Thermosetting resin compositions, cured materials, semiconductor sealants, semiconductor devices, insulating materials for printed wiring boards, and printed wiring boards.

Abstract

The problem this disclosure aims to solve is to provide a thermosetting resin composition that can reduce the coefficient of linear thermal expansion and the modulus of elasticity. This disclosure provides 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 microparticles 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. Furthermore, this disclosure provides a cured product of the thermosetting resin composition, as well as a semiconductor sealing material, a semiconductor device, an insulating material for printed circuit boards, and a printed circuit board comprising the thermosetting resin composition.

Description

Technical Field

[0001] This disclosure relates to a thermosetting resin composition, a cured material, a semiconductor sealing material, a semiconductor device, an insulating material for printed wiring boards, and a printed wiring board. Prior Technology

[0002] Resin compositions containing thermosetting resins are widely used in a wide range of fields, including sealing materials for semiconductor components such as capacitors, diodes, transistors, and thyristors; sealing materials for integrated circuits (ICs) and large-scale integrated circuits (LSIs); and insulating materials used in printed circuit boards. On the other hand, molded articles using these thermosetting resin compositions become composites with various dissimilar materials. Therefore, due to the difference in thermal expansion coefficients between the resin composition and each dissimilar material, warping can occur during the manufacturing of the composite, sometimes causing problems with the dimensional accuracy of the molded article. Furthermore, if the molded article is exposed to temperature variations in its operating environment, defects may sometimes occur in the molded article due to the difference in thermal expansion coefficients between the resin composition and each dissimilar material (for example, see Patent Document 1). [Existing Technical Documents] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2003-82241 [Patent Document 2] Japanese Patent Application Publication No. 2021-038356 Summary of the Invention

[0004] [The problem that the invention aims to solve] The inventors have discovered that when a thermoplastic resin (modified resin) having at least one of the groups selected from hydroxyl and carboxyl groups is added to a thermosetting resin composition, the coefficient of linear thermal expansion of the thermosetting resin composition decreases (see Patent Document 2). However, the inventors have conducted in-depth research and found that even with the addition of a previously modified resin, it is difficult to sufficiently achieve a decrease in the coefficient of linear thermal expansion and a reduction in the modulus of elasticity in thermosetting resin compositions containing a specific hardener.

[0005] The problem this disclosure seeks to solve is to provide a thermosetting resin composition that can reduce the coefficient of linear thermal expansion and the modulus of elasticity. [Methods for solving problems]

[0006] The inventors conducted further in-depth research and found that the phenomenon was caused by the combination of the type of hardener and the modified resin. Furthermore, by adding a specific modified resin to a thermosetting resin composition containing a specific hardener, the problem could be solved without impairing the function performed by the specific hardener.

[0007] This disclosure includes the following implementation methods. [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 microparticles and fibers. 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. [2] The thermosetting resin composition as described in [1], wherein the compound (C) is a compound selected from the group of compounds represented by the following chemical formulas (I) to (III).

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

[0009] [Chemistry 2] (In the chemical formula (II), R3 and R4 are each independently any functional group comprising one or more combinations of a group selected from the group consisting of hydrocarbon, ether, ester, carbamate, urea, amide and amine groups with 1 to 30 carbon atoms, and at least one of R3 and R4 is a functional group comprising an ether and / or ester group; n2 is a real number in the range of 1 to 6)

[0010] [Chemistry 3] (In the chemical formula (III), R5 is any functional group comprising one or more combinations of a group selected from the group consisting of hydrocarbon, ether, ester and sulfonyl groups with 1 to 20 carbon atoms; R6 is any functional group comprising one or more combinations of a group consisting of hydrocarbon, ether, ester, carbamate, urea, amide and amino groups with 1 to 30 carbon atoms; at least one of R5 and R6 is a functional group comprising an ether and / or an ester group; n3 is a real number in the range of 1 to 6.) [3] The thermosetting resin composition as described in [1] or [2], wherein the compound (C) is a reaction product of a monofunctional alcohol (IA) and a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB). [4] The thermosetting resin composition as described in [1] or [2], wherein the compound (C) is a reaction product of a monofunctional alcohol (IA) and a polyester and / or polyether ester (IC) having a carboxyl group at one or both ends. [5] The thermosetting resin composition as described in [3] or [4], wherein the monofunctional alcohol (IA) 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 as described in [1] or [2], 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). [7] The thermosetting resin composition as described in [1] or [2], wherein the compound (C) is a reaction product of a monofunctional or polyfunctional alcohol (III-A) and a monofunctional isocyanate (III-B). [8] The thermosetting resin composition as described in any one of [1] to [7], wherein the hydroxyl valence of the compound (C) is 0 or more and 10 or less. [9] The thermosetting resin composition as described in any one of [1] to [8], wherein the number of compounds (C) has an average molecular weight of 500 to 50,000.

[10] The thermosetting resin composition as described in any one of [1] to [9], wherein the content of the compound (C) is 5% to 45% by mass of the non-volatile components of the composition after removing the filler (D).

[11] A hardened material is a hardened material of the thermosetting resin composition as described in any one of [1] to

[10] .

[12] A semiconductor sealing material comprising a thermosetting resin composition as described in any one of [1] to

[10] .

[13] A semiconductor device comprising a semiconductor sealing material as described in

[12] .

[14] An insulating material for printed wiring boards, comprising a thermosetting resin composition as described in any one of [1] to

[10] .

[15] A printed wiring board comprising an insulating material for printed wiring boards as described in

[14] . [The effects of the invention]

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

[0012] [Thermosetting resin composition] The thermosetting resin composition disclosed herein contains at least a thermosetting resin (A), an acid anhydride (B), a compound (C), and one or more fillers (D) selected from the group consisting of inorganic microparticles and fibers as essential components, 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 following is a detailed description of the composition and other components of the thermosetting resin composition disclosed herein. Furthermore, in this specification, compound (C) is sometimes referred to as a "specific modified resin".

[0014] [1] Thermosetting resin (A) As the thermosetting resin (A), for example, epoxy resin, resin containing a benzoxazine structure, maleimide resin, vinyl benzyl compound, acrylic compound, copolymer of styrene and maleic anhydride, etc., can be used. These resins can be used alone or in combination of two or more. Among these, epoxy resin and / or maleimide resin are preferred in terms of their ease of forming a phase-separated structure with the compound (C) described later and their greater ability to obtain the effects disclosed herein, and epoxy resin is even more preferred.

[0015] For example, the following epoxy resins can be used: bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, diglycidoxynaphthalene compounds (1,6-diglycidoxynaphthalene, 2,7-diglycidoxynaphthalene, etc.), phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, bisphenol A phenolic varnish type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, and dicyclopentadiene-phenol addition reaction type epoxy resin. Epoxy resins include phenolic alkyl-type epoxy resins, naphthol phenolic varnish-type epoxy resins, naphthol alkyl-type epoxy resins, naphthol-phenol co-condensed phenolic varnish-type epoxy resins, naphthol-cresol co-condensed phenolic varnish-type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resin-type epoxy resins, biphenyl phenolic varnish-type epoxy resins, 1,1-bis(2,7-diglycidoxy-1-naphthyl)alkanes, and phosphorus-modified epoxy resins in which phosphorus atoms have been introduced into these various epoxy resins. Additionally, hydrides of these epoxy resins (hydrogenated epoxy resins) can be used.

