Resin composition

Abstract

To provide a resin composition that is cured into a product having a low dielectric loss tangent (Df) and can prevent occurrence of unevenness after its lamination.SOLUTION: A resin composition contains (A) a phosphorus-containing curing catalyst, (B) an epoxy resin, (C) an active ester compound, and (C) an inorganic filler, a content of the component (C) being 10 mass% or more with the nonvolatile component in the resin composition being 100 mass%, and a content of the component (D) being 60 mass% or more with the nonvolatile component in the resin composition being 100 mass%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition containing an epoxy resin. Further, it relates to a cured product, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

Background Art

[0002] As a manufacturing technique for printed wiring boards, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately laminated is known. In the manufacturing method by the build-up method, generally, the insulating layer is formed by curing a resin composition. In recent years, it has been required to further suppress the dielectric tangent of the insulating layer.

[0003] Heretofore, it has been known that by using an epoxy resin composition in which an active ester compound and an inorganic filler are highly blended as a resin composition for forming an insulating layer, the dielectric tangent of the insulating layer can be further suppressed (Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, when an epoxy resin composition in which an active ester compound and an inorganic filler are highly blended is used, the occurrence of unevenness after lamination has been a problem (see Test Example 2 for details of the unevenness after lamination).

[0006] An object of the present invention is to provide a resin composition capable of suppressing the dielectric tangent (Df) of a cured product to a low level and suppressing the occurrence of unevenness after lamination.

Means for Solving the Problems

[0007] In order to achieve the object of the present invention, the inventors have conducted intensive studies. As a result, in an epoxy resin composition in which (C) an active ester compound and (D) an inorganic filler are highly compounded at 10% by mass or more and 60% by mass or more, respectively, by using (A) a phosphorus-containing curing catalyst, surprisingly, the dielectric tangent (Df) of the cured product can be kept low, and the occurrence of unevenness after lamination treatment can be suppressed. Based on this finding, the present invention has been completed.

[0008] That is, the present invention includes the following. [1] A resin composition containing (A) a phosphorus-containing curing catalyst, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler, wherein the content of component (C) is 10% by mass or more when the non-volatile components in the resin composition are 100% by mass, and the content of component (D) is 60% by mass or more when the non-volatile components in the resin composition are 100% by mass. [2] The resin composition according to [1] above, wherein component (A) contains a phosphorus-containing curing catalyst selected from the group consisting of quaternary phosphonium salts and tertiary phosphines. [3] The resin composition according to [2] above, wherein component (A) contains a quaternary phosphonium salt. [4] The resin composition according to any one of [1] to [3] above, wherein the content of component (A) is 0.01% by mass or more when the non-volatile components in the resin composition are 100% by mass. [5] The resin composition according to any one of [1] to [4] above, wherein the content of component (A) is 3% by mass or less when the non-volatile components in the resin composition are 100% by mass. [6] The resin composition according to any one of [1] to [5] above, wherein the content of component (B) is 1% by mass to 20% by mass when the non-volatile components in the resin composition are 100% by mass. [7] The resin composition according to any one of [1] to [6] above, wherein the mass ratio of component (B) to component (A) ((B) component / (A) component) is 3 to 500. The resin composition according to any one of [1] to [7] above, wherein the mass ratio of component (C) to component (A) ((C) component / (A) component) is 5 to 1000. The resin composition according to any one of [1] to [8] above, wherein the mass ratio of component (D) to component (A) ((D) component / (A) component) is 30 to 5000. The resin composition according to any one of [1] to [9] above, wherein component (D) is silica. The resin composition according to any one of [1] to

[10] above, wherein the content of component (D) is 70% by mass or more when the non-volatile components in the resin composition are 100% by mass. The resin composition according to any one of [1] to

[11] above, further comprising an imidazole-based curing accelerator. The resin composition according to any one of [1] to

[12] above, further comprising a curing agent selected from the group consisting of a phenolic curing agent and a carbodiimide-based curing agent.

[14] The minimum melt viscosity is (500 Pa·s) 5000 poise or less, and the resin composition according to any one of [1] to

[13] above. The resin composition according to any one of [1] to

[14] above, wherein the dielectric tangent (Df) of the cured product of the resin composition is 0.0030 or less when measured at 5.8 GHz and 23°C. The cured product of the resin composition according to any one of [1] to

[15] above. A sheet-like laminated material containing the resin composition according to any one of [1] to

[15] above. A resin sheet having a support and a resin composition layer formed from the resin composition according to any one of [1] to

[15] above provided on the support. A printed wiring board including an insulating layer made of the cured product of the resin composition according to any one of [1] to

[15] above. A semiconductor device including the printed wiring board according to

[19] above.

Advantages of the Invention

[0009] According to the resin composition of the present invention, the dielectric tangent (Df) of the cured product can be kept low and the occurrence of unevenness after lamination can be suppressed.

