circuit board may be heated (preheated) as necessary.

[0121] The lamination conditions are preferably a pressure-bonding temperature (lamination temperature) of 70 to 140°C, and a pressure-bonding pressure of preferably 1 to 11 kgf / cm 2 (9.8×104 to 107.9×104 N / m 2 ) and it is preferable to laminate under a reduced pressure of an air pressure of 20 mmHg (26.7 hPa) or less.

[0122] As a method for obtaining the cured product of the present disclosure, it may conform to a general method for curing a thermosetting resin composition. For example, the heating temperature conditions may be appropriately selected depending on the type and use of the curing agent to be combined, etc., but the composition obtained by the above method may be heated in a temperature range of about 20 to 300°C.

[0123] [Modifier for thermosetting resin (modified resin)] The modifier for thermosetting resin (modified resin) of the present disclosure is an oligomer selected from the group consisting of a terminal-blocked polyester oligomer, a terminal-blocked polyether oligomer, and a terminal-blocked polyether ester oligomer. The modifier for thermosetting resin (modified resin) of the present disclosure can be a compound represented by any of the following chemical formulas (I) to (III).

[0124]

[0125] In the above chemical formula (I), R1, R2, and n1 have the same definitions as described above.

[0126]

[0127] In the above chemical formula (II), R3, R4, and n2 are the same as defined above.

[0128]

[0129] In the above chemical formula (III), R5, R6, and n3 have the same definitions as described above.

[0130] The thermosetting resin modifier (modified resin) of this disclosure, when mixed with a thermosetting resin, forms a phase-separated structure, which can lower the thermal expansion coefficient and elastic modulus of the mixture and suppress warping during curing. The thermosetting resin modifier of this disclosure can be used to modify the thermosetting resin in the thermosetting resin composition of this disclosure described above, and is preferably an epoxy resin modifier (modified resin). In particular, in a thermosetting resin composition using an acid anhydride as a curing agent for the thermosetting resin (especially epoxy resin), using the thermosetting resin modifier (modified resin) of this disclosure can exhibit the above-mentioned effects more significantly compared to using other modifiers.

[0131] The details of the thermosetting resin modifier (modified resin) of this disclosure can be the same as the details of compound (C) in the thermosetting resin composition of this disclosure described above, so a detailed explanation is omitted here.

[0132] This disclosure is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of this disclosure and produces similar effects is included within the technical scope of this disclosure.

[0133] The present disclosure will be explained in more detail below with reference to examples and comparative examples.

[0134] [Example 1] In a mixing container, 9.08 parts by mass of epoxy resin 1 (DIC Corporation's "EPICLON 830CRP"), 9.67 parts by mass of alicyclic acid anhydride 1 (Resonac Corporation's "HN-5500"), and 6.25 parts by mass of compound (C1) as a modified resin (a reaction product obtained by reacting polypropylene glycol monobutyl ether (Sanyo Chemical Industries, Ltd.'s "Newpol LB-285", number average molecular weight 1170) and sebacic acid (molecular weight 202.25) in a molar ratio of 2:1, number average molecular weight: 2500, hydroxyl value: 2.7, acid value: 3.3, ether concentration: 15.1 mol / kg) were mixed and stirred at an internal temperature of 70°C until the mixture became miscible. Next, 75 parts by mass of fused silica 1 (FB-5SDC manufactured by Denka Co., Ltd.) and 0.075 parts by mass of a curing accelerator (2-ethyl-4-methylimidazole) were uniformly blended to obtain a thermosetting resin composition. Compound (C1) corresponds to a compound in which R1 in the above chemical formula (I) is represented by the following formula (3), R2 is represented by the following formula (4), and n1=2. Specifically, it is an end-encapsulated polyether ester oligomer represented by the following chemical formula (5).

[0135]

[0136]

[0137] (In formulas (3) to (5) above, one R7 and R8 is a hydrogen atom and the other is a methyl group, and n4 has an average value of 18.9.)

[0138] [Example 2] In a mixing container, 9.63 parts by mass of epoxy resin 2 (YX8000, manufactured by Mitsubishi Chemical Corporation), 11.62 parts by mass of alicyclic acid anhydride 2 (YH306, manufactured by Mitsubishi Chemical Corporation), and 3.75 parts by mass of compound (C2) as a modified resin (a reaction product obtained by reacting 2-butyl-2-ethyl-1,3-propanediol (molecular weight 160.26), dodecanediol (molecular weight 230.3), and 2-octyldodecanol (Calcol 200GD, manufactured by Kao Corporation, hydroxyl value 185) in a molar ratio of 3.37:4.37:2, number average molecular weight: 2000, hydroxyl value: 1.4, acid value: 1.7, ether concentration: 0 mol / kg) were mixed and stirred at an internal temperature of 70°C until the mixture became miscible. Next, 75 parts by mass of fused silica 1 (FB-5SDC manufactured by Denka Co., Ltd.) and 0.075 parts by mass of a curing accelerator (2-ethyl-4-methylimidazole) were uniformly blended to obtain a thermosetting resin composition. Compound (C2) corresponds to a compound in which R1 in the above chemical formula (I) is represented by the following formula (6), R2 is represented by the following formula (7), and n1 = 2.