[0016] Of particular interest, the epoxy resins that provide excellent heat resistance and produce cured products are preferably cresol varnish-type epoxy resins, phenol aralkyl type epoxy resins, biphenyl varnish-type epoxy resins, or naphthol varnish-type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol cocondensed phenol varnish-type epoxy resins, naphthol-cresol cocondensed phenol varnish-type epoxy resins, or crystalline biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, xanthanene type epoxy resins, or alkoxy-containing aromatic ring modified phenolic varnish-type epoxy resins (compounds formed by linking an aromatic ring containing a glycidyl group to an alkoxy-containing aromatic ring using formaldehyde), and hydrogenates of these epoxy resins (hydrogenated epoxy resins), etc.

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

[0018] [Chemistry 4]

[0019] [In formula (1), R1 represents an organogroup with an a1 valence, R2 and R3 independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms, respectively, and a1 represents an integer greater than 1.]

[0020] [Chemistry 5]

[0021] [In formula (2), R4, R5 and R6 independently represent hydrogen atoms, alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, halogen atoms, hydroxyl groups or alkoxy groups with 1 to 20 carbon atoms, respectively; L1 and L2 independently represent saturated hydrocarbon groups with 1 to 5 carbon atoms, aromatic hydrocarbon groups with 6 to 10 carbon atoms, or groups with 6 to 15 carbon atoms formed by combining saturated hydrocarbon groups with aromatic hydrocarbon groups; a3, a4 and a5 independently represent integers 1 to 3, and n represents integers 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 a maximum of 100% by mass.

[0023] The content of the thermosetting resin (A) in the non-volatile components of the composition after removing the filler (D) from the thermosetting resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, more preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0024] [2] Acid anhydride (B) The acid anhydride (B) functions as a curing agent, enabling the thermosetting resin composition to harden and reducing its viscosity. By using the acid anhydride, the thermosetting resin composition achieves a longer pot life and superior electrical properties of the cured product.

[0025] As the acid anhydride (B), compounds having one or more acid anhydride groups within one molecule can be listed. Preferably, compounds having two or more acid anhydride groups within one molecule are preferred. The acid anhydride (B) may include, in addition to acid anhydrides, acid anhydrides with substituents (preferably hydrocarbon groups), hydrides of acid anhydrides, and modified acid anhydrides. Specific examples of the anhydride (B) may include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, glutaric anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, terephthalic anhydride, methylterephthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, methylneodynetetrahydrophthalic anhydride, succinic anhydride that may have substituents (preferably hydrocarbon groups, more preferably alkyl or alkenyl groups), methyl nadic anhydride, etc. These compounds may be used alone or in combination of two or more.

[0026] Commercially available anhydrides (B) include: "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Rikka Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Co., Ltd.; "HN-2200" and "HN-5500" manufactured by Resonac Co., Ltd.; and "EF-30", "EF-40", "EF-60", "EF-80" manufactured by Cray Valley Co., Ltd.

[0027] The content of the anhydride (B) in the thermosetting resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 90% by mass or less, and more preferably 80% by mass or less, in the non-volatile components of the composition after removing the filler (D) from the thermosetting resin composition.

[0028] [3] Compound (C) 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. End-capped polyester oligomers, end-capped polyether oligomers, and end-capped polyether ester oligomers are oligomers that substantially lack acid groups such as hydroxyl or carboxyl groups at at least one end. Preferably, they are oligomers that substantially lack acid groups such as hydroxyl or carboxyl groups at both ends, and more preferably, they are oligomers that substantially lack acid groups such as hydroxyl or carboxyl groups within the molecule. In this disclosure, the term "end" of each compound refers to the end along the length of the molecular backbone. Furthermore, "substantially lack" means that the hydroxyl valence and acid valence are within the range described later. The thermosetting resin composition disclosed herein may contain one or more compounds (C).

[0029] The hydroxyl value of the compound (C) is preferably 0 or higher and 10 or lower, more preferably 0 or higher and 5 or lower, further preferably 0 or higher and 2 or lower, and most preferably 0. Additionally, the acid value of the compound (C) is preferably 0 or higher and 10 or lower, more preferably 0 or higher and 5 or lower, further preferably 0 or higher and 2 or lower, and most preferably 0. The hydroxyl value and acid value of the compound (C) can be adjusted by the type of raw material and the reaction ratio (mole ratio) of the compound (C).

[0030] As the compound (C), for example, compounds selected from the group consisting of compounds represented by chemical formulas (I) to (III) below can be listed. One or more of these can be used. Specifically, as end-capped polyester oligomers and end-capped polyether ester oligomers, one or more compounds selected from the group consisting of compounds represented by chemical formulas (I) to (III) below can be used. Additionally, as end-capped polyether oligomers, one or more compounds represented by chemical formula (III) below can be used.

[0031] [Chemistry 6]

[0032] (In the chemical formula (I), R1 and R2 are each independently any functional group comprising one or more combinations of a group selected from the group consisting of hydrocarbon, ether, ester, carbamate, urea, amide, and amine groups with 1 to 30 carbon atoms, and at least one of R1 and R2 is a functional group comprising an ether and / or ester group; n1 is a real number in the range of 1 to 6) Wherein, 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] [Chemistry 7]

[0034] (In the chemical formula (II), R3 and R4 are each independently any functional group comprising one or more combinations of a group selected from the group consisting of hydrocarbon, ether, ester, carbamate, urea, amide and amine groups with 1 to 30 carbon atoms, and at least one of R3 and R4 is a functional group comprising an ether and / or ester group; n2 is a real number in the range of 1 to 6) Wherein, 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] [Chemistry 8]

[0036] (In the chemical formula (III), R5 is any functional group comprising one or more combinations of a group selected from the group consisting of hydrocarbon, ether, ester and sulfonyl groups with 1 to 20 carbon atoms; R6 is any functional group comprising one or more combinations of a group consisting of hydrocarbon, ether, ester, carbamate, urea, amide and amino groups with 1 to 30 carbon atoms; at least one of R5 and R6 is a functional group comprising an ether and / or an ester group; n3 is a real number in the range of 1 to 6.) Wherein, 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] -The compound (C) represented by the chemical formula (I)- Examples of compounds (C) represented by the chemical formula (I) include: reaction products of monofunctional alcohols (IA) with monofunctional or polyfunctional carboxylic acids and / or their anhydrides (IB), reaction products of monofunctional alcohols (IA) with polyesters and / or polyether esters (IC) having carboxyl groups at one or both ends.

[0038] The monofunctional alcohol (IA) used as a raw material for the compound represented by the chemical formula (I) is one having a hydroxyl group in the compound. Preferably, the monofunctional alcohol (IA) is a functional group other than a hydroxyl group that can react with monofunctional or polyfunctional carboxylic acids and / or their anhydrides (IB), and polyesters and / or polyether esters (IC) having carboxyl groups at one or both ends.

