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

Abstract

The present invention addresses the problem of providing a thermosetting resin composition that contains a low-viscosity modified resin and that can realize a low thermal expansion and low elastic modulus. The present invention provides a thermosetting resin composition that contains a thermosetting resin (A), a curing agent (B), a modified resin (C), and at least one filler (D) selected from the group consisting of inorganic fine particles and fibers, the thermosetting resin composition being characterized by containing a modified resin (C) in which the ether concentration is 11.5 to 23 mol / kg. The present invention also provides a cured product from the thermosetting resin composition, as well as a semiconductor sealing agent, a semiconductor device, an insulating material for printed wiring boards, and a printed wiring board, in each instance containing the thermosetting resin composition.

Description

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

[0001] The present invention relates to a thermosetting resin composition, a cured product, a semiconductor encapsulant, a semiconductor device, an insulating material for printed wiring boards, and a printed wiring board.

[0002] Thermosetting resins are used in a wide range of fields, including semiconductor elements such as capacitors, diodes, transistors, and thyristors, sealing materials for protecting integrated circuits such as ICs and LSIs, and insulating materials for printed wiring boards. On the other hand, molded products using the thermosetting resins are composites of various different materials, and differences in the thermal expansion coefficients of the materials can cause warping during the production of the composite, resulting in problems with dimensional accuracy. Also, when exposed to temperature changes in the usage environment, defects can occur due to differences in the thermal expansion coefficients, which often poses major manufacturing problems (see, for example, Patent Document 1). Furthermore, in recent years, there has been a strong demand for thermosetting resin compositions to have even lower viscosity, and there is a particular demand for modified resins that can contribute to this.

[0003] Japanese Patent Application Laid-Open No. 2003-82241

[0004] The problem to be solved by the present invention is to provide a thermosetting resin composition that contains a modified resin having low viscosity and can achieve low thermal expansion and low elastic modulus.

[0005] The present invention provides a thermosetting composition comprising a thermosetting resin (A), a curing agent (B), a modified resin (C), and one or more fillers (D) selected from the group consisting of inorganic fine particles and fibers, wherein the modified resin (C) has an ether concentration of 11.5 to 23 mol / kg.

[0006] The present invention also provides a cured product of the thermosetting resin composition, as well as a semiconductor encapsulant, a semiconductor device, an insulating material for printed wiring boards, and a printed wiring board, each containing the thermosetting resin composition.

[0007] That is, the present invention includes the following embodiments. [1] A thermosetting composition comprising a thermosetting resin (A), a curing agent (B), a modified resin (C), and one or more fillers (D) selected from the group consisting of inorganic fine particles and fibers, wherein the modified resin (C) has an ether concentration of 11.5 to 23 mol / kg. [2] The thermosetting resin composition according to [1] above, wherein the modified resin (C) is one or more selected from the group consisting of polyether ester polyols, urethane resins derived from polyether polyols, and urethane resins derived from polyether ester polyols. [3] The thermosetting resin composition according to [1] or [2] above, wherein the modified resin (C) is a terminal-capped polyether oligomer and / or a terminal-capped polyether ester oligomer. [4] The thermosetting resin composition according to [3] above, wherein the terminal-capped polyether oligomer and / or the terminal-capped polyether ester oligomer has a hydroxyl value of 0 or more and 10 or less. [5] The thermosetting resin composition according to [3] or [4], wherein the end-capped polyether oligomer is a reaction product of a monofunctional alcohol (IA) and a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB), or a reaction product of a monofunctional alcohol (IA) and a polyester and / or polyether ester (IC) having carboxyl groups at one or both ends. [6] The thermosetting resin composition according to any one of [3] to [5], wherein the end-capped polyether ester oligomer is a reaction product of a monofunctional alcohol (IA) containing a monofunctional polypropylene glycol and a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB). [7] The thermosetting resin composition according to [3] or [4], wherein the end-capped polyether ester oligomer is a reaction product of a monofunctional or polyfunctional alcohol (II-A) having one or more ether groups and a monofunctional carboxylic acid (II-B). [8] The thermosetting resin composition according to [3] or [4], wherein the end-capped polyether oligomer and / or the end-capped polyether ester oligomer is a reaction product of a monofunctional or polyfunctional alcohol (III-A) having one or more ether groups and a monofunctional isocyanate (III-B).[9] The thermosetting resin composition according to any one of [1] to [8], wherein the number average molecular weight of the modifying resin (C) is 500 to 50,000.

[10] The thermosetting resin composition according to any one of [1] to [9], wherein the content of the modifying resin (C) is 5 to 45 mass%.

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

[10] .

[12] A semiconductor encapsulant comprising the thermosetting resin composition according to any one of [1] to

[11] .

[13] A semiconductor device comprising the semiconductor encapsulant according to

[12] .

[14] An insulating material for printed wiring boards comprising the thermosetting resin composition according to any one of [1] to

[10] .

[15] A printed wiring board comprising the insulating material for printed wiring boards according to

[14] .

[16] An epoxy resin modifier which is a terminal-capped polyether oligomer and / or a terminal-capped polyether ester oligomer.

[17] The epoxy resin modifier according to

[16] , wherein the end-capped polyether oligomer is a reaction product of a monofunctional alcohol (IA) with a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB), or a reaction product of a monofunctional alcohol (IA) with a polyester and / or polyether ester (IC) having carboxyl groups at one or both ends.

[18] The epoxy resin modifier according to

[16] , wherein the end-capped polyester oligomer is a reaction product of a monofunctional alcohol (IA) containing a monofunctional polypropylene glycol with a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB).

[19] The epoxy resin modifier according to

[16] , wherein the end-capped polyether ester oligomer is a reaction product of a monofunctional or polyfunctional alcohol (II-A) having one or more ether groups with a monofunctional carboxylic acid (II-B).

[20] The epoxy resin modifier according to

[16] , wherein the end-capped polyether oligomer and / or the end-capped polyetherester oligomer is a reaction product of a monofunctional or polyfunctional alcohol (III-A) having one or more ether groups and a monofunctional isocyanate (III-B).

[0008] In the thermosetting resin composition of the present invention, the modified resin has a low viscosity, and as a result, the thermosetting resin composition containing the modified resin also has a low viscosity, and further has excellent low thermal expansion properties and low elastic modulus.

[0009] [Thermosetting Resin Composition] The thermosetting resin composition of the present invention contains, as essential components, a thermosetting resin (A), a curing agent (B), a modified resin (C), and one or more fillers (D) selected from the group consisting of inorganic fine particles and fibers.