[0139]

[0140]

[0141] (In equation (7) above, m1 is an average of 3.37.)

[0142] [Example 3] In a mixing container, 9.07 parts by mass of epoxy resin 2, 10.93 parts by mass of alicyclic acid anhydride 2, and 5.00 parts by mass of compound (C2) as a modified resin were mixed and stirred at an internal temperature of 70°C until miscible. Then, 75 parts by mass of fused silica 1 (FB-5SDC manufactured by Denka Co., Ltd.) and 0.075 parts by mass of curing accelerator (2-ethyl-4-methylimidazole) were uniformly mixed to obtain a thermosetting resin composition.

[0143] [Example 4] In a mixing container, 8.50 parts by mass of epoxy resin 2, 10.25 parts by mass of alicyclic acid anhydride 2, and 6.25 parts by mass of compound (C2) as a modified resin were mixed and stirred at an internal temperature of 70°C until miscible. Then, 75 parts by mass of fused silica 1 (FB-5SDC manufactured by Denka Co., Ltd.) and 0.075 parts by mass of curing accelerator (2-ethyl-4-methylimidazole) were uniformly mixed to obtain a thermosetting resin composition.

[0144] [Comparative Example 1] A thermosetting resin composition was obtained in the same manner as in Example 1, except that 6.25 parts by mass of polyester resin A (referred to as modified resin (CE1)) synthesized in Synthesis Example 1 below was used instead of compound (C1).

[0145] [Synthesis Example 1] In a reaction apparatus for the synthesis of polyester resin A, 779.1 parts by mass of bisphenol A type glycol ether (trademark; manufactured by DIC Corporation, "Hyprox MDB-561"), 132.9 parts by mass of isophthalic acid (hereinafter referred to as "iPA"), and 40.4 parts by mass of sebacic acid (hereinafter referred to as "SebA") were charged, and heating and stirring were started. Next, after raising the internal temperature to 230°C, 0.10 parts by mass of TiPT were charged, and the reaction was carried out at 230°C for 24 hours to synthesize the polyester resin. The obtained polyester resin had a hydroxyl value of 36.9 mgKOH / g, a number average molecular weight of 3,040, and a glass transition temperature of -14°C.

[0146] [Comparative Example 2] 12.17 parts by mass of epoxy resin 1 (DIC Corporation's "EPICLON 830CRP") and 12.83 parts by mass of alicyclic acid anhydride 1 ("HN-5500") were mixed in a mixing container and stirred at an internal temperature of 70°C until miscible. Then, 75 parts by mass of fused silica 1 (Denka Corporation's "FB-5SDC") and 0.075 parts by mass of curing accelerator (2-ethyl-4-methylimidazole) were uniformly mixed to obtain a thermosetting resin composition that does not contain modified resin (compound (C)).

[0147] [Comparative Example 3] 11.33 parts by mass of epoxy resin 2 and 13.67 parts by mass of alicyclic acid anhydride 2 were mixed in a mixing container and stirred at an internal temperature of 70°C until miscible. Next, 75 parts by mass of fused silica 1 (FB-5SDC, manufactured by Denka Co., Ltd.) and 0.075 parts by mass of curing accelerator (2-ethyl-4-methylimidazole) were uniformly mixed to obtain a thermosetting resin composition that does not contain modified resin (compound (C)). [Evaluation] <Thermal expansion> After thermosetting the thermosetting resin compositions obtained in the examples and comparative examples at 100°C for 1 hour and 175°C for 2 hours, the linear thermal expansion coefficient in the range of 40 to 60°C was measured using a TMA6200 (manufactured by Seiko Instruments Corporation) as a thermal analyzer, with a heating rate of 3°C / min, and the thermal expansion was judged according to the following criteria. (Criterion 1: Comparison of Example 1, Comparative Example 1, and Comparative Example 2) Linear thermal expansion coefficient of Example 1 and Comparative Example 1 relative to the linear thermal expansion coefficient of Comparative Example 2 "○": Less than 0.9 times that of Comparative Example 2 "×": 0.9 times or more that of Comparative Example 2 (Criterion 2: Comparison of Examples 2-4 and Comparative Example 3) Linear thermal expansion coefficient of Examples 2-4 relative to the linear thermal expansion coefficient of Comparative Example 3 "○": Less than 0.9 times that of Comparative Example 3 "×": 0.9 times or more that of Comparative Example 3