[0039] As a monofunctional alcohol (IA), it is sufficient to have only one hydroxyl group. Examples include aliphatic alcohols, monofunctional polyethylene glycol, monofunctional polypropylene glycol, monofunctional polyoxybutylene, monofunctional polycaprolactone, and monofunctional polyesters. One or more of these can be used together. Furthermore, when the compound reacting with the monofunctional alcohol (IA) is a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB), the aliphatic alcohol used as the monofunctional alcohol (IA) is preferably a long-chain aliphatic alcohol. Additionally, when the compound reacting with the monofunctional alcohol (IA) is a polyester and / or polyether ester (IC) with carboxyl groups at one or both ends, the aliphatic alcohol used as the monofunctional alcohol (IA) can be either a long-chain or short-chain aliphatic alcohol. From the viewpoint that it is easy to form a phase-separated structure, the monofunctional alcohol (IA) 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 are preferably composed of 5 to 25 carbon atoms, and more preferably 6 to 23 carbon atoms. Examples of such long-chain aliphatic alcohols include: pentanol, hexanol, octanol, decanol, lauryl alcohol, myristol, cetyl alcohol, stearyl alcohol, eicosanol, behenol, 2-methyl-decane-1-ol, 2-ethyl-decane-1-ol, 2-hexyl-octane-1-ol, 2-octyldodecaneol, 2-isoheptylisoundecaneol, 2-decyltetradecaneol, etc., as well as straight-chain or branched long-chain aliphatic unsaturated alcohols such as hexenol, 2-hexen-1-ol, 1-hexen-3-ol, pentenol, 2-methyl-1-pentenol, etc. These can be used alone or in combination of two or more. From the viewpoint of readily becoming liquid and exhibiting decreased crystallinity, branched aliphatic saturated alcohols are preferred.

[0041] Examples of monofunctional polyethylene glycols include: polyethylene glycol monobutyl ether, polyethylene glycol monododecyl ether, and other polyethylene glycol monoalkyl ethers; polyethylene glycol monoacetate and other polyethylene monoesters. These can be used alone or in combination of two or more.

[0042] As monofunctional polypropylene glycols, examples include compounds with one-sidedly closed ends, such as: polypropylene glycol monobutyl ether and other polypropylene monoalkyl ethers; polyoxypropylene methyl ether, polyoxypropylene ethyl ether, polyoxypropylene butyl ether, polyoxypropylene-2-ethylhexyl ether, polyoxypropylene oil ether, polyoxypropylene-2-octyldodecyl ether and other polyoxypropylene glycol monoalkyl ethers; polypropylene glycol monoacetate, polypropylene glycol monoacetate and other polypropylene glycol monoesters, etc. These can be used alone or in combination of two or more.

[0043] In addition to the exemplified compounds, other examples of monofunctional alcohols (IA) include: compounds used as polyols in the raw materials of polyesters and / or polyether esters (IC), (IC-1), (IC-2) having carboxyl groups at one or both ends, which are classified as compounds having one hydroxyl group (monofunctional alcohols); compounds used as compounds having more than one hydroxyl group (II-A), which are classified as compounds having one hydroxyl group (monofunctional alcohols) in the raw materials of compounds represented by chemical formula (II); and so on. These can be used alone or in combination of two or more.

[0044] The molecular weight of the monofunctional alcohol (IA) is preferably in the range of 100 to 20,000, and more preferably in the range of 150 to 10,000. The molecular weight is expressed as a value calculated based on the valence of the hydroxyl group using potentiometric titration according to Japanese Industrial Standards (JIS) K 0070:1992.

[0045] The monofunctional or polyfunctional carboxylic acids and / or their anhydrides (IBs) used as raw materials for the compound represented by the chemical formula (I) are not particularly limited, but are preferably aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and / or their anhydrides.

[0046] As the aliphatic dicarboxylic acid and its anhydride, it is preferred to have a carboxyl group at at least one end, and more preferably at both ends. Examples include: malonic acid, adipic acid, succinic acid, azelaic acid, octanoic acid, sebacic acid, glutaric acid, dodecanoic acid, eicosanoic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, etc. As the alicyclic dicarboxylic acid and its anhydride, it is preferred to have a carboxyl group at at least one end, and more preferably a carboxyl group at both ends. Examples include: tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenetetrahydrophthalic anhydride, nitrile anhydride, methylnitrile anhydride, 1,4-cyclohexanedicarboxylic acid, etc. Examples of aromatic dicarboxylic acids and / or their anhydrides include, for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid. These compounds may be used alone or in combination.

[0047] In addition, examples of monofunctional or polyfunctional carboxylic acids and / or their anhydrides (IB) may also be included: compounds exemplified as polybasic acids in the raw materials of polyesters and / or polyether esters (IC), (IC-1), (IC-2) having carboxyl groups at one or both ends, as described later; compounds exemplified as monofunctional or polyfunctional carboxylic acids and / or their anhydrides in the raw materials of compounds represented by compound (II) described later; and so on. These may be used alone or in combination of two or more.

[0048] Regarding the monofunctional or polyfunctional carboxylic acids and / or their anhydrides (IB), in terms of low viscosity and ease of phase separation, straight-chain aliphatic dicarboxylic acids are preferred, with compounds selected from the group consisting of adipic acid, azelaic acid, sebacic acid and dodecanoic acid being more preferred.

[0049] The molecular weight of the monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB) is preferably in the range of 110 to 400, more preferably in the range of 140 to 350. The molecular weight is expressed as a value calculated based on the acid value according to the potentiometric titration method of JIS K 0070:1992.

[0050] In the compounds represented by chemical formula (I), the reaction of a monofunctional alcohol (IA) with a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB) is preferably carried out in a mole equivalence ratio (hydroxyl / carboxyl group) of 0.5 to 2, more preferably in a range of 0.7 to 1.4, and even more preferably in a range of 0.9 to 1.1. By setting the mole equivalence ratio within the aforementioned range, the carboxyl group of the monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB) can be blocked by the monofunctional alcohol (IA).

[0051] Polyesters and / or polyether esters (ICs) having carboxyl groups at one or both ends, which serve as raw materials for compounds represented by the chemical formula (I), may, for example, be reaction products of polyether polyols and polyacids. These polyols may be used alone or in combination of two or more.

[0052] As the polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. can be used. Among these, polypropylene glycol is preferred in terms of more easily obtaining the effects brought about by compound (C).

[0053] As the polyacids mentioned above, one or more can be used, such as aliphatic polycarboxylic acids such as malonic acid, adipic acid, succinic acid, azelaic acid, octanoic acid, sebacic acid, glutaric acid, dodecanoic acid, eicosanoic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, etc.; alicyclic polycarboxylic acids such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenetetrahydrophthalic anhydride, nitrosic anhydride, methylnitrosic anhydride, 1,4-cyclohexanedicarboxylic acid, etc.; and aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, pyromellitic acid, etc.

[0054] In addition, polyesters and / or polyether esters (ICs) having carboxyl groups at one or both ends as raw materials for compounds represented by the chemical formula (I) can be exemplified by, for example, polyesters (IC-1) or polyether esters (IC-2) obtained by reacting a polyol with a polycarboxylic acid (polyacid); polyesters obtained by copolymerizing the polyester (IC-1) or polyether ester (IC-2) with a polyester obtained by ring-opening polymerization of a cyclic ester compound, etc.