[0010] Examples of the thermosetting resin (A) that can be used include epoxy resins, benzoxazine structure-containing resins, maleimide resins, vinylbenzyl compounds, acrylic compounds, and copolymers of styrene and maleic anhydride. These resins may be used alone or in combination of two or more. Among these, epoxy resins and / or maleimide resins are preferred, and epoxy resins are more preferred, because they are more likely to form a phase-separated structure with the modified resin (C) described below and thus more likely to achieve the effects of the present invention.

[0011] Examples of the epoxy resin 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, dicyclopentadiene-phenol addition reaction type epoxy resin, Examples of epoxy resins that can be used include phenol resins, phenol aralkyl type epoxy resins, naphthol novolac type epoxy resins, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resins, biphenyl novolac type epoxy resins, naphthalene skeleton-containing epoxy resins such as 1,1-bis(2,7-diglycidyloxy-1-naphthyl)alkane, and phosphorus-modified epoxy resins in which phosphorus atoms have been introduced into these various epoxy resins.

[0012] Among these, as the epoxy resin, 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 co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy resins, crystalline biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, xanthene type epoxy resins, and 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 by formaldehyde) are particularly preferred because they can give cured products with excellent heat resistance.

[0013] As the maleimide resin, for example, a resin represented by any one of the following structural formulas can be used.

[0014]

[0015] [In formula (1), R 1 represents an a-valent organic group, and R 2 and R 3 each 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 greater.

[0016]

[0017] [In formula (2), R 4 , R 5 and R 6 each 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 independently represents a saturated hydrocarbon group having 1 to 5 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group having 6 to 15 carbon atoms formed by combining a saturated hydrocarbon group and an aromatic hydrocarbon group. a3, a4, and a5 each independently represent an integer of 1 to 3, and n represents an integer of 0 to 10.]

[0018] 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 the upper limit being 100% by mass.

[0019] The content of the thermosetting resin (A) is preferably 3% by mass or more, more preferably 5% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, of the non-volatile content of the components excluding the filler (D) from the thermosetting resin composition.

[0020] The curing agent (B) may be any agent capable of curing the thermosetting resin composition, and may include, for example, an amine compound, an amide compound, an active ester resin, an acid anhydride, a phenol resin, a cyanate ester resin, etc. Among these, at least one selected from an amine compound, an active ester resin, a phenol resin, and a cyanate resin is preferred, and an amine compound or a phenol resin is more preferred.

[0021] Examples of the amine compound that can be used include diethyltoluenediamine, diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivatives.

[0022] As the amide compound, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, or the like can be used.

[0023] Preferred examples of the activated ester resin include compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. The activated ester resin is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. From the perspective of improving heat resistance, activated ester resins obtained from a carboxylic acid compound or a halide thereof and a hydroxy compound are preferred, and activated ester resins obtained from a carboxylic acid compound or a halide thereof and a phenol compound and / or a naphthol compound are more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like, or halides thereof. Examples of phenol compounds or naphthol compounds that can be used include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and dicyclopentadiene-phenol adduct resins.

[0024] Examples of the acid anhydride that can be used include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0025] Examples of the phenolic resin include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Xyloc resin), naphthol aralkyl resin, triphenylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenolic resin (a polyhydric phenolic hydroxyl group-containing compound in which phenol nuclei are linked by bismethylene groups), naphthalene skeleton-containing phenolic resin, biphenyl-modified naphthol resin (a polyhydric naphthol in which phenol nuclei are linked by bismethylene groups). compounds), polyhydric phenolic hydroxyl group-containing resins such as aminotriazine-modified phenolic resins (polyhydric phenolic hydroxyl group-containing compounds in which a phenol nucleus is linked by melamine, benzoguanamine, or the like) and alkoxy group-containing aromatic ring-modified novolak resins (polyhydric phenolic hydroxyl group-containing compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked by formaldehyde); bisphenol compounds such as bisphenol A and bisphenol F; biphenyl compounds such as biphenyl and tetramethylbiphenyl; triphenylolmethane, tetraphenylolethane; dicyclopentadiene-phenol addition reaction type resins; and phosphorus-modified phenolic compounds in which a phosphorus atom has been introduced into any of these various phenolic hydroxyl group-containing compounds.

[0026] The cyanate ester resin may be one or more types, and examples thereof include bisphenol A type cyanate ester resins, bisphenol F type cyanate ester resins, bisphenol E type cyanate ester resins, bisphenol S type cyanate ester resins, bisphenol sulfide type cyanate ester resins, phenylene ether type cyanate ester resins, naphthylene ether type cyanate ester resins, biphenyl type cyanate ester resins, tetramethylbiphenyl type cyanate ester resins, polyhydroxynaphthalene type cyanate ester resins, phenol novolac type cyanate ester resins, and cresol novolac type cyanate ester resins. Examples of cyanate ester resins that can be used include triphenylmethane cyanate ester resins, tetraphenylethane cyanate ester resins, dicyclopentadiene-phenol addition reaction type cyanate ester resins, phenol aralkyl type cyanate ester resins, naphthol novolac type cyanate ester resins, naphthol aralkyl type cyanate ester resins, naphthol-phenol co-condensed novolac type cyanate ester resins, naphthol-cresol co-condensed novolac type cyanate ester resins, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate ester resins, biphenyl-modified novolac type cyanate ester resins, and anthracene type cyanate ester resins.

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

[0028] The thermosetting resin composition of the present invention may further contain a curing accelerator (B1). Examples of the curing accelerator (B1) that can be used include phosphorus-based compounds, tertiary amines, imidazole compounds, organic acid metal salts, Lewis acids, and amine complex salts. When the curing accelerator (B1) is used, the content thereof is, for example, 0.005% by mass or more and 5% by mass or less of the nonvolatile content of the components excluding the filler (D) from the thermosetting resin composition.

[0029] In order to obtain the effects of the present invention, it is essential that the modified resin (C) contains one having an ether concentration of 11.5 to 23 mol / kg. Furthermore, the ether concentration is more preferably 13 to 20 mol / kg. When a single modified resin (C) is used, the ether concentration of the modified resin (C) indicates the concentration of ether groups relative to the total mass of the raw material. When a mixture of multiple modified resins (C) is used, the ether concentration of the modified resin with the highest ether concentration among the modified resins contained is indicated.

[0030] In the present invention, by using the specific modified resin (C), a phase separation structure is formed with the thermosetting resin (A) (particularly, an epoxy resin), which results in a lower thermal expansion coefficient and a lower elastic modulus than a completely compatible system. Therefore, warping during production can be suppressed, and low viscosity can also be achieved.