Mode for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail according to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0011] <Resin Composition> The resin composition of the present invention contains (A) a phosphorus-containing curing catalyst, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler, the content of (C) the active ester compound is 10% by mass or more, and the content of (D) the inorganic filler is 60% by mass or more. By using such a resin composition, the dielectric tangent (Df) of the cured product can be kept low and the occurrence of unevenness after lamination can be suppressed.

[0012] In addition to (A) a phosphorus-containing curing catalyst, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler, the resin composition of the present invention may further contain an arbitrary component. Examples of the arbitrary component include (A') other curing accelerators, (C') other curing agents, (E) radical polymerizable compounds, (F) thermoplastic resins, (G) other additives, and (H) organic solvents. Hereinafter, each component contained in the resin composition will be described in detail.

[0013] <(A) Phosphorus-Containing Curing Catalyst> The resin composition of the present invention contains (A) a phosphorus-containing curing catalyst. (A) The phosphorus-containing curing catalyst has a function as a curing catalyst that promotes the curing reaction of (B) the epoxy resin. (A) The phosphorus-containing curing catalyst may be used alone or in combination of two or more.

[0014] (A) As the phosphorus-containing curing catalyst, it is preferable to include a phosphorus-containing curing catalyst selected from the group consisting of quaternary phosphonium salts and tertiary phosphines, and it is particularly preferable to include a quaternary phosphonium salt.

[0015] The quaternary phosphonium salt can be a salt composed of a quaternary phosphonium cation and an anion.

[0016] The quaternary phosphonium cation constituting the quaternary phosphonium salt is not particularly limited, but preferably has the formula (1):

[0017]

Chemical formula

[0018] (In the formula, R 1 , R 2 , R 3 and R 4 each independently represents an aryl group which may be substituted with a substituent selected from an alkyl group and an alkoxy group; or an alkyl group which may be substituted with a substituent selected from an aryl group and an alkoxy group.) is a quaternary phosphonium cation represented by.

[0019] The alkyl group is preferably an alkyl group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group and the like. The alkoxy group is preferably an alkoxy group having 1 to 14 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, and even more preferably an alkoxy group having 1 to 6 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group and the like. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like, and the phenyl group is particularly preferred.

[0020] Specific examples of the quaternary phosphonium cation constituting the quaternary phosphonium salt include tetraalkylphosphonium cations such as tetraethylphosphonium cation, tetrapropylphosphonium cation, tetraisopropylphosphonium cation, tetrabutylphosphonium cation, tetraisobutylphosphonium cation, tetra-tert-butylphosphonium cation, tetra pentylphosphonium cation, tetrahexylphosphonium cation, di-tert-butyldimethylphosphonium cation; tetraarylphosphonium cations such as tetraphenylphosphonium cation, (4-methylphenyl)triphenylphosphonium cation, (4-methoxyphenyl)triphenylphosphonium cation, phenyltris(4-methylphenyl)phosphonium cation, phenyltris(4-methoxyphenyl)phosphonium cation, tetrakis(4-methylphenyl)phosphonium cation, tetrakis(4-methoxyphenyl)phosphonium cation; alkyltriarylphosphonium cations such as methyltriphenylphosphonium cation, methoxymethyltriphenylphosphonium cation, ethyltriphenylphosphonium cation, propyltriphenylphosphonium cation, isopropyltriphenylphosphonium cation, butyltriphenylphosphonium cation, tris(4-methylphenyl)ethylphosphonium cation, tris(3-methylphenyl)ethylphosphonium cation, tris(2-methoxyphenyl)ethylphosphonium cation; aralkyltriarylphosphonium cations such as benzyltriphenylphosphonium cation and the like. Among them, the quaternary phosphonium cation selected from tetraalkylphosphonium cations and tetraarylphosphonium cations is preferred.

[0021] Specific examples of the anions constituting the quaternary phosphonium salt include halide ions such as chloride ion, bromide ion, iodide ion; hydroxide ion; dicyanamide ion; thiocyanate ion; aliphatic monocarboxylic acid ions such as formate ion, acetate ion, propionate ion, butyrate ion, valerate ion, caproate ion (hexanoate ion), enanthate ion, caprylate ion, pelargonate ion, caprate ion (decanoate ion), undecylate ion, laurate ion, tridecylate ion, myristate ion, palmitate ion, stearate ion, arachidate ion, α-linolenate ion, linoleate ion, palmitoleate ion, oleate ion, trimethylacetate ion, etc. (preferably having 1 to 30 carbon atoms); aromatic monocarboxylic acid ions such as benzoate ion, 4-methylbenzoate ion, etc. (preferably having 7 to 30 carbon atoms); hydrogen aliphatic dicarboxylate ions such as hydrogen hexahydrophthalate ion, etc. (preferably having 2 to 30 carbon atoms); hydrogen aromatic dicarboxylate ions such as hydrogen phthalate ion, 4-methylhydrogen phthalate ion, 4-methoxyhydrogen phthalate ion, etc. (preferably having 8 to 30 carbon atoms); hydrogen aliphatic tetracarboxylate ions such as dihydrogen hexahydropyromellitate ion, etc. (preferably having 6 to 30 carbon atoms); hydrogen aromatic tetracarboxylate ions such as dihydrogen pyromellitate ion, etc. (preferably having 10 to 30 carbon atoms); aryloxide ions such as phenolate ion, 4-methylphenolate ion, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate ion, etc. (preferably having 6 to 30 carbon atoms); aromatic borate ions such as tetraphenylborate ion, tetrakis(4-methylphenyl)borate ion, etc. (preferably aromatic borate ions having 4 aryls with 6 to 30 carbon atoms), and the like. Among them, anions selected from aliphatic monocarboxylic acid ions, hydrogen aliphatic dicarboxylate ions, hydrogen aromatic dicarboxylate ions, and aryloxide ions are preferred.