[0055] As the raw material for the polyester (IC-1), the polyol can be one or more, such as: 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, tetraethylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3- Propylene glycol, 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, pentaerythritol, and other aliphatic polyols; cyclopentanediol, cyclohexanediol, cyclohexanediol, hydrogenated bisphenol A, and their epoxide adducts, and other polyols with alicyclic structures; bisphenol A and bisphenol F, and other polyols with aromatic structures; and polyols obtained by epoxide modification of the aforementioned polyols with aromatic structures, etc.

[0056] The molecular weight of the polyol used as the raw material for the polyester (IC-1) is preferably 50 or higher, and more preferably 1,500 or lower, more preferably 1,000 or lower, and even more preferably 700 or lower. Furthermore, the molecular weight is a value calculated based on the valence of the hydroxyl group using potentiometric titration according to JIS K 0070:1992.

[0057] In addition, the polyols used as raw materials for the polyether ester (IC-2) may include, for example, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. One or more of these may be used.

[0058] The polyol used as the raw material for the polyether ester (IC-2) preferably has a molecular weight of 400 or higher, more preferably 700 or higher, and preferably a molecular weight of 4,000 or lower, more preferably 2,000 or lower. Furthermore, the molecular weight is a value calculated based on the valence of the hydroxyl group using potentiometric titration according to JIS K 0070:1992.

[0059] The polycarboxylic acid (polyacid) used as the raw material for the polyester and / or polyether ester (IC) can be one or more, such as malonic acid, adipic acid, succinic acid, azelaic acid, octanoic acid, sebacic acid, glutaric acid, dodecanoic acid, eicosanoic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride and other aliphatic polycarboxylic acids; tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenetetrahydrophthalic anhydride, terephthalic anhydride, methylterephthalic anhydride, 1,4-cyclohexanedicarboxylic acid and other alicyclic polycarboxylic acids; phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, pyromellitic acid and other aromatic polycarboxylic acids, etc.

[0060] In addition, the polycarboxylic acids (polyacids) mentioned above, which are raw materials for polyesters and / or polyether esters (IC), can also include compounds classified as polycarboxylic acids (polyacids) among those exemplified as monofunctional or polyfunctional carboxylic acids and / or their anhydrides (IB); etc. These can be used alone or in combination of two or more.

[0061] Polyesters and / or polyether esters (ICs) having carboxyl groups at one or both ends can be obtained, for example, by reacting the polyol with a polycarboxylic acid under conditions where the amount of carboxyl groups contained in the reactants is greater than the amount of hydroxyl groups.

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

[0063] The same as the monofunctional alcohol (IA) that reacts with polyesters and / or polyether esters (IC) having carboxyl groups at one or both ends. Additionally, examples of monofunctional alcohols (IA) that react with polyesters and / or polyether esters (IC) having carboxyl groups at one or both ends include: compounds used as polyols in the raw materials of polyesters and / or polyether esters (IC), (IC-1), (IC-2) having carboxyl groups at one or both ends, classified as compounds having one hydroxyl group (monofunctional alcohols); compounds used as raw materials of compounds represented by chemical formula (II) described later, classified as compounds having one or more hydroxyl groups (II-A), classified as compounds having one hydroxyl group (monofunctional alcohols); etc. These can be used alone or in combination of two or more.

[0064] In the compounds represented by chemical formula (I), the reaction of a monofunctional alcohol (IA) with a polyester and / or polyether ester (IC) having carboxyl groups at one or both ends is preferably carried out in a mole equivalence ratio (hydroxyl / carboxyl) of 0.5 to 2, more preferably in a range of 0.7 to 1.4, and even more preferably in a range of 0.9 to 1.1. By setting the equivalence ratio within the range described above, the carboxyl groups of the polyester and / or polyether ester (IC) having carboxyl groups at one or both ends can be blocked by the monofunctional alcohol (IA).

[0065] The reaction product of a monofunctional alcohol (IA) and a polyester and / or polyether ester (IC) having carboxyl groups at one or both ends, namely compound (C), can be obtained by reacting the polyester and / or polyether ester (IC) raw material (in other words, the raw material of polyester (IC-1) or polyether ester (IC-2)) i.e., a polyol and a polycarboxylic acid (polyacid) after reacting the polyester and / or polyether ester (IC) with carboxyl groups at one or both ends with a monofunctional alcohol (IA). Alternatively, it can be obtained by simultaneously reacting the polyester and / or polyether ester (IC) raw material (in other words, the raw material of polyester (IC-1) or polyether ester (IC-2)) i.e., a polyol and a polycarboxylic acid (polyacid) with a monofunctional alcohol (IA).

[0066] -The compound (C) represented by the chemical formula (II)- As the compound (C) represented by the chemical formula (II), examples include the reaction products of compounds having one or more hydroxyl groups (II-A) and monofunctional carboxylic acids (II-B).

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

[0068] As a specific compound of a monofunctional alcohol, it may be set to be the same as the compound exemplified by the monofunctional alcohol (IA) used in the raw materials of the compound represented by the chemical formula (I).

[0069] In addition, specific compounds that are monofunctional alcohols may also be listed as such: compounds used in the raw materials of the compounds represented by the chemical formula (I), compounds used in the raw materials of polyesters and / or polyether esters (IC), (IC-1), (IC-2) having carboxyl groups at one or both ends, and compounds classified as monofunctional alcohols; etc. These may be used alone or in combination of two or more.

[0070] Low molecular weight polyols among the polyfunctional alcohols include, for example, polyols with a molecular weight of less than 300. Examples of such low molecular weight polyols 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-dihydroxymethylheptane, diethylene glycol, dipropylene glycol, neopentanediol, cyclohexane-1,4-diol, cyclohexane-1,4-diethanol, dimer glycol, ethylene oxide or propylene oxide adducts of bisphenol A, bis(β-hydroxyethyl)benzene, phenyl dimethyl diol, etc.; trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, etc., which are low molecular weight polyols with trifunctionality or higher.

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

[0072] Additionally, examples of polyfunctional alcohols include: compounds used as polyols in the raw materials of polyesters and / or polyether esters (IC), (IC-1), (IC-2) having carboxyl groups at one or both ends; and compounds classified as polyfunctional alcohols. These may be used alone or in combination of two or more.

[0073] The compound (II-A) having one or more hydroxyl groups is preferably a high molecular weight polyol, more preferably a polyester polyol, polyether polyol, polyether ester polyol, or a hydroxyl-containing urethane resin made from these polyols. One of these compounds may be used alone, or two or more may be used in combination. Preferably, these compounds have a hydroxyl group at at least one end, and more preferably, they have hydroxyl groups at both ends.

[0074] The molecular weight of compounds having one or more hydroxyl groups (II-A) is preferably in the range of 100 to 20,000. The molecular weight of high molecular weight polyols 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 molecular weight is a value calculated based on the valence of the hydroxyl group according to the potentiometric titration method of JIS K 0070:1992.

[0075] Monofunctional carboxylic acids (II-B) that serve as raw materials for compounds represented by the chemical formula (II) can include, for example, aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids. These can be used alone or in combination. Among these, aliphatic monocarboxylic acids are preferred for ease of phase separation and esterification. Aliphatic monocarboxylic acids preferably have 5 to 20 carbon atoms.