[0031] The importance of low viscosity is also noted below. For example, in the manufacture of semiconductor packages, there are many issues, such as fine-wire connections using gold wires when connecting a chip to a wiring substrate, narrow connection gaps via bump electrodes, and narrow gaps between chips when mounting multiple chips. To ensure connection reliability after the package is completed, these fine gaps must be filled with various encapsulants, such as solid encapsulants, liquid encapsulants, and underfill encapsulants, in a high-temperature liquid state for a short period of time and then cured to reinforce the adhesion. To prevent defects such as voids and unfilled areas after filling narrow gaps with encapsulant, the viscosity of the encapsulant must be sufficiently reduced during injection. Generally, encapsulants containing resin components with a large thermal expansion coefficient must minimize the thermal expansion gap with chips that have a small thermal expansion coefficient. Furthermore, the encapsulant must be heavily loaded with a large amount of inorganic filler with a low thermal expansion coefficient. Therefore, resin materials used in encapsulants are strongly required to have low viscosity so that their viscosity at high temperatures during melting can be kept low even when heavily loaded with inorganic filler. Furthermore, it would be even more ideal if the thermal expansion coefficient could be reduced even with a reduced inorganic filler loading. Furthermore, insulating materials such as build-up films and prepregs that constitute package substrates on which fine circuit patterns are formed must have a sufficiently low viscosity when melted in order to facilitate circuit embedding during vacuum lamination and high-temperature press molding. These insulating resin materials must be given properties such as toughness, crack resistance, low warpage, and low elasticity by adding and dispersing a phase-separable modified resin. However, most phase-separable additives generally have a large molecular weight, which increases and deteriorates the melt viscosity.In contrast, the present invention provides a modified resin material that, as a property that can be imparted by the modified resin material, exhibits an effect of lowering the thermal expansion coefficient, which has previously been unthinkable except for inorganic fillers, and that exhibits low thermal expansion with a greater effect than inorganic materials, despite being a resin material.Furthermore, the phase separation mechanism of the modified resin for forming phase separation is such that, before the base resin, the thermosetting resin (A), which is the base resin, is in a low-viscosity state where the base resin and the low-viscosity modified resin are compatible with each other and in a low-viscosity state, and when cured, a reaction-induced type is formed in which a sea-island structure is formed.This makes it possible to form sea-island phase separation after curing, despite the low molecular weight and low viscosity, and the obtained phase-separated structure exhibits a low thermal expansion coefficient and low elasticity, and also has the effect of reducing warping of the molded product, making this an extremely rare modified resin.

[0032] Specifically, the modified resin (C) can be polyether polyol, polyether ester polyol, urethane resin made from polyether polyol, urethane resin made from polyether ester polyol, etc. These resins can be used alone or in combination of two or more. Among these, polyether ester polyol and / or urethane resin made from polyether polyol are preferred, and polyether ester polyol is more preferred, in order to further obtain the effects of the present invention.

[0033] Examples of the polyetherester polyol that can be used include a reaction product of a polyether polyol with a polybasic acid, a reaction product of a polyether polyol with a lactone compound, etc. These polyols may be used alone or in combination of two or more.

[0034] Examples of the polyether polyol that can be used include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Among these, polypropylene glycol is preferred in terms of further achieving the effects of the present invention.

[0035] The polybasic acid may be used alone or in combination of two or more kinds. Examples of the polybasic acid that can be used include 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.

[0036] Examples of the lactone compound that can be used include γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, ε-methylcaprolactone, ε-ethylcaprolactone, ε-propylcaprolactone, 3-penten-4-olide, 12-dodecanolide, γ-dodecanolactone, etc. Among these, ε-caprolactone is preferred.

[0037] As the polyether polyol in the urethane resin made from the polyether polyol as a raw material, the same polyether polyols as those mentioned above can be used, and polypropylene glycol is preferred.

[0038] As the polyetherester polyol in the urethane resin made from the polyetherester polyol as a raw material, the same polyetherester polyols as those described above can be used.

[0039] In addition to the polyether polyols, polyisocyanates can also be used as raw materials for the urethane resin. For example, aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, triene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; and alicyclic structure-containing polyisocyanates such as cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate can be used.

[0040] Furthermore, as the modified resin (C) capable of exhibiting a predetermined ether concentration, one or more types of end-capped polyether oligomers or end-capped polyether ester oligomers can be used. End-capped polyether oligomers or end-capped polyether ester oligomers are compounds that contain ether groups and have substantially no acid groups such as hydroxyl groups or carboxyl groups at the ends at least in the length direction of the main chain. Among these, end-capped polyether oligomers or end-capped polyether ester oligomers are preferably compounds that have substantially no acid groups such as hydroxyl groups or carboxyl groups in the molecule. "Substantially no" means that the hydroxyl value and acid value are within the ranges described below.

[0041] As the modified resin (C), for example, one or more compounds selected from the group consisting of compounds represented by the following chemical formulas (I) to (III) can be used. In particular, as 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, as the end-capped polyether oligomer, one or more compounds represented by the following chemical formula (III) can be used.

[0042]

[0043] (In the chemical formula (I), R1 and R2 each independently represent any functional group consisting of one or a combination of two or more 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. n1 is a real number ranging from 1 to 6.) Of these, n1 is preferably a real number ranging from 1 to 3, and more preferably a real number ranging from 1 to 2.

[0044]

[0045] (In the chemical formula (II), R3 and R4 each independently represent any functional group consisting of one or a combination of two or more 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. n2 is a real number ranging from 1 to 6.) Of these, n2 is preferably a real number ranging from 1 to 3, and more preferably a real number ranging from 1 to 2.

[0046]

[0047] (In the chemical formula (III), R5 is any functional group consisting of one or a combination of two or more selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms, ether groups, ester groups, and sulfonyl groups; R6 is any functional group consisting of one or a combination of two or more 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. n3 is a real number ranging from 1 to 6.) Of these, n3 is preferably a real number ranging from 1 to 3, and more preferably a real number ranging from 1 to 2.