[0022] Specific examples of the quaternary phosphonium salts include aliphatic quaternary phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium hydrogen phthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; aromatic quaternary phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium iodide, butyltriphenylphosphonium bromide, methoxymethyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium hydrogen hexahydrophthalate, tetraphenylphosphonium hydrogen phthalate, tetraphenylphosphonium phenolate, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, ethyltriphenylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc.

[0023] Specific examples of the tertiary phosphine include aliphatic tertiary phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine; aromatic tertiary phosphines such as dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether; aromatic tertiary phosphine-borane complexes such as triphenylphosphine·triphenylborane; aromatic tertiary phosphine-quinone adducts such as triphenylphosphine·p-benzoquinone addition reactant, etc.

[0024] (A) The molecular weight of the phosphorus-containing curing catalyst is not particularly limited, but is preferably 2000 or less, more preferably 1500 or less, and particularly preferably 1000 or less. The lower limit is not particularly limited, but can be, for example, 200 or more, 300 or more, etc.

[0025] As the (A) phosphorus-containing curing catalyst, commercially available products may be used. For example, "TBP-DA", "TBP-LA", "TBP-3PC", "TBP-3S", "TPP-phthalic acid", etc. manufactured by Hokko Chemical Industry Co., Ltd. can be mentioned.

[0026] The content of the (A) phosphorus-containing curing catalyst in the resin composition is not particularly limited. However, from the viewpoint of suppressing the melt viscosity of the resin composition, when the non-volatile components in the resin composition are 100% by mass, it is preferably 7% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, even more preferably 2.5% by mass or less, and particularly preferably 2% by mass or less. The lower limit of the content of the (A) phosphorus-containing curing catalyst in the resin composition is not particularly limited. However, from the viewpoint of more significantly obtaining the desired effects of the present invention, when the non-volatile components in the resin composition are 100% by mass, it is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, still more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.07% by mass or more.

[0027] <(A’) Other curing accelerators> The resin composition of the present invention may further contain, as an optional component, (A’) other curing accelerators other than the (A) phosphorus-containing curing catalyst. (A’) Other curing accelerators may have a function as a curing catalyst that promotes the curing of the (B) epoxy resin, similar to the (A) phosphorus-containing curing catalyst.

[0028] (A’) As other curing accelerators, for example, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, etc. may be mentioned. Among them, from the viewpoint of improving crosslinkability, the resin composition of the present invention preferably contains an imidazole-based curing accelerator. (A’) Other curing accelerators may be used alone or in combination of two or more.

[0029] Examples of urea-based curing accelerators include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; aromatic dimethylureas such as 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N’,N’-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N’,N’-dimethylurea) [toluene bisdimethylurea], etc.

[0030] Examples of the guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, and the like.

[0031] Examples of imidazole-based curing accelerators include imidazole compounds such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

[0032] As the imidazole-based curing accelerator, commercially available products may be used. For example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Kasei Kogyo Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. can be mentioned.

[0033] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0034] Examples of amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, and the like.

[0035] As the amine-based hardening accelerator, commercially available products may be used. For example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc. and the like can be mentioned.

[0036] The content of (A') other hardening accelerators in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 1% by mass or less. The lower limit of the content of (A') other hardening accelerators in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, it can be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, and the like.

[0037] When the total of (A) phosphorus-containing curing catalyst and (A') other curing accelerators in the resin composition is 100% by mass, the content of (A) phosphorus-containing curing catalyst in the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more.

[0038] <(B) Epoxy resin> The resin composition of the present invention contains (B) an epoxy resin. (B) The epoxy resin is a curable resin having an epoxy group.

[0039] Examples of (B) epoxy resin include, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimide type epoxy resin, phenolphthalein type epoxy resin, and the like. (B) The epoxy resin may be used alone or in combination of two or more.

[0040] The resin composition preferably contains, as the (B) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more with respect to 100% by mass of the non-volatile component of the (B) epoxy resin.

[0041] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition of the present invention may contain only a liquid epoxy resin as the epoxy resin, or may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0042] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0043] Preferred liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, and epoxy resins having a butadiene structure.