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

[0077] In addition, aliphatic monocarboxylic acids can be either saturated or unsaturated, but for the sake of preservation stability, saturated aliphatic monocarboxylic acids are preferred.

[0078] Examples of aliphatic monocarboxylic acids include: hexanoic acid, 2-ethylhexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanic acid, stearic acid, arachidic acid, etc. These can be used alone or in combination with two or more.

[0079] Additionally, examples of monofunctional carboxylic acids (II-B) may include compounds used as raw materials for compounds represented by the chemical formula (I) that are exemplified as monofunctional or polyfunctional carboxylic acids and / or their anhydrides (IB), and compounds classified as monofunctional carboxylic acids and / or their anhydrides. These may be used alone 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, more preferably in the range of 120 to 350. The molecular weight is expressed as a value calculated based on the acid value according to the potentiometric titration method of JIS K 0070:1992.

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

[0082] -The compound (C) represented by the chemical formula (III)- As the compound (C) represented by the chemical formula (III), for example, the reaction product of a monofunctional or polyfunctional alcohol (III-A) and a monofunctional isocyanate (III-B) can be listed.

[0083] Examples of monofunctional or polyfunctional alcohols (III-A) used as raw materials for compounds represented by formula (III) include: compounds exemplified as monofunctional alcohols (IA) used as raw materials for compounds represented by formula (I); compounds exemplified as polyols used as raw materials for polyesters and / or polyether esters (IC) having carboxyl groups at one or both ends; compounds exemplified as compounds having one or more hydroxyl groups (II-A) used as raw materials for compounds represented by formula (II); and so on. One of these may be used alone, or two or more may be used in combination. The monofunctional or polyfunctional alcohol (III-A) has one or more hydroxyl groups, preferably at least at one end, and more preferably at both ends. The monofunctional or polyfunctional alcohol (III-A) is preferably a high molecular weight polyol, preferably a polyester polyol, polyether polyol, polyether ester polyol, or a hydroxyl-containing urethane resin made from these polyols. One or more of these can be used alone or in combination. Preferably, it has at least one hydroxyl group at one end, and more preferably at both ends.

[0084] The preferred range of molecular weight of the monofunctional or polyfunctional alcohol (III-A) and the high molecular weight polyol may be set to be the same as the preferred range of molecular weight of the monofunctional or polyfunctional alcohol and the high molecular weight polyol exemplified in the raw material of the compound represented by the chemical formula (II), i.e., the compound (II-A) having one or more hydroxyl groups.

[0085] Monofunctional isocyanates (III-B) that can be used as raw materials for compounds represented by the chemical formula (III) include, for example: aliphatic isocyanates such as ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, etc.; aromatic isocyanates such as phenyl isocyanate, benzyl isocyanate, p-toluenesulfonyl isocyanate, etc.

[0086] The number-average molecular weight of the monofunctional isocyanate (III-B) is preferably in the range of 70 to 500, more preferably in the range of 90 to 300. The molecular weight is expressed as a value calculated by potentiometric titration according to JIS K-1603-1:2007 using the n-dibutylamine method.

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

[0088] End-capped polyester oligomers representing any of the compounds (C) in chemical formulas (I) to (III) can be, for example, compounds of polyester polyols with hydroxyl groups blocked at one or both ends; in other words, the compounds can be called end-capped polyester polyols. In addition, the end-capped polyether oligomers that are compounds (C) represented by any one of the chemical formulas (I) to (III) can be, for example, compounds of polyether polyols with hydroxyl groups blocked at one or both ends; in other words, the compounds can be called end-capped polyether polyols. In addition, the end-capped polyether ester oligomers that are compounds (C) represented by any one of the chemical formulas (I) to (III) can be, for example, compounds with hydroxyl groups blocked at one or both ends of polyether ester polyols; in other words, the compounds can be called end-capped polyether ester polyols. Furthermore, the compound (C) does not substantially have isocyanate groups at one or both ends.

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

[0090] Measurement equipment: High-speed GPC device (HLC-8220GPC manufactured by Tosoh Corporation) Tube Column: The following tube columns manufactured by Tosoh Corporation are connected in series for use. "TSKgel G5000" (7.8 mmI.D.×30 cm)×1 "TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1 stick "TSKgel G3000" (7.8 mmI.D.×30 cm)×1 "TSKgel G2000" (7.8 mm I.D. × 30 cm) × 1 stick Detector: RI (Differential Refractometer) Column temperature: 40℃ Washing solution: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (0.4% by mass tetrahydrofuran solution containing the sample) Standard samples: The standard curve was 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 compound (C) may or may not have ether groups within its molecule. When the compound (C) has ether groups, the thermosetting resin composition disclosed herein, in addition to achieving low elasticity, also more easily achieves low viscosity and a decrease in the coefficient of linear expansion. Therefore, the ether concentration of the compound (C) is preferably 11.5 mol / kg to 23 mol / kg, more preferably 13 mol / kg to 20 mol / kg. The ether concentration of the compound (C) represents the concentration of ether groups relative to the total mass of the raw materials when using one compound (C), and represents the concentration of the ether groups of the compound with the highest ether concentration when using two or more compounds (C).

[0093] The total content of the compound (C) in the non-volatile components of the composition after removing the filler (D) from the thermosetting resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less.

[0094] [4] Filler (D) One or more fillers (D) selected from the group consisting of inorganic microparticles and fibers are essential components for reducing the thermal expansion of the insulation layer to a specified level. Examples of such inorganic microparticles include: silicon dioxide (fused silicon dioxide, crystalline silicon dioxide, 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., preferably silicon dioxide, and more preferably fused silicon dioxide. Furthermore, the silicon dioxide can be either fragmented or spherical; from the viewpoint of increasing the dosage while suppressing the melt viscosity of the thermosetting resin composition, spherical shape is preferred.

[0095] The volume average particle size of the inorganic microparticles is, for example, 0.01 μm or more, more preferably 0.03 μm or more, more preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 μm or less. The volume average particle size of the inorganic microparticles can be determined by laser diffraction.

[0096] Examples of fibers include inorganic fibers such as glass fibers and carbon fibers, as well as organic fibers. The inorganic fibers can be long or short fibers. The carbon fibers can be either 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 fibers that can be dispersed in a thermosetting resin composition and are arranged in a single direction, or they may be fibers that can be used to make woven or non-woven fabrics. The thickness of the woven or non-woven fabric is preferably less than 100 μm, more preferably more than 2 μm, and even more preferably more than 5 μm.

[0098] The content of the filler (D) in the non-volatile components of the thermosetting composition is 40% by mass or more, preferably 60% by mass or more, and more preferably 99% by mass or less, and even more preferably 95% by mass or less.

[0099] [5] Thermosetting resin composition The thermosetting resin composition disclosed herein contains components (A) to (D) as essential components, but may contain any other components as needed.

[0100] The thermosetting resin composition disclosed herein may include a curing accelerator (E). Examples of the curing accelerator (E) include phosphorus compounds, tertiary amines, imidazole compounds, organic acid metal salts, Lewis acids, and amine chelate salts. The content of the curing accelerator (E) when used is preferably 0.005% by mass or more and 5% by mass or less of the non-volatile components after removing the filler (D) from the thermosetting resin composition.