[0048] The hydroxyl value of the end-capped polyether oligomer or end-capped polyether ester oligomer (for example, the compounds represented by the chemical formulas (I) to (III)) is preferably from 0 to 10, more preferably from 0 to 5, even more preferably from 0 to 2, and particularly preferably 0. The acid value of the end-capped polyether oligomer or end-capped polyether ester oligomer (for example, the compounds represented by the chemical formulas (I) to (III)) is preferably from 0 to 10, more preferably from 0 to 5, even more preferably from 0 to 2, and particularly preferably 0. The hydroxyl value and acid value of the end-capped polyether oligomer or end-capped polyether ester oligomer (the compounds represented by the chemical formulas (I) to (III)) can be adjusted by the types and reaction ratios (molar ratios) of the raw materials for the end-capped polyether oligomer or end-capped polyether ester oligomer (the compounds represented by the chemical formulas (I) to (III)).

[0049] Examples of the compound represented by chemical formula (I) (end-capped polyether oligomer) include a reaction product of a monofunctional alcohol (IA) with a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB), a reaction product of a monofunctional alcohol (IA) with a polyester and / or polyether ester (IC) having carboxyl groups at one or both ends, etc. "Both ends" refers to the respective ends in the length direction of the main chain.

[0050] The monofunctional alcohol (IA) used as a raw material for the compound represented by the chemical formula (I) has one hydroxyl group in the compound. It is preferable that the monofunctional alcohol (IA) does not have any functional groups other than the one hydroxyl group that can react with the monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB), and the polyester and / or polyether ester (IC) having carboxyl groups at one or both ends.

[0051] The monofunctional alcohol (IA) may have one hydroxyl group, and examples thereof include aliphatic alcohols, monofunctional polyethylene glycols, monofunctional polypropylene glycols, monofunctional polyoxybutylenes, monofunctional polycaprolactones, and monofunctional polyesters. These may be used alone or in combination of two or more. When the compound to react with the monofunctional alcohol (IA) is a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB), the aliphatic alcohol used as the monofunctional alcohol (IA) is preferably a long-chain aliphatic alcohol. When the compound to react with the monofunctional alcohol (IA) is a polyester and / or polyether ester (IC) having a carboxyl group at one or both ends, the aliphatic alcohol used as the monofunctional alcohol (IA) may be a long-chain aliphatic alcohol or a short-chain aliphatic alcohol.

[0052] Among these, the monofunctional alcohol (IA) is preferably a compound selected from the group consisting of monofunctional polyethylene glycol, monofunctional polypropylene glycol, and long-chain aliphatic alcohol, from the viewpoint of facilitating the formation of a phase-separated structure.

[0053] The long-chain aliphatic alcohol preferably has 5 to 25 carbon atoms, more preferably 6 to 23. 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-decan-1-ol, 2-ethyl-decan-1-ol, and 2-hexyl-octan-1-ol; and 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 alone or in combination of two or more. Among these, branched aliphatic saturated alcohols are preferred from the viewpoint of their tendency to become liquid and their reduced crystallinity.

[0054] 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 alone or in combination of two or more.

[0055] Examples of monofunctional polypropylene glycols include compounds in which one end of polypropylene glycol is blocked, such as polypropylene monoalkyl ethers such as 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-octyldodecaether; and polypropylene glycol monoesters such as polypropylene glycol monoacetate and polypropylene glycol monoacetate.

[0056] The molecular weight of the monofunctional alcohol (IA) is preferably in the range of 100 to 20,000, more preferably in the range of 150 to 10,000. The molecular weight is a value calculated based on the hydroxyl value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0057] The monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB) serving as a raw material for the compound represented by chemical formula (I) is not particularly limited, but is preferably a compound exemplified as a monofunctional carboxylic acid (II-B) described later and / or its acid anhydride, or a dicarboxylic acid and / or its acid anhydride, such as an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, or an aromatic dicarboxylic acid. The aliphatic dicarboxylic acid and its acid anhydride preferably have a carboxyl group at at least one end, and more preferably have carboxyl groups at both ends, and examples thereof 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 alicyclic dicarboxylic acid and its acid anhydride preferably have a carboxyl group at at least one end, and more preferably have carboxyl groups at both ends, and examples thereof include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, and 1,4-cyclohexanedicarboxylic acid. Examples of the aromatic dicarboxylic acid and / or its acid anhydride include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid. These may be used alone or in combination.

[0058] Of the monofunctional or polyfunctional carboxylic acids and / or acid anhydrides thereof (IB), linear aliphatic dicarboxylic acids are more preferred because they have low viscosity and are likely to form phase separation, and among these, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid are preferred.

[0059] The molecular weight of the monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB) is preferably in the range of 110 to 400, more preferably in the range of 140 to 350. The molecular weight is a value calculated based on the acid value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0060] In the compound represented by the chemical formula (I), the reaction between the monofunctional alcohol (IA) and a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB) is carried out in such a manner that the molar equivalent ratio (hydroxyl groups / carboxyl groups) of the molar equivalent number of hydroxyl groups in the monofunctional alcohol (IA) to the molar equivalent number of carboxyl groups in the monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB) is preferably in the range 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 in the above range, the carboxyl groups of the monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB) can be blocked with the monofunctional alcohol (IA).

[0061] The polyester and / or polyether ester (IC) having a carboxyl group at one or both ends, which is the raw material for the compound represented by chemical formula (I), can be, for example, a reaction product of a polyether polyol and a polybasic acid. These polyols can be used alone or in combination of two or more.

[0062] Examples of the polyether polyol that can be used include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Among these, polypropylene glycol is preferred in terms of further achieving the effects of the present invention.

[0063] The polybasic acid may be used alone or in combination of two or more kinds. Examples of the polybasic acid that can be used include 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.

[0064] Furthermore, examples of the polyester and / or polyether ester (IC) having a carboxyl group at one end or both ends, which is used as a raw material for the compound represented by chemical formula (I), include polyester (IC-1) or polyether ester (IC-2) obtained by reacting a polyol with a polycarboxylic acid; and polyester obtained by copolymerizing the polyester (IC-1) with a polyester obtained by ring-opening polymerization of a cyclic ester compound.

[0065] The polyol used as a raw material for the polyester (IC-1) may be one or more kinds, and examples thereof include 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-propanediol, and the like. Examples include aliphatic polyols such as bisphenol A, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl-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 modifying the above-mentioned polyols having an aromatic structure with alkylene oxide.

[0066] The molecular weight of the polyol that is a raw material for the polyester (IC-1) is preferably 50 or more, and preferably 1,500 or less, more preferably 1,000 or less, and even more preferably 700 or less. The molecular weight is a value calculated based on the hydroxyl value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0067] Furthermore, examples of polyols that can be used as raw materials for the polyether ester (IC-2) include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. These can be used alone or in combination of two or more.