[0044] Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycerol-type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidylamine-type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene-type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600", "JP-100", "JP-200" (epoxy resin having a butadiene structure) manufactured by Nippon Soda Co., Ltd.; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd., etc. These may be used alone or in combination of two or more.

[0045] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0046] Examples of the solid epoxy resin include a biphenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a naphthol novolak type epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, a phenol aralkyl type epoxy resin, a tetraphenylethane type epoxy resin, a phenolphthalimide type epoxy resin, and a phenolphthalein type epoxy resin.

[0047] Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" (naphthylene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolak-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", and "NC3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" and "ESN4100V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", and "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenolphthalimide-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and the like.These may be used alone or in combination of two or more.

[0048] (B) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, and particularly preferably 7:1 to 1:7.

[0049] (B) The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., still more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0050] (B) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by the gel permeation chromatography (GPC) method.

[0051] The content of the (B) epoxy resin in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably less than 30% by mass, more preferably 25% by mass or less, still more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of the (B) epoxy resin in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more.

[0052] The mass ratio of (B) epoxy resin to (A) phosphorus-containing curing catalyst in the resin composition ((B) component / (A) component) is preferably 0.5 or more, more preferably 3 or more, and particularly preferably 30 or more. The upper limit of the mass ratio of (B) epoxy resin to (A) phosphorus-containing curing catalyst in the resin composition ((B) component / (A) component) is preferably 1000 or less, more preferably 500 or less, and particularly preferably 200 or less.

[0053] <(C) active ester compound> The resin composition of the present invention contains (C) an active ester compound. The (C) active ester compound may be used alone or in combination of two or more in any ratio. The (C) active ester compound may have a function as an epoxy resin curing agent that reacts with the (B) epoxy resin to cause curing.

[0054] (C) As the active ester compound, generally, compounds having two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferably used. The active ester compound is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, dicyclopentadiene-type diphenol compound, phenol novolak, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0055] Specifically, as the (C) active ester compound, a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolak, and an active ester compound containing a benzoylated product of phenol novolak are preferable. Among them, at least one selected from a dicyclopentadiene type active ester compound and a naphthalene type active ester compound is more preferable, and a dicyclopentadiene type active ester compound is even more preferable. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferable.

[0056] Examples of commercially available products of the (C) active ester compound include, as the active ester compound containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC); as the active ester compound containing a naphthalene structure, "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC); as the phosphorus-containing active ester compound, "EXB9401" (manufactured by DIC), as the active ester compound which is an acetylated product of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation), as the active ester compound which is a benzoylated product of phenol novolak, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and as the active ester compound containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Inc.) and the like.

[0057] (C) The active ester group equivalent of the active ester compound is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., still more preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester compound per equivalent of the active ester group.

[0058] When the non-volatile components in the resin composition are taken as 100% by mass, the content of the (C) active ester compound in the resin composition is 10% by mass or more, preferably 11% by mass or more, more preferably 12% by mass or more, still more preferably 13% by mass or more, and particularly preferably 14% by mass or more. The upper limit of the content of the (C) active ester compound in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

[0059] The mass ratio of the (C) active ester compound to the (A) phosphorus-containing curing catalyst in the resin composition ((C) component / (A) component) is preferably 1 or more, more preferably 5 or more, and particularly preferably 50 or more. The upper limit of the mass ratio of the (C) active ester compound to the (A) phosphorus-containing curing catalyst in the resin composition ((C) component / (A) component) is preferably 2000 or less, more preferably 1000 or less, and particularly preferably 400 or less.

[0060] <(C’) Other curing agent> The resin composition of the present invention may further contain, as an optional component, a (C’) curing agent other than the (C) component. The (C’) other curing agent may be used alone or in any combination of two or more. Similar to the (C) active ester compound, the (C’) other curing agent may have a function as an epoxy resin curing agent that reacts with the (B) epoxy resin to cause curing.

[0061] (C’) As other curing agents, there are no particular limitations, but examples include phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol curing agents. The resin composition of the present invention particularly preferably contains a curing agent selected from the group consisting of phenolic curing agents and carbodiimide curing agents.

[0062] As phenolic curing agents, from the viewpoints of heat resistance and water resistance, phenolic curing agents having a novolac structure are preferred. Also, from the viewpoint of adhesion to the adherend, nitrogen-containing phenolic curing agents are preferred, and phenolic curing agents containing a triazine skeleton are more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, phenolic novolac resins containing a triazine skeleton are preferred. Specific examples of phenolic curing agents include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd., "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M", etc. manufactured by DIC Corporation.

[0063] Examples of the carbodiimide-based curing agent include curing agents having one or more, preferably two or more carbodiimide structures in one molecule, such as aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xilylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly(methylenebiscyclohexylene carbodiimide), and poly(isophorone carbodiimide); and aromatic polycarbodiimides such as poly(phenylene carbodiimide), poly(naphthylene carbodiimide), poly(tolylene carbodiimide), poly(methyldiisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), poly(diisopropylphenylene carbodiimide), poly(xylylene carbodiimide), poly(tetramethylxylylene carbodiimide), poly(methylenediphenylene carbodiimide), and poly[methylenebis(methylphenylene) carbodiimide].