[0101] The thermosetting resin composition disclosed herein may contain one or more curing agents (F) other than acid anhydride (B). As a curing agent (F) other than acid anhydride (B), any curing agent capable of curing the thermosetting resin composition may be used, such as amine compounds, amide compounds, reactive ester resins, phenolic 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 in the non-volatile components of the thermosetting resin composition after removing the filler (D).

[0102] The thermosetting resin composition disclosed herein may include a resin (G) other than compound (C) capable of forming a phase-separable structure with the thermosetting resin, but preferably does not include said resin (G). Examples of resins (G) capable of forming a phase-separable structure with the thermosetting resin other than compound (C) include: polyethylene glycol, polypropylene glycol, polybutane glycol, polyolefin polyols, polybutadiene polyols, polyester polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, and other polyols, or hydroxyl-containing urethane resins, acrylic resins, styrene-butadiene copolymers, etc., made from one or more of these polyols. The content of said resin (G) in the non-volatile components of the thermosetting resin composition after removing filler (D) 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.

[0103] Other additives (H) may be used in the thermosetting resin composition disclosed herein. These other additives (H) may include, for example, flame retardants, organic solvents, conductive particles, rubber, fillers, silane coupling agents, release agents, pigments, emulsifiers, etc.

[0104] [Curved materials, semiconductor sealing materials, semiconductor devices, insulating materials for printed wiring boards, printed wiring boards] The thermosetting resin composition disclosed herein is obtained by mixing the aforementioned components and can be thermosetting to form a cured product. Examples of the cured product's shape include laminates, castings, adhesive layers, coatings, and films.

[0105] Examples of applications for the thermosetting resin composition disclosed herein include: semiconductor sealing materials, printed circuit board materials, resin casting materials, adhesives, interlayer insulating materials for add-on substrates, and adhesive films for add-on layers. Among these applications, in the use of insulating materials for printed circuit boards or electronic circuit boards, and adhesive films for add-on layers, they can be used as insulating materials for so-called electronic component embedded substrates, where passive components such as capacitors or active components such as IC chips are embedded within the substrate. Of these, those with high heat resistance, low thermal expansion, low viscosity, low modulus of elasticity, and solvent solubility are preferred for use in printed circuit board materials or adhesive films for add-on layers.

[0106] As a method for preparing semiconductor sealing materials from the thermosetting composition disclosed herein, the thermosetting resin composition can be fully melted and mixed until it becomes homogeneous using, for example, an extruder, a kneader, or a roller.

[0107] When the thermosetting resin composition disclosed herein is used as a semiconductor sealing material, semiconductor encapsulation molding can be performed. Specifically, by casting the composition or molding the composition using a transfer molding machine, injection molding machine, etc., and then heating it at 50°C to 200°C for 2 to 10 hours, a semiconductor device as a molded product can be obtained.

[0108] Furthermore, when manufacturing printed circuit boards using the thermosetting resin composition disclosed herein, a method can be described as impregnating the thermosetting resin composition with a reinforcing substrate and then overlapping copper foil for heat pressing. Examples of the reinforcing substrate include: paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving. More specifically, firstly, by heating the thermosetting resin composition (preferably 50°C to 170°C, depending on the type of organic solvent), a prepreg as a cured material can be obtained. The resin content in the prepreg is preferably 20% by mass or more and 60% by mass or less. Then, the prepreg volume layer is overlapped with copper foil, and under a pressure of 1 MPa to 10 MPa, it is heat-pressed at 170°C to 300°C for 10 minutes to 3 hours, thereby obtaining the target printed circuit board.

[0109] When the thermosetting resin composition disclosed herein is used as a conductive paste, examples include: a method for preparing an anisotropic conductive film composition by dispersing conductive particles (fine conductive particles) in the thermosetting resin composition; and a method for preparing a circuit connection paste resin composition or anisotropic conductive adhesive that is liquid at room temperature.

[0110] As a method for obtaining an interlayer insulating material for a build-up substrate from the thermosetting resin composition disclosed herein, for example, the thermosetting resin composition is applied to a wiring substrate on which circuitry is formed using a spray coating method or a curtain coating method, and then cured. Then, as needed, predetermined through-holes are made, and the surface is treated with a roughening agent, washed with hot water to create an uneven surface, and then plated with a metal such as copper. As the plating method, electroless plating or electrolytic plating is preferred. Examples of roughening agents include oxidants, alkalis, and organic solvents. This operation is repeated sequentially as needed to alternately build up resin insulating layers and conductor layers with predetermined circuit patterns, thereby obtaining a build-up substrate. The through-holes are made after the outermost resin insulating layer is formed. Alternatively, the addition substrate can be fabricated by heating and pressing a resin-coated copper foil, which is formed by semi-curing the thermosetting resin composition on the copper foil, at 170°C to 300°C onto a wiring substrate with circuitry formed, thereby omitting the steps of forming a roughened surface and plating.

[0111] Regarding the method for manufacturing a multilayer film from the thermosetting resin composition disclosed herein, for example, a method can be described in which the thermosetting resin composition disclosed herein is coated onto a support film to form a resin composition layer, and a multilayer film for use in a multilayer printed circuit board is prepared.

[0112] When using the thermosetting resin composition disclosed herein for the laminated film, it is important that the film softens under the lamination temperature conditions (typically 70°C to 140°C) in the vacuum lamination process, while laminating the circuit board, exhibiting a fluidity (resin flow) that allows for resin filling within via holes or through holes present in the circuit board. To exhibit this characteristic, it is preferable to formulate the components accordingly.

[0113] Here, the diameter of the through-hole in the multilayer printed circuit board is typically 0.1 mm to 0.5 mm, and the depth is typically 0.1 mm to 1.2 mm, preferably within this range for resin filling. Furthermore, when laminating both sides of the circuit board, it is ideal to fill approximately half of the through-hole.

[0114] Specifically, the method for manufacturing the adhesive film described above can be carried out by the following method: after preparing a varnish-like thermosetting resin composition disclosed herein, the varnish-like composition is coated on the surface of a support film (Y), and then the organic solvent is dried by heating or hot air blowing to form a layer (X) of thermosetting composition.

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

[0116] Furthermore, the layer (X) disclosed herein can be protected by the protective film described later. By being protected by the protective film, dirt and other contaminants can be prevented from adhering to the surface of the resin composition layer or causing damage to the surface of the resin composition layer.

[0117] The supporting film and protective film may include: polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"); polyesters such as polyethylene naphthalate; polycarbonate; polyimide; and release paper or metal foils such as copper foil and aluminum foil. Furthermore, the supporting film and protective film may undergo matte treatment, corona treatment, and release treatment.

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

[0119] The support film (Y) is peeled off after being laminated onto the circuit board or after forming an insulating layer by heat curing. Peeling off the support film (Y) after heat curing the adhesive film prevents the adhesion of contaminants or other contaminants during the curing process. In cases where peeling is performed after curing, the support film is typically pre-treated with a demolding process.

[0120] Subsequently, regarding the method for manufacturing a multilayer printed circuit board using the adhesive film obtained as described above, for example, after peeling off the protective film while layer (X) is protected by a protective film, layer (X) is laminated onto one or both sides of the circuit board in direct contact with the circuit board, for example, by vacuum lamination. The lamination method can be batch lamination or continuous lamination using rollers. Furthermore, the adhesive film and the circuit board can be heated (preheated) as needed before lamination.