[0068] The molecular weight of the polyol used as a raw material for the polyetherester (IC-2) is preferably 400 or more, and more preferably 700 or more, and is preferably 4,000 or less, more preferably 2,000 or less, in terms of the upper molecular weight. The molecular weight is a value calculated based on the hydroxyl value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0069] The polycarboxylic acid that is a raw material for the polyester and / or polyetherester (IC) can be one or more types. Examples of the polycarboxylic acid that can be used include 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.

[0070] The polyester and / or polyetherester (IC) having a carboxyl group 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 of the carboxyl group contained in the reaction raw materials is greater than the equivalent of the hydroxyl group.

[0071] The molecular weight of the polyester and / or polyetherester (IC) having a carboxyl group at one or both ends is preferably in the range of 140 to 40000, more preferably in the range of 140 to 20000. The molecular weight is a value calculated based on the acid value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0072] In the compound represented by the chemical formula (I), the reaction between the monofunctional alcohol (IA) and the polyester and / or polyether ester (IC) having carboxyl groups at one or both ends is preferably carried out in a molar equivalent ratio (hydroxyl group / carboxyl group) of the molar equivalent number of hydroxyl groups in the monofunctional alcohol (IA) to the molar equivalent number of carboxyl groups in the polyester and / or polyether ester (IC) having carboxyl groups at one or both ends, in the range of 0.5 to 2, more preferably 0.7 to 1.4, and even more preferably 0.9 to 1.1. By setting the equivalent ratio in the above range, the carboxyl groups at both ends of the polyester and / or polyether ester (IC) having carboxyl groups can be blocked with the monofunctional alcohol (IA).

[0073] The compound represented by the chemical formula (II) (end-capped polyether oligomer) may be, for example, a reaction product of a compound (II-A) having one or more hydroxyl groups with a monofunctional carboxylic acid (II-B).

[0074] Examples of the monofunctional or polyfunctional alcohol (II-A) having one or more ether groups, which is a raw material for the compound represented by the chemical formula (II), include the monofunctional alcohols exemplified for the monofunctional alcohol (IA) described above, polyether polyols, polyether ester polyols, hydroxyl group-containing urethane resins made from polyether polyols, and hydroxyl group-containing urethane resins made from polyether ester polyols. These may be used alone or in combination of two or more. The monofunctional or polyfunctional alcohol (II-A) having one or more ether groups has one or more hydroxyl groups, and preferably has a hydroxyl group at at least one end in the longitudinal direction of the main chain, and more preferably has a hydroxyl group at each of both ends.

[0075] The molecular weight of the monofunctional or polyfunctional alcohol (II-A) having an ether group 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 hydroxyl value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0076] Examples of the monofunctional carboxylic acid (II-B) that serves as a raw material for the compound represented by the chemical formula (II) include aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids. These may be used alone or in combination of two or more. Among these, aliphatic monocarboxylic acids are preferred because they are prone to phase separation and esterification reactions. The aliphatic monocarboxylic acid preferably has 5 to 20 carbon atoms.

[0077] The aliphatic monocarboxylic acid may be linear or branched.

[0078] The aliphatic monocarboxylic acid may be a saturated aliphatic monocarboxylic acid or an unsaturated aliphatic monocarboxylic acid, but is preferably a saturated aliphatic monocarboxylic acid for reasons of storage stability.

[0079] Examples of aliphatic monocarboxylic acids include caproic acid, 2-ethylhexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, etc. These may be used alone or in combination of two or more.

[0080] The 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 a value 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 chemical formula (II), the reaction between the monofunctional or polyfunctional alcohol (II-A) having an ether group and the monofunctional carboxylic acid (II-B) is carried out in such a manner that the molar equivalent ratio (hydroxyl group / carboxyl group) of the molar equivalent number of hydroxyl groups in the monofunctional or polyfunctional alcohol (II-A) having an ether group to the molar equivalent number of carboxyl groups in the monofunctional carboxylic acid (II-B) is preferably carried out in the range 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 in the above range, the hydroxyl groups of the monofunctional or polyfunctional alcohol (II-A) having an ether group can be blocked with the monofunctional carboxylic acid (II-B).

[0082] Examples of the compound represented by chemical formula (III) (end-capped polyether oligomer and / or end-capped polyether ester oligomer) include a reaction product of a monofunctional or polyfunctional alcohol (III-A) having one or more ether groups with a monofunctional isocyanate (III-B).

[0083] Examples of the monofunctional or polyfunctional alcohol (III-A) having one or more ether groups, which is a raw material for the compound represented by the chemical formula (III), include the compounds exemplified for the monofunctional alcohol (IA) described above, polyether polyols, polyether ester polyols, hydroxyl group-containing urethane resins made from polyether polyols, hydroxyl group-containing urethane resins made from polyether ester polyols, etc. The monofunctional or polyfunctional alcohol compound (III-A) has one or more hydroxyl groups, and preferably has a hydroxyl group at at least one end in the longitudinal direction of the main chain, and more preferably has a hydroxyl group at each of both ends.

[0084] The molecular weight of the monofunctional or polyfunctional alcohol (III-A) having one or more ether groups is preferably in the range of 300 to 40,000, more preferably in the range of 800 to 20,000. The molecular weight is a value calculated based on the hydroxyl value in accordance with the potentiometric titration method of JIS K 0070:1992.

[0085] Examples of the monofunctional isocyanate (III-B) that is a raw material for the compound represented by the 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 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 indicates a value 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 chemical formula (III), the reaction between a monofunctional or polyfunctional alcohol (III-A) having one or more ether groups and a monofunctional isocyanate (III-B) is carried out in such a manner that the equivalent ratio (OH / NCO) of the number of equivalents of hydroxyl groups in the monofunctional or polyfunctional alcohol (III-A) having one or more ether groups (OH) to the number of equivalents of isocyanate groups in the monofunctional isocyanate (III-B) (NCO) is preferably carried out 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) in the above range, the hydroxyl groups of the monofunctional or polyfunctional alcohol (III-A) having one or more ether groups can be blocked with the monofunctional isocyanate (III-B).

[0088] The number average molecular weight of the modified resin (C) having an ether concentration of 11.5 to 23 mol / kg is preferably 500 to 50,000, more preferably 1,000 to 30,000, in order to further obtain the effects of the present invention. The number average molecular weight of the modified resin (C) is measured by gel permeation chromatography (GPC) under the following conditions.

[0089] Measurement apparatus: High-speed GPC apparatus ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used, connected in series: "TSKgel G5000" (7.8 mm I.D. x 30 cm) x 1, "TSKgel G4000" (7.8 mm I.D. x 30 cm) x 1, "TSKgel G3000" (7.8 mm I.D. x 30 cm) x 1, "TSKgel G2000" (7.8 mm I.D. x 30 cm) x 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% by mass) Standard sample: A calibration curve was prepared using the following standard polystyrene.