[0064] Examples of commercially available carbodiimide-based curing agents include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; "Stabaxol P", "Stabaxol P400", "Highcadyl 510", etc. manufactured by Rhein Chemie.

[0065] Examples of the acid anhydride-based curing agent include curing agents having one or more acid anhydride groups in one molecule, and curing agents having two or more acid anhydride groups in one molecule are preferred. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as a styrene-maleic acid resin copolymerized from styrene and maleic acid. Commercially available products of the acid anhydride-based curing agent include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Rika Co., Ltd., "YH-306", "YH-307" manufactured by Mitsubishi Chemical Corporation, "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd., and "EF-30", "EF-40", "EF-60", "EF-80" manufactured by Cray Valley Co., Ltd., etc.

[0066] The amine-based curing agent may be a curing agent having one or more, preferably two or more, amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propane. propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. As the amine-based curing agent, commercially available products may be used, and examples thereof include "SEIKACURE-S" manufactured by Seika Corporation, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0067] Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0068] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; prepolymers in which part of these cyanate resins is triazine-ized, and the like. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230", "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazine-ized to form trimers), etc. manufactured by Lonza Japan Co., Ltd.

[0069] Examples of thiol curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl) isocyanurate, and the like.

[0070] (C’) The reaction group equivalent of other curing agents is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., still more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reaction group equivalent is the mass of the curing agent per equivalent of the reaction group.

[0071] The content of (C') other curing agents in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of (C') other curing agents in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, for example, it can be 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, etc.

[0072] When the total of (C) active ester compounds and (C') other curing agents in the resin composition is 100% by mass, the content of (C) active ester compounds in the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more.

[0073] <(D) Inorganic filler> The resin composition of the present invention contains (D) inorganic filler. The (D) inorganic filler is contained in the resin composition in a particulate state.

[0074] (D) As the material of the inorganic filler, an inorganic compound is used. (D) As the material of the inorganic filler, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. may be mentioned. Among these, silica is particularly preferred. As silica, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. may be mentioned. Also, spherical silica is preferred as silica. (D) The inorganic filler may be used alone or in combination of two or more in any ratio.

[0075] (D) Examples of commercially available products of the inorganic filler include, for example, "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd.; "SP60-05", "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs Co., Ltd.; "DAW-03", "FB-105FD" manufactured by Denka Co., Ltd., etc.

[0076] (D) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less. The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis using a laser diffraction / scattering type particle size distribution measuring device and taking the median diameter as the average particle size. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample can be used to measure the volume-based particle size distribution of the inorganic filler using a laser diffraction type particle size distribution measuring device with the light source wavelengths of blue and red and in a flow cell method, and the average particle size can be calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0077] (D) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, still more preferably 1 m 2 / g or more, and particularly preferably 3 m 2 / g or more. The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 70 m 2 / g or less, still more preferably 50 m 2 / g or less, and particularly preferably 40 m 2 / g or less. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) in accordance with the BET method and calculating the specific surface area using the BET multipoint method.

[0078] (D) From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is preferably treated with a surface treatment agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazane compounds, titanate-based coupling agents, and the like. Further, the surface treatment agent may be used alone or in any combination of two or more kinds.

[0079] Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane), "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc., all manufactured by Shin-Etsu Chemical Co., Ltd.

[0080] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent preferably falls within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably surface-treated with 0.2% to 3% by mass, and even more preferably surface-treated with 0.3% to 2% by mass.

[0081] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, and 0.1 mg / m2 The above is more preferable, and 0.2 mg / m 2 or more is even more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, 1.0 mg / m 2 or less is preferable, 0.8 mg / m 2 or less is more preferable, and 0.5 mg / m 2 or less is even more preferable.

[0082] (D) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 °C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0083] When the content of the (D) inorganic filler in the resin composition is based on 100% by mass of the non-volatile components in the resin composition, it is 60% by mass or more, preferably 63% by mass or more, more preferably 66% by mass or more, even more preferably 68% by mass or more, and particularly preferably 70% by mass or more. The upper limit of the content of the (D) inorganic filler in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it can be preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, and particularly preferably 75% by mass or less.

[0084] The mass ratio of the (D) inorganic filler to the (A) phosphorus-containing curing catalyst in the resin composition ((D) component / (A) component) is preferably 5 or more, more preferably 30 or more, and particularly preferably 300 or more. The upper limit of the mass ratio of the (D) inorganic filler to the (A) phosphorus-containing curing catalyst in the resin composition ((D) component / (A) component) is preferably 10,000 or less, more preferably 5,000 or less, and particularly preferably 2,000 or less.

[0085] <(E) Radical polymerizable compound> The resin composition of the present invention may contain an (E) radical polymerizable compound as an optional component. The (E) radical polymerizable compound may be used alone or in any combination of two or more.