[0121] Regarding the lamination conditions, it is preferable to set the pressing temperature (lamination temperature) to 70℃~140℃, the pressing pressure to 1 kgf / cm2~11 kgf / cm2 (9.8×104 N / m2~107.9×104 N / m2), and to carry out lamination under reduced pressure of 20 mmHg (26.7 hPa).

[0122] As a method for obtaining the cured material disclosed herein, a general curing method for thermosetting resin compositions can be used. For example, the heating temperature conditions can be appropriately selected according to the type or purpose of the combined curing agent. The composition obtained by the method can be heated within a temperature range of about 20°C to 300°C.

[0123] Modifiers for thermosetting resins (modified resins) The thermosetting resin modifier (modified resin) disclosed herein is an oligomer selected from the group consisting of end-capped polyester oligomers, end-capped polyether oligomers, and end-capped polyether ester oligomers. The thermosetting resin modifier (modified resin) disclosed herein may be a compound represented by any one of the following chemical formulas (I) to (III).

[0124] [Chemistry 9]

[0125] R1, R2, and n1 in the chemical formula (I) are the same as those defined above.

[0126] [Chemistry 10]

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

[0128] [Chemistry 11]

[0129] R5, R6, and n3 in the chemical formula (III) are the same as defined above.

[0130] The thermosetting resin modifier (modified resin) disclosed herein forms a phase-separated structure by mixing with the thermosetting resin, which reduces the thermal expansion coefficient and elastic modulus of the mixture and suppresses warping during curing. The thermosetting resin modifier disclosed herein can be used to modify the thermosetting resin in the thermosetting resin composition disclosed herein, preferably as an epoxy resin modifier (modified resin). In thermosetting resin compositions using acid anhydrides as curing agents for the thermosetting resin (including epoxy resin), the effects are significantly enhanced by using the thermosetting resin modifier (modified resin) disclosed herein compared to using other modifiers.

[0131] Details regarding the modifier (modified resin) for the thermosetting resin disclosed herein can be assumed to be the same as the details of compound (C) in the thermosetting resin composition disclosed herein, therefore, the description is omitted here.

[0132] This disclosure is not limited to the described embodiments. The described embodiments are examples and have a structure that is substantially the same as the technical concept described in the claims of this disclosure. Any embodiment that achieves the same effect is included within the technical scope of this disclosure. [Example]

[0133] The following examples and comparative examples are provided to illustrate this disclosure in more detail.

[0134] [Example 1] In a mixing container, 9.08 parts by weight of epoxy resin 1 (EPICLON 830CRP manufactured by DIC Corporation), 9.67 parts by weight of alicyclic acid anhydride 1 (HN-5500 manufactured by Resonac Corporation), and 6.25 parts by weight of compound (C1) as a modified resin (a reaction product obtained by reacting polypropylene glycol monobutyl ether (Newpol LB-285 manufactured by Sanyo Chemical Industries, Ltd., with a quantity average molecular weight of 1170) and sebacic acid (molecular weight of 202.25) at a molar ratio of 2:1 equivalence concentration, quantity average molecular weight: 2500, hydroxyl value: 2.7, acid value: 3.3, ether concentration: 15.1 mol / kg) were prepared and stirred at an internal temperature of 70°C until the mixture was compatible. Subsequently, 75 parts by weight of molten silicon dioxide 1 ("FB-5SDC" manufactured by Denka Co., Ltd.) and 0.075 parts by weight of curing accelerator (2-ethyl-4-methylimidazolium) were uniformly mixed to obtain a thermosetting resin composition. Furthermore, compound (C1) is equivalent to the compound in the chemical formula (I) where R1 is represented by formula (3) below, R2 is represented by formula (4) below, and n1=2. Specifically, it is a capped polyether ester oligomer represented by formula (5) below.

[0135] [Chemistry 12]

[0136] [Chemistry 13]

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

[0138] [Example 2] In a mixing container, 9.63 parts by weight of epoxy resin 2 (YX8000 manufactured by Mitsubishi Chemical Corporation), 11.62 parts by weight of alicyclic acid anhydride 2 (YH306 manufactured by Mitsubishi Chemical Corporation), and 3.75 parts by weight of compound (C2) as a modified resin (a reaction product obtained by reacting 2-butyl-2-ethyl-1,3-propanediol (molecular weight 160.26) with dodecanoic acid (molecular weight 230.3) and 2-octyldodecanool (KALCOL 200GD manufactured by Kao Corporation, hydroxyl value 185) at a molar ratio of 3.37:4.37:2, with a quantity average molecular weight of 2000, a hydroxyl value of 1.4, an acid value of 1.7, and an ether concentration of 0 mol / kg) were prepared and stirred at an internal temperature of 70°C until the mixture was compatible. Subsequently, 75 parts by weight of molten silicon dioxide 1 ("FB-5SDC" manufactured by Denka Co., Ltd.) and 0.075 parts by weight of curing accelerator (2-ethyl-4-methylimidazolium) were uniformly mixed to obtain a thermosetting resin composition. Furthermore, compound (C2) is equivalent to the compound in the chemical formula (I) in which R1 is represented by the following formula (6), R2 is represented by the following formula (7), and n1=2.

[0139] [Chemistry 14]

[0140] [Chemistry 15]

[0141] (The average value of m1 in equation (7) is 3.37)

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

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

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

[0145] [Synthesis Example 1] Synthesis of Polyester Resin A 779.1 parts by weight of bisphenol A glycol ether (trademark: manufactured by DIC Corporation, 'Hyprox MDB-561'), 132.9 parts by weight of isophthalic acid (hereinafter referred to as "iPA"), and 40.4 parts by weight of sebacic acid (hereinafter referred to as "SebA") were charged into the reaction apparatus, and heating and stirring were initiated. Subsequently, after the internal temperature was raised to 230°C, 0.10 parts by weight of tetraisopropyl titanate (TiPT) were added, and the reaction was carried out at 230°C for 24 hours to synthesize polyester resin. The obtained polyester resin has a hydroxyl value of 36.9 mgKOH / g, a number average molecular weight of 3,040, and a glass transition temperature of -14℃.

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

[0147] [Comparative Example 3] In a mixing container, 11.33 parts by weight of epoxy resin 2 and 13.67 parts by weight of alicyclic acid anhydride 2 were mixed and stirred at an internal temperature of 70°C until they were compatible. Then, 75 parts by weight of molten silicon dioxide 1 ("FB-5SDC" manufactured by Denka Co., Ltd.) and 0.075 parts by weight of curing accelerator (2-ethyl-4-methylimidazolium) were uniformly mixed to obtain a thermosetting resin composition that does not contain modified resin (compound (C)). [evaluate] Thermal expansion The thermosetting resin compositions obtained in the examples and comparative examples were thermosetting at 100°C for 1 hour and at 175°C for 2 hours. Using a TMA6200 (manufactured by Seiko Instruments) as a thermal analysis device, the heating rate was set to 3°C / minute, and the linear thermal expansion coefficient in the range of 40°C to 60°C was measured. The thermal expansion was judged according to the following criteria. (Benchmark 1: Comparison of Example 1, Comparative Example 1, and Comparative Example 2) The linear thermal expansion rates of Example 1 and Comparative Example 1 relative to Comparative Example 2 "○": Less than 0.9 times compared to the comparison example. "×": More than 0.9 times that of Comparative Example 2. (Benchmark 2: Comparison of Examples 2-4 and Comparative Example 3) The linear thermal expansion rates of Examples 2 through 4, relative to the linear thermal expansion rate of Comparative Example 3. "○": Less than 0.9 times compared to Comparative Example 3. "×": More than 0.9 times that of Comparative Example 3.