[0090] (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

[0091] The content of the ether having an ether concentration of 11.5 to 23 mol / kg 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, based on the non-volatile content of the thermosetting resin composition.

[0092] As the modified resin (C), modified resins other than those having an ether concentration of 11.5 to 23 mol / kg can also be used in combination, for example, polyethylene glycol, polypropylene glycol, polybutylene glycol, polyolefin polyol, polybutadiene polyol, polyester polyol, polycarbonate polyol, etc. Polyols, or hydroxyl group-containing urethane resins, acrylic resins, styrene-butadiene copolymers, etc., made from one or more of these polyols can be used. The content of the modified resin (C) having an ether concentration of 11.5 to 23 mol / kg is preferably 50 mass% or more, more preferably 70 mass% or more, even more preferably 90 mass% or more, and particularly preferably substantially 100 mass%.

[0093] 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 base level. Examples of inorganic fine particles that can be used 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, and titanium oxide. Silica is preferred, and fused silica is more preferred. The shape of the silica may be either crushed or spherical, and spherical is preferred from the viewpoint of increasing the blending amount while suppressing the melt viscosity of the thermosetting resin composition.

[0094] The volume average particle diameter of the inorganic fine particles is, for example, 0.01 μm or more, more preferably 0.03 μm or more, and is 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 inorganic fine particles can be measured by a laser diffraction method.

[0095] Examples of the fibers include inorganic fibers such as glass fibers and carbon fibers, and organic fibers may also be used. The inorganic fibers may be long or short fibers. The carbon fibers may 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, and, for example, 30 μm or less, preferably 20 μm or less, and more preferably 15 μm or less.

[0096] The fibers may be dispersed in the thermosetting resin composition, may be oriented in a single direction, or may be 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.

[0097] The content of the filler (D) in the nonvolatile content of the thermosetting composition is 40% by mass or more, preferably 60% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less.

[0098] The thermosetting resin composition of the present invention contains the above components (A) to (D) as essential components, but may also contain other additives as needed.

[0099] Examples of the other additives that can be used include flame retardants, organic solvents, conductive particles, rubber, fillers, silane coupling agents, release agents, pigments, and emulsifiers.

[0100] The thermosetting resin composition of the present invention can be obtained by mixing the above-mentioned components and can be cured by heat curing to form a cured product. The cured product may be in the form of a laminate, a cast, an adhesive layer, a coating film, a film, or the like.

[0101] Applications of the thermosetting resin composition of the present invention include semiconductor encapsulation materials, printed wiring board materials, resin casting materials, adhesives, interlayer insulating materials for build-up substrates, and adhesive films for build-up substrates. Among these applications, in the insulating materials for printed wiring boards and electronic circuit boards and adhesive films for build-up substrates, the composition can be used as an insulating material for so-called substrates with built-in electronic components, in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. Among these, the composition is preferably used for printed wiring board materials and adhesive films for build-up substrates because of its properties such as high heat resistance, low thermal expansion, low viscosity, low elastic modulus, and solvent solubility.

[0102] The semiconductor encapsulating material can be prepared from the thermosetting composition of the present invention by thoroughly melt-mixing the thermosetting resin composition using, for example, an extruder, kneader, rolls, or the like until it becomes homogeneous.

[0103] When the thermosetting resin composition of the present invention is used as a semiconductor encapsulating material, it can be molded into a semiconductor package. Specifically, the composition is molded using a casting machine, a transfer molding machine, an injection molding machine, or the like, and then heated at 50 to 200°C for 2 to 10 hours to obtain a molded product, that is, a semiconductor device.

[0104] In addition, a method for producing a printed circuit board using the thermosetting resin composition of the present invention includes impregnating a reinforcing substrate with the thermosetting resin composition, overlaying copper foil, and thermocompression bonding. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. More specifically, the thermosetting resin composition is first heated (preferably at 50 to 170°C depending on the type of organic solvent (F)) to obtain a prepreg, which is a cured product. The resin content in the prepreg is preferably 20% by mass or more and 60% by mass or less. The prepreg is then laminated, copper foil is overlaid, and thermocompression bonding is performed at 170 to 300°C for 10 minutes to 3 hours under a pressure of 1 to 10 MPa to obtain the desired printed circuit board.

[0105] When the thermosetting resin composition of the present invention is used as a conductive paste, for example, a method in which conductive particles (fine conductive particles) are dispersed in the thermosetting resin composition to form a composition for an anisotropic conductive film, or a method in which the composition is made into a paste resin composition for circuit connection that is liquid at room temperature or an anisotropic conductive adhesive can be mentioned.

[0106] For example, a method for obtaining an interlayer insulating material for build-up substrates from the thermosetting resin composition of the present invention involves applying the thermosetting resin composition to a circuit-formed wiring board using a spray coating method, curtain coating method, or the like, followed by curing. Subsequently, if necessary, desired through-holes or other holes are drilled, followed by treatment with a roughening agent, rinsing the surface with hot water to form a roughened surface, and then plating with a metal such as copper. The plating method is preferably electroless plating or electrolytic plating, and examples of the roughening agent include oxidizing agents, alkalis, and organic solvents. This process is repeated as desired to alternately build up resin insulating layers and conductor layers with a predetermined circuit pattern, thereby obtaining a build-up substrate. However, drilling through-holes is performed after forming the outermost resin insulating layer. Alternatively, a build-up substrate can be produced by forming a resin-coated copper foil, in which the thermosetting resin composition is semi-cured on copper foil, and then thermocompressing the resulting copper foil onto a circuit-formed wiring board at 170 to 300°C to form a roughened surface, thereby eliminating the plating process.

[0107] A method for producing a build-up film from the thermosetting resin composition of the present invention includes, for example, applying the thermosetting resin composition of the present invention onto a support film to form a resin composition layer, thereby producing a build-up film for a multilayer printed wiring board.

[0108] When the thermosetting resin composition of the present invention is used for a build-up film, it is essential that the film softens under the lamination temperature conditions (usually 70°C to 140°C) in a vacuum lamination method and exhibits fluidity (resin flow) that allows the resin to fill via holes or through holes present in the circuit board simultaneously with lamination of the circuit board. It is preferable to blend the above-mentioned components so as to exhibit such properties.

[0109] Here, the diameter of the through-holes in a multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to make it possible to fill the resin within this range. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes.