[0086] In one embodiment, the (E) radical polymerizable compound is a radical polymerizable compound having an ethylenically unsaturated bond. The (E) radical polymerizable compound is not particularly limited, and examples thereof include unsaturated hydrocarbon groups such as allyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, p-vinylphenyl group, m-vinylphenyl group, o-vinylphenyl group; α,β-unsaturated carbonyl groups such as acryloyl group, methacryloyl group, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group), etc. It may have a radical polymerizable group. The (E) radical polymerizable compound preferably has two or more radical polymerizable groups.

[0087] Examples of the (E) radical polymerizable compound may include (meth)acrylic radical polymerizable compounds, styrene radical polymerizable compounds, allyl radical polymerizable compounds, maleimide radical polymerizable compounds, etc.

[0088] (Meth)acrylic radical polymerizable compounds are, for example, compounds having one or more, preferably two or more acryloyl groups and / or methacryloyl groups. Examples of (meth)acrylic radical polymerizable compounds include low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylate compounds such as cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate; low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylate compounds such as dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylate compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate; high molecular weight (molecular weight 1000 or more) acrylate compounds such as (meth)acryl-modified polyphenylene ether resin, and the like.Examples of commercially available (meth)acrylic radical polymerizable compounds include, for example, "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate), "KAYARAD R-604" (dioxane glycol diacrylate) manufactured by Nippon Kayaku Co., Ltd., "SA9000", "SA9000-111" (methacrylic modified polyphenylene ether) manufactured by SABIC Innovative Plastics, etc.

[0089] Styrene-based radical polymerizable compounds are, for example, compounds having one or more, preferably two or more vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene-based radical polymerizable compounds include low molecular weight (molecular weight less than 1000) styrene-based compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether; high molecular weight (molecular weight 1000 or more) styrene-based compounds such as vinylbenzyl modified polyphenylene ether resin, styrene-divinylbenzene copolymer, etc. Examples of commercially available styrene-based radical polymerizable compounds include, for example, "ODV-XET(X03)", "ODV-XET(X04)", "ODV-XET(X05)" (styrene-divinylbenzene copolymer) manufactured by Nippon Steel Chemical & Material Co., Ltd., "OPE-2St 1200", "OPE-2St 2200" (vinylbenzyl modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Company, Inc.

[0090] An allyl-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more allyl groups. Examples of the allyl-based radically polymerizable compound include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, diallyl 2,3-naphthalenecarboxylate; allyl ester compounds of isocyanuric acid such as 1,3,5-triallyl isocyanurate, 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; allyl silane compounds such as diallyl diphenyl silane and the like. Commercially available products of the allyl-based radically polymerizable compound include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nittsu Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., the product name "DAND" (diallyl 2,3-naphthalenecarboxylate) manufactured by Nippon Distillation Industry Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Kasei Kogyo Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Co., Ltd. and the like.

[0091] The maleimide-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide-based radically polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. Examples of commercially available products include, for example, "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (a dimer diamine structure-containing maleimide compound) manufactured by Designer Molecules, Inc., "BMI-6100" (an aromatic maleimide compound) manufactured by Designer Molecules, Inc., "MIR-5000-60T", "MIR-3000-70MT" (biphenyl aralkyl type maleimide compounds) manufactured by Nippon Kayaku Co., Ltd., "BMI-70", "BMI-80" manufactured by K.I. Kasei Co., Ltd., "BMI-2300", "BMI-TMH" manufactured by Daiwa Kasei Kogyo Co., Ltd., and the like. Further, as the maleimide-based radically polymerizable compound, a maleimide resin (an indane ring skeleton-containing maleimide compound) disclosed in Invention Association Publication Technical Report Publication No. 2020-500211 may be used.

[0092] (E) The ethylene unsaturated bond equivalent of the radically polymerizable compound is preferably 20 g / eq. to 3000 g / eq., more preferably 50 g / eq. to 2500 g / eq., still more preferably 70 g / eq. to 2000 g / eq., and particularly preferably 90 g / eq. to 1500 g / eq. The ethylene unsaturated bond equivalent is the mass of the radically polymerizable compound per equivalent of the ethylene unsaturated bond.

[0093] (E) The weight average molecular weight (Mw) of the radically polymerizable compound is preferably 40000 or less, more preferably 10000 or less, still more preferably 5000 or less, and particularly preferably 3000 or less. The lower limit is not particularly limited, but may be, for example, 150 or more.

[0094] The content of the (E) radically polymerizable compound in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, it is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of the (E) radically polymerizable compound in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, for example, it is 0% by mass or more, 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more.

[0095] <(F) thermoplastic resin> The resin composition of the present invention may further contain an (F) thermoplastic resin as an optional component. The (F) thermoplastic resin described here is a component other than those corresponding to the (E) radically polymerizable compound described above.