[0148] <Modulus of elasticity> After the thermosetting resin compositions obtained in the examples and comparative examples were thermosetting at 100°C for 1 hour and at 175°C for 2 hours, the flexural modulus was measured according to JIS K7171, and the elasticity of the cured thermosetting resin compositions was judged according to the following criteria. (Benchmark 1: Comparison of Example 1, Comparative Example 1, and Comparative Example 2) The flexural modulus of Example 1 and Comparative Example 1 relative to the flexural modulus of Comparative Example 2 "○": Less than 0.9 times compared to Comparative Example 2. "×": More than 0.9 times that of Comparative Example 2. (Benchmark 2: Comparison of Examples 2-4 and Comparative Example 3) The flexural modulus of each of Examples 2 to 4 relative to the flexural modulus of Comparative Example 3 "○": Less than 0.9 times compared to Comparative Example 3. "×": More than 0.9 times that of Comparative Example 3.

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

[0150] [Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 thermal expansion ○ ○ ○ ○ elastic modulus ○ ○ ○ ○

[0151] [Table 2] Table 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 thermal expansion × × × elastic modulus ○ × ×

Claims

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 microparticles and fibers, wherein the compound (C) is one or more compounds selected from the group consisting of compounds represented by chemical formulas (I) to (III) below, (in the chemical formula (I), R1 and R2 are each independently any functional group comprising one or more combinations of saturated hydrocarbon groups, ether groups, ester groups, carbamate groups, urea groups, amide groups and amine groups having 1 to 30 carbon atoms, at least one of R1 and R2 is a functional group comprising an ether group and / or an ester group; n1 is a real number in the range of 1 to 6) (In the chemical formula (II), R3 and R4 are each independently any functional group comprising one or more combinations of saturated hydrocarbon groups, ether groups, ester groups, carbamate groups, urea groups, amide groups and amine groups selected from the group consisting of 1 to 30 carbon atoms, and at least one of R3 and R4 is a functional group comprising an ether group and / or an ester group; n2 is a real number in the range of 1 to 6) (In the chemical formula (III), R5 is any functional group comprising one or more combinations of saturated hydrocarbon groups, ether groups, ester groups and sulfonyl groups selected from the group consisting of saturated hydrocarbon groups, ether groups, ester groups, carbamate groups, urea groups, amide groups and amine groups selected from the group consisting of saturated hydrocarbon groups, ether groups, ester groups, carbamate groups, urea groups, amide groups and amine groups selected from the group consisting of saturated hydrocarbon groups, ether groups, ester groups, carbamate groups, urea groups and amine groups selected from the group consisting of saturated hydrocarbon groups, ether groups, ester groups, carbamate groups, urea groups and amine groups selected from the group consisting of saturated hydrocarbon groups, ether groups, ester groups, carbamate groups, urea groups and amine groups selected from the group consisting of saturated hydrocarbon groups, ether groups, ester groups, carbamate groups, urea groups and amine groups selected from the group consisting of saturated hydrocarbon groups, ether groups, ester groups and ester groups selected from the group consisting of saturated hydrocarbon groups, ether ...

2. 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 microparticles and fibers, wherein the compound (C) is one or more compounds selected from the group consisting of compounds represented by chemical formulas (I) to (III) below, (in the chemical formula (I), R1 and R2 are each independently a functional group comprising one or more combinations of one or more of the group consisting of hydrocarbon groups, ether groups, ester groups, carbamate groups, urea groups, amide groups and amine groups having 1 to 30 carbon atoms, at least one of R1 and R2 is a functional group comprising an ether group and / or an ester group; n1 is a real number in the range of 2 to 6) (In the chemical formula (II), R3 and R4 are each independently a combination of one or more functional groups selected from the group consisting of hydrocarbon, ether, ester, carbamate, urea, amide and amino groups with 1 to 30 carbon atoms, and at least one of R3 and R4 is a functional group containing an ether and / or ester group; n2 is a real number in the range of 2 to 6.) (In the chemical formula (III), R5 is a combination of one or more functional groups selected from the group consisting of hydrocarbon, ether, ester and sulfonyl groups with 1 to 20 carbon atoms, and R6 is a combination of one or more functional groups selected from the group consisting of hydrocarbon, ether, ester, carbamate, urea, amide and amino groups with 1 to 30 carbon atoms, and at least one of R5 and R6 is a functional group containing an ether and / or ester group; n3 is a real number in the range of 2 to 6.) 3. The thermosetting resin composition as claimed in claim 1 or 2, wherein, The compound (C) is a reaction product of a monofunctional alcohol (IA) with a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB).

4. The thermosetting resin composition as claimed in claim 1 or 2, wherein, The compound (C) is a reaction product of a monofunctional alcohol (IA) and a polyester and / or polyether ester (IC) having a carboxyl group at one or both ends.

5. The thermosetting resin composition as claimed in claim 3, wherein, The monofunctional alcohol (IA) is selected from one or more of the group consisting of monofunctional polyethylene glycol, monofunctional polypropylene glycol and long-chain aliphatic alcohols.

6. The thermosetting resin composition as claimed in claim 4, wherein, The monofunctional alcohol (IA) is selected from one or more of the group consisting of monofunctional polyethylene glycol, monofunctional polypropylene glycol and long-chain aliphatic alcohols.

7. The thermosetting resin composition as claimed in claim 1 or 2, wherein, The compound (C) is the reaction product of a compound (II-A) having one or more hydroxyl groups and a monofunctional carboxylic acid (II-B).

8. The thermosetting resin composition as claimed in claim 1 or 2, wherein, The compound (C) is a reaction product of a monofunctional or polyfunctional alcohol (III-A) and a monofunctional isocyanate (III-B).

9. The thermosetting resin composition as claimed in claim 1 or 2, wherein, The hydroxyl valence of the compound (C) is greater than 0 and less than 10.

10. The thermosetting resin composition as claimed in claim 1 or 2, wherein, The number of compounds (C) has an average molecular weight of 500 to 50,000.

11. The thermosetting resin composition as claimed in claim 1 or 2, wherein, The content of compound (C) is 5% to 45% by mass in the non-volatile components of the component after removing filler (D).

12. A cured compound, which is a cured compound of a thermosetting resin composition as described in any one of claims 1 to 11.

13. A semiconductor sealing material comprising a thermosetting resin composition as described in any one of claims 1 to 11.

14. A semiconductor device comprising a semiconductor sealing material as described in claim 13.

15. An insulating material for printed wiring boards, comprising a thermosetting resin composition as described in any one of claims 1 to 11.

16. A printed wiring board comprising an insulating material for a printed wiring board as described in claim 15.