[0110] Specifically, the adhesive film can be produced by preparing a varnish-like thermosetting resin composition of the present invention, applying the varnish-like composition to the surface of the support film (Y), and then drying the organic solvent by heating or blowing hot air or the like to form a layer (X) of the thermosetting composition.

[0111] The thickness of the layer (X) to be formed is usually equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

[0112] The layer (X) in the present invention may be protected with a protective film described below. By protecting the layer with a protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be prevented.

[0113] Examples of the support film and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be subjected to a mud treatment, a corona treatment, or a release treatment.

[0114] The thickness of the support film is not particularly limited, but is usually in the range of 10 to 150 μm, preferably 25 to 50 μm, and the thickness of the protective film is preferably 1 to 40 μm.

[0115] The support film (Y) is peeled off after laminating it onto the circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat cured, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is usually subjected to a release treatment in advance.

[0116] Next, a method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, to peel off a protective film if the layer (X) is protected by the protective film, and then laminate the layer (X) onto one or both sides of the circuit board so that the layer (X) is in direct contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be a batch method or a continuous method using a roll. Furthermore, the adhesive film and the circuit board may be heated (preheated) before lamination, if necessary.

[0117] The lamination conditions are a pressure-bonding temperature (lamination temperature) of preferably 70 to 140°C and a pressure-bonding pressure of preferably 1 to 11 kgf / cm. 2 (9.8×104~107.9×104N / m 2 ) and lamination is preferably carried out under reduced pressure of 20 mmHg (26.7 hPa) or less.

[0118] The method for obtaining the cured product of the present invention may be in accordance with a general method for curing a thermosetting resin composition. For example, the heating temperature conditions may be appropriately selected depending on the type of curing agent to be combined, the intended use, etc., and the composition obtained by the above method may be heated in a temperature range of about 20 to 300°C.

[0119] [Epoxy Resin Modifier] The epoxy resin modifier of the present invention is a terminal-capped polyether oligomer and / or a terminal-capped polyether ester oligomer. The terminal-capped polyether oligomer and / or the terminal-capped polyether ester oligomer may be a compound represented by any one of the following chemical formulas (I) to (III).

[0120]

[0121] R1, R2 and n1 in the chemical formula (I) are the same as defined above.

[0122]

[0123] In the chemical formula (II), R3, R4, and n2 are the same as defined above.

[0124]

[0125] In the chemical formula (III), R5, R6, and n3 are the same as defined above.

[0126] When mixed with an epoxy resin, the epoxy resin modifier of the present invention forms a phase-separated structure, which can reduce the thermal expansion coefficient and elastic modulus of the mixture and suppress warping during curing.

[0127] Examples of the end-capped polyether oligomer represented by the chemical formula (I) include a reaction product of a monofunctional alcohol (IA) with a monofunctional or polyfunctional carboxylic acid and / or its acid anhydride (IB), or a reaction product of a monofunctional alcohol (IA) with a polyester and / or polyether ester (IC) having carboxyl groups at one or both ends. Among these, it is preferable that the monofunctional alcohol (IA) contains a monofunctional polypropylene glycol.

[0128] The end-capped polyester oligomer represented by the chemical formula (II) may be, for example, a reaction product of a monofunctional or polyfunctional alcohol (II-A) having one or more ether groups with a monofunctional carboxylic acid (II-B).

[0129] Examples of the end-capped polyether oligomer and / or end-capped polyether ester oligomer represented by the chemical formula (III) include a reaction product of a monofunctional or polyfunctional alcohol (III-A) having one or more ether groups with a monofunctional isocyanate (III-B).

[0130] Details of the terminal-capped polyether oligomer and / or terminal-capped polyether ester oligomer, which are the epoxy resin modifier of the present invention, can be the same as the details of the terminal-capped polyether oligomer and / or terminal-capped polyether ester oligomer used in the modified resin (C) in the thermosetting resin composition of the present invention described above, and therefore will not be described here.

[0131] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any configuration that is substantially identical to the technical idea described in the claims of the present disclosure and that provides similar effects is included within the technical scope of the present disclosure.

[0132] The present invention will be described in more detail below with reference to examples.

[0133] Example 1 6.55 parts by mass of epoxy resin 1 (EPICLON 830CRP manufactured by DIC Corporation), 6.55 parts by mass of epoxy resin 2 (jER 630 manufactured by Mitsubishi Chemical Corporation), 6.90 parts by mass of amine curing agent (KAYAHARD A-A manufactured by Nippon Kayaku Co., Ltd.), and 5 parts by mass of polyetherester polyol 1 (a reaction product of bifunctional polypropylene glycol having a number average molecular weight of 1,000, isophthalic acid, and sebacic acid; number average molecular weight: 2,000, ether concentration: 14.9 mol / kg) were blended into a mixing vessel and stirred at an internal temperature of 100° C. until the mixture was dissolved. Next, 37.5 parts by mass of fused silica 1 (FB-5SDC manufactured by Denka Company Limited) and 37.5 parts by mass of fused silica 2 (FB-5604FC manufactured by Denka Company Limited) were uniformly blended to obtain a thermosetting resin composition.

[0134] Example 2 A thermosetting resin composition was obtained in the same manner as in Example 1, except that the amount of the epoxy resin 1 used was changed from 6.55 parts by mass to 7.37 parts by mass, the amount of the epoxy resin 2 used was changed from 6.55 parts by mass to 7.37 parts by mass, the amount of the amine curing agent used was changed from 6.90 parts by mass to 7.76 parts by mass, and the amount of the polyetherester polyol 1 used was changed from 5 parts by mass to 2.5 parts by mass.

[0135] Example 3 A thermosetting resin composition was obtained in the same manner as in Example 1, except that the amount of the epoxy resin 1 used was changed from 6.55 parts by mass to 5.74 parts by mass, the amount of the epoxy resin 2 used was changed from 6.55 parts by mass to 5.74 parts by mass, the amount of the amine curing agent used was changed from 6.90 parts by mass to 6.02 parts by mass, and the amount of the polyetherester polyol 1 used was changed from 5 parts by mass to 7.5 parts by mass.

[0136] Example 4 A thermosetting resin composition was obtained in the same manner as in Example 1, except that the polyetherester polyol 1 was changed to polyetherester polyol 2 (a reaction product of bifunctional polypropylene glycol having a number average molecular weight of 3,000 and ε-caprolactone; number average molecular weight: 3,300; ether concentration: 15.3 mol / kg).