[0096] Examples of the (F) thermoplastic resin include polyimide resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, etc. In one embodiment, the (F) thermoplastic resin preferably contains a thermoplastic resin selected from the group consisting of polyimide resin and phenoxy resin, and more preferably contains phenoxy resin. Also, the thermoplastic resin may be used alone or in combination of two or more.

[0097] Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Ricacote SN20" and "Ricacote PN20" manufactured by Nippon Rika Kogyo Co., Ltd., etc.

[0098] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0099] Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are bisphenol A skeleton-containing phenoxy resins); "YX8100" manufactured by Mitsubishi Chemical Corporation (bisphenol S skeleton-containing phenoxy resin); "YX6954" manufactured by Mitsubishi Chemical Corporation (bisphenol acetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation; and the like.

[0100] Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and the polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Kabushiki Kaisha; Esrec BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series manufactured by Sekisui Chemical Co., Ltd.; and the like.

[0101] Examples of polyolefin resins include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; polyolefin polymers such as polypropylene and ethylene-propylene block copolymer, etc.

[0102] Examples of polybutadiene resins include, for example, resins containing a hydrogenated polybutadiene backbone, hydroxy group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, polyphenylene ether-polybutadiene resins, etc.

[0103] Specific examples of polyamideimide resins include "Vylon Max HR11NN" and "Vylon Max HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins also include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane backbone) manufactured by Hitachi Chemical Co., Ltd.

[0104] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0105] Specific examples of polysulfone resins include polysulfones "P1700", "P3500", etc. manufactured by Solvay Advanced Polymers, LLC.

[0106] Specific examples of polyphenylene ether resins include "NORYL SA90" manufactured by SABIC. Specific examples of polyetherimide resins include "ULTEM" manufactured by GE.

[0107] Examples of the polycarbonate resin include a hydroxy group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an isocyanate group-containing carbonate resin, a urethane group-containing carbonate resin, and the like. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd., and the like. Specific examples of the polyetheretherketone resin include "Sumipro EK" manufactured by Sumitomo Chemical Company, Limited.

[0108] Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethylene terephthalate resin, and the like.

[0109] (F) From the viewpoint of significantly obtaining the effects of the present invention, the weight average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less.

[0110] The content of the (F) thermoplastic resin in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, from the viewpoint of significantly obtaining the desired effects of the present invention, it may preferably be 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. The lower limit of the content of the (F) thermoplastic resin in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, for example, it may be 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.3% by mass or more, etc.

[0111] <(G) Other additives> The resin composition of the present invention may further contain an optional additive as a non-volatile component. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; thermosetting resins other than epoxy resins such as epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, and silicone resins; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as benton and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic-based flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers, etc. (G) These other additives may be used alone or in combination of two or more in any ratio. (G) The content of these other additives can be appropriately set by those skilled in the art.

[0112] <(H) Organic solvent> In addition to the above-described non-volatile components, the resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component. (H) As the organic solvent, known ones can be appropriately used, and the type thereof is not particularly limited. (H) Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (H) The organic solvent may be used alone or in combination of two or more in any ratio.

[0113] In one embodiment, the content of the (H) organic solvent is not particularly limited, but when the total components in the resin composition are 100% by mass, it can be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, etc.

[0114] <Method for producing resin composition> The resin composition of the present invention can be produced, for example, by adding (A) a phosphorus-containing curing catalyst, (B) an epoxy resin, (C) an active ester compound, (D) an inorganic filler, optionally (A') other curing accelerators, optionally (C') other curing agents, optionally (E) a radically polymerizable compound, optionally (F) a thermoplastic resin, optionally (G) other additives, and optionally (H) an organic solvent to an arbitrary preparation container in an arbitrary order and / or partially or entirely simultaneously and mixing them. Also, during the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling can be performed temporarily or throughout. Further, during or after the process of adding and mixing, the resin composition may be stirred or shaken using a stirring device or a shaking device such as a mixer to be uniformly dispersed. Also, defoaming may be performed under low-pressure conditions such as under vacuum simultaneously with stirring or shaking.

[0115] <Properties of resin composition> The resin composition of the present invention contains (A) a phosphorus-containing curing catalyst, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler, the content of the (C) active ester compound is 10% by mass or more, and the content of the (D) inorganic filler is 60% by mass or more. By using such a resin composition, the dielectric tangent (Df) of the cured product can be suppressed low and the occurrence of unevenness after lamination can be suppressed.

[0116] The cured product of the resin composition of the present invention may have the characteristic of having a low dissipation factor (Df). Therefore, in one embodiment, when measured at 5.8 GHz and 23 °C as in Test Example 1 below, the dissipation factor (Df) of the cured product of the resin composition is preferably 0.0200 or less, 0.0100 or less, more preferably 0.0080 or less, 0.0070 or less, 0.0060 or less, 0.0050 or less, still more preferably 0.0040 or less, 0.0035 or less, 0.0030 or less, particularly preferably 0.0027 or less, 0.0026 or less.

[0117] The resin composition of the present invention may have the characteristic of being able to suppress the occurrence of unevenness after lamination. Therefore, in one embodiment, when the resin composition of the present invention is laminated on an inner layer substrate as in Test Example 2 below and the recesses of the resin around the inner layer substrate are observed, no recesses can be observed.

[0118] In one embodiment, the resin composition of the present invention may have a good melt viscosity. Therefore, in one embodiment, the minimum melt viscosity of the resin composition when measured as in Test Example 3 below is preferably 5000 poise (500 Pa·s) hereinafter, more preferably 4000 poise (400 Pa·s) hereinafter, still more preferably 3000 poise (300 Pa·s) hereinafter, particularly preferably 2000 poise (200 Pa·s) hereinafter and may be, and its lower limit is preferably 100 poise from the viewpoint of maintaining the thickness stability of the resin composition layer (10 Pa·s) above, more preferably 200 poise (20 Pa·s) above, still more preferably 300 poise (30 Pa·s) above, particularly preferably 400 poise (40 Pa·s) as above may be.

[0119] <Use of the resin composition> The resin composition of the present invention can be suitably used as a resin composition for insulating applications, particularly as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming the insulating layer (resin composition for forming an insulating layer for a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer. Further, in a printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of the printed wiring board (resin composition for forming an insulating layer of the printed wiring board). The resin composition of the present invention can also be widely used in applications where a resin composition is required, such as resin sheets, sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, etc.

[0120] Also, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring formation layer as an insulating layer for forming a rewiring layer (resin composition for forming a rewiring formation layer), and as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the encapsulation layer. (1) Step of laminating a temporary fixing film on a base material, (2) Step of temporarily fixing a semiconductor chip on the temporary fixing film, (3) Step of forming an encapsulation layer on the semiconductor chip, (4) Step of peeling the base material and the temporary fixing film from the semiconductor chip, (5) Step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring formation layer

[0121] Further, since the resin composition of the present invention provides an insulating layer with good component embedding properties, it can also be suitably used when the printed wiring board is a circuit board with built-in components.

[0122] <Sheet-like laminated material> Although the resin composition of the present invention can also be used by applying it in a varnish state, industrially, it is generally preferable to use it in the form of a sheet-like laminated material containing the resin composition.

[0123] As the sheet-like laminated material, the resin sheets and prepregs shown below are preferable.

[0124] In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

[0125] From the viewpoints of thinning the printed wiring board and providing a cured product having excellent insulation even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it can usually be 5 μm or more, 10 μm or more, etc.

[0126] Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

[0127] When using a film made of a plastic material as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

[0128] When using a metal foil as the support, examples of the metal foil include, for example, copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0129] The support may be subjected to matting treatment, corona treatment, or antistatic treatment on the surface that joins the resin composition layer.

[0130] Also, as the support, a support with a release layer having a release layer on the surface that joins the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. As the support with a release layer, commercially available products may be used. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin-based release agent, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc.

[0131] The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferred, and a range of 10 μm to 60 μm is more preferred. When using a support with a release layer, it is preferable that the total thickness of the support with a release layer is within the above range.

[0132] In one embodiment, the resin sheet may further include an arbitrary layer as needed. Examples of such an arbitrary layer include, for example, a protective film similar to the support provided on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0133] The resin sheet can be produced, for example, by directly using a liquid resin composition or preparing a resin varnish by dissolving the resin composition in an organic solvent, applying this onto a support using a die coater or the like, and further drying to form a resin composition layer.

[0134] Examples of the organic solvent include the same ones as those described as components of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0135] Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but drying is carried out so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it also varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% to 60% by mass of the organic solvent, a resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0136] The resin sheet can be wound and stored in a roll shape. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0137] In one embodiment, the prepreg is formed by impregnating a sheet-shaped fiber base material with the resin composition of the present invention.

[0138] The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-shaped fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited. Usually, it is 10 μm or more.

[0139] The prepreg can be manufactured by known methods such as the hot melt method and the solvent method.

[0140] The thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.

[0141] The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board).

[0142] <Printed Wiring Board> The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

[0143] The printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) using the resin sheet described above. (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is joined to the inner layer substrate (II) A step of curing the resin composition layer (for example, thermosetting) to form an insulating layer

[0144] The "inner layer substrate" used in step (I) is a member that becomes the substrate of the printed wiring board. Examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Further, the substrate may have a conductor layer on one or both sides thereof, and this conductor layer may be pattern-processed. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". Also, in the manufacture of a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0145] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. As a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member"), for example, a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll) can be mentioned. Note that it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the inner layer substrate instead of directly pressing the thermocompression bonding member against the resin sheet.

[0146] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination can preferably be carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

[0147] The lamination can be carried out by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nichco Materials Co., Ltd., a batch type vacuum pressure laminator, and the like.

[0148] After the lamination, under normal pressure (atmospheric pressure), for example, the resin sheet that has been laminated may be smoothed by pressing the thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the thermocompression