[0148] <Module of Elasticity> After heat curing the thermosetting resin compositions obtained in the examples and comparative examples at 100°C for 1 hour and 175°C for 2 hours, the flexural modulus was measured in accordance with JIS K7171, and the elasticity of the cured thermosetting resin compositions was judged according to the following criteria. (Criterion 1: Comparison of Example 1, Comparative Example 1, and Comparative Example 2) Flexural modulus of Example 1 and Comparative Example 1 relative to the flexural modulus of Comparative Example 2 "○": Less than 0.9 times that of Comparative Example 2 "×": 0.9 times or more that of Comparative Example 2 (Criterion 2: Comparison of Examples 2-4 and Comparative Example 3) Flexural modulus of Examples 2-4 relative to the flexural modulus of Comparative Example 3 "○": Less than 0.9 times that of Comparative Example 3 "×": 0.9 times or more that of Comparative Example 3

[0149] The results are shown in the table below.

[0150]

[0151]

Claims

It comprises a thermosetting resin (A), an acid anhydride (B), a compound (C), and one or more fillers (D) selected from the group consisting of inorganic fine particles and fibers. A thermosetting resin composition in which the compound (C) is one or more selected from the group consisting of end-capped polyester oligomers, end-capped polyether oligomers, and end-capped polyether ester oligomers. 　 The thermosetting resin composition according to claim 1, wherein the compound (C) is a compound selected from the group of compounds represented by the following chemical formulas (I) to (III). (In the above chemical formula (I), R1 and R2 are each independently any functional group consisting of one or more combinations selected from the group consisting of hydrocarbon groups, ether groups, ester groups, urethane groups, urea groups, amide groups, and amino groups having 1 to 30 carbon atoms, and at least one of R1 and R2 is a functional group containing an ether group and / or an ester group. n1 is a real number in the range of 1 to 6.) (In the above chemical formula (II), R3 and R4 are each independently any functional group composed of one or more combinations selected from the group consisting of hydrocarbon groups having 1 to 30 carbon atoms, ether groups, ester groups, urethane groups, urea groups, amide groups, and amino groups, and at least one of R3 and R4 is a functional group containing an ether group and / or an ester group. n2 is a real number in the range of 1 to 6.) (In the above chemical formula (III), R5 is any functional group consisting of one or more combinations selected from the group consisting of hydrocarbon groups, ether groups, ester groups, and sulfonyl groups having 1 to 20 carbon atoms, and R6 is any functional group consisting of one or more combinations selected from the group consisting of hydrocarbon groups, ether groups, ester groups, urethane groups, urea groups, amide groups, and amino groups having 1 to 30 carbon atoms, and at least one of R5 and R6 is a functional group containing an ether group and / or an ester group. n3 is a real number in the range of 1 to 6.) 　 The thermosetting resin composition according to claim 1, wherein the compound (C) is a reaction product of a monofunctional alcohol (I-A) and a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (I-B). 　 The thermosetting resin composition according to claim 1, wherein the compound (C) is a reaction product of a monofunctional alcohol (I-A) and a polyester and / or polyether ester (I-C) having carboxyl groups at one or both ends. 　 The thermosetting resin composition according to claim 3 or 4, wherein the monofunctional alcohol (I-A) is one or more selected from the group consisting of monofunctional polyethylene glycol, monofunctional polypropylene glycol, and long-chain aliphatic alcohols. 　 The thermosetting resin composition according to claim 1, wherein the compound (C) is a reaction product of a compound (II-A) having one or more hydroxyl groups and a monofunctional carboxylic acid (II-B). 　 The thermosetting resin composition according to claim 1, wherein the compound (C) is a reaction product of a monofunctional or polyfunctional alcohol (III-A) and a monofunctional isocyanate (III-B). 　 The thermosetting resin composition according to any one of claims 1 to 6, wherein the hydroxyl value of compound (C) is 0 or more and 10 or less. 　 The thermosetting resin composition according to any one of claims 1 to 8, wherein the number average molecular weight of compound (C) is 500 to 50,000. 　 The thermosetting resin composition according to any one of claims 1 to 9, wherein the content of compound (C) is 5 to 45% by mass of the nonvolatile content of the components excluding the filler (D). 　 A cured product of the thermosetting resin composition according to any one of claims 1 to 10. 　 A semiconductor encapsulant comprising the thermosetting resin composition according to any one of claims 1 to 10. 　 A semiconductor device comprising the semiconductor encapsulant material according to claim 12. 　 An insulating material for printed wiring boards comprising the thermosetting resin composition according to any one of claims 1 to 10. 　 A printed circuit board comprising the insulating material for printed circuit boards according to claim 14.

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