[0137] Example 5 6.55 parts by mass of epoxy resin 1 (EPICLON 830CRP manufactured by DIC Corporation), 6.55 parts by mass of epoxy resin 2 (jER 630 manufactured by Mitsubishi Chemical Corporation), 6.90 parts by mass of an amine curing agent (KAYAHARD A-A manufactured by Nippon Kayaku Co., Ltd.), and 5 parts by mass of end-capped polyether ester oligomer (a reaction product of polypropylene glycol monobutyl ether (NEWPOL LB-285 manufactured by Sanyo Chemical Industries, Ltd., monofunctional polypropylene glycol, molecular weight 1170) and sebacic acid (molecular weight 202.25) at a molar ratio of 2:1; number average molecular weight: 2,500, hydroxyl value: 2.7, acid value: 3.3, ether concentration: 15.1 mol / kg) were blended into a mixing vessel, and the mixture was stirred at an internal temperature of 100°C until the mixture was dissolved. Next, 37.5 parts by mass of fused silica 1 ("FB-5SDC" manufactured by Denka Company Limited) and 37.5 parts by mass of fused silica 2 ("FB-5604FC" manufactured by Denka Company Limited) were uniformly blended to obtain a thermosetting resin composition.

[0138] The end-capped polyether ester oligomer corresponds to a compound in which R1 in the chemical formula (I) is represented by the following formula (3), R2 is represented by the following formula (4), and n1 = 2. Specifically, it is a compound represented by the following chemical formula (5).

[0139]

[0140]

[0141] (In the formulas (3) to (5), one of R7 and R8 is a hydrogen atom and the other is a methyl group, and n4 is an average of 18.9.)

[0142] Example 6 9.34 parts by mass of epoxy resin 3 ("EPICLON HP-4700" manufactured by DIC Corporation), 3.11 parts by mass of epoxy resin 4 ("jER YX-4000H" manufactured by Mitsubishi Chemical Corporation), 7.55 parts by mass of phenol novolac curing agent ("PHENOLITE TD-2131" manufactured by DIC Corporation), and 5 parts by mass of polyether ester polyol 1 were blended into a mixing vessel and stirred at an internal temperature of 130° C. until they were compatible. Next, 37.5 parts by mass of fused silica 1 ("FB-5SDC" manufactured by Denka Company Limited), 37.5 parts by mass of fused silica 2 ("FB-5604FC" manufactured by Denka Company Limited), and 0.125 parts by mass of triphenylphosphine were uniformly blended to obtain a thermosetting resin composition.

[0143] Comparative Example 1 A thermosetting resin composition was obtained in the same manner as in Example 1, except that the amount of the epoxy resin 1 used was changed from 6.55 parts by mass to 8.19 parts by mass, the amount of the epoxy resin 2 used was changed from 6.55 parts by mass to 8.19 parts by mass, the amount of the amine curing agent used was changed from 6.90 parts by mass to 8.62 parts by mass, and the amount of the polyetherester polyol 1 used was changed from 5 parts by mass to 0 parts by mass.

[0144] Comparative Example 2 A thermosetting resin composition was obtained in the same manner as in Example 1, except that a polyester polyol (a reaction product of ethylene glycol and adipic acid; number average molecular weight 2,000, ether concentration: 0 mol / kg) was used instead of the polyether ester polyol 1.

[0145] Comparative Example 3 A thermosetting resin composition was obtained in the same manner as in Example 6, except that the amount of the epoxy resin 3 used was changed from 9.34 parts by mass to 11.67 parts by mass, the amount of the epoxy resin 4 used was changed from 3.11 parts by mass to 3.89 parts by mass, the amount of the phenol novolac curing agent used was changed from 7.55 parts by mass to 9.44 parts by mass, and the amount of the polyether ester polyol 1 used was changed from 5 parts by mass to 0 parts by mass.

[0146] [Method for measuring thermal expansion coefficient] The thermosetting resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were thermally cured at 100°C for 1 hour and at 175°C for 2 hours, and the thermosetting resin compositions obtained in Example 6 and Comparative Example 3 were thermally cured at 175°C for 5 hours. Then, the linear thermal expansion coefficient was measured in the range of 40 to 60°C using a thermal analyzer TMA6200 (manufactured by Seiko Instruments Inc.) at a heating rate of 3°C / min. "Good": Less than 16 ppm / °C "Poor": 16 ppm / °C or more

[0147] [Method for measuring elastic modulus] The thermosetting resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were thermally cured at 100°C for 1 hour and 175°C for 2 hours, and the thermosetting resin compositions obtained in Example 6 and Comparative Example 3 were thermally cured at 175°C for 5 hours, and then the flexural modulus was measured in accordance with JIS K7171. "Good": Less than 14,000 MPa "Poor": 14,000 MPa or more

[0148] [Method of measuring viscosity] The viscosity of the modified resin (C) used in the examples and comparative examples was measured at 75°C using a cone and plate viscometer. "◎": Less than 200 mPa·s "◯": 200 mPa·s or more and less than 1000 mPa·s "×": 1000 mPa·s or more

[0149]

[0150]

[0151] The thermosetting resin composition of the present invention was found to have excellent low thermal expansion, low elastic modulus, and low viscosity. On the other hand, Comparative Examples 1 and 3, which are embodiments that do not use the modified resin (C), had poor low thermal expansion and low elastic modulus. Furthermore, Comparative Example 2, which is an embodiment that uses a polyester polyol that does not contain an ether group instead of the modified resin (C), had poor low thermal expansion.

Claims

1. A thermosetting composition comprising a thermosetting resin (A), a curing agent (B), a modified resin (C), and one or more fillers (D) selected from the group consisting of inorganic fine particles and fibers, The ether concentration of the modified resin (C) is 11.5 to 23 mol / kg. A thermosetting resin composition characterized in that the modified resin (C) comprises one or more selected from the group consisting of polyether ester polyols, urethane resins made from polyether polyols, and urethane resins made from polyether ester polyols.

2. The thermosetting resin composition according to claim 1, wherein the number average molecular weight of the modified resin (C) is 500 to 50,000.

3. The thermosetting resin composition according to claim 1, wherein the content of the modified resin (C) is 5 to 45% by mass.

4. A cured product of the thermosetting resin composition according to claim 1.

5. A semiconductor encapsulant comprising the thermosetting resin composition according to any one of claims 1 to 3.

6. A semiconductor device comprising the semiconductor encapsulant described in claim 5.

7. An insulating material for printed wiring boards comprising the thermosetting resin composition according to any one of claims 1 to 3.

8. A printed circuit board comprising the insulating material for printed circuit boards according to claim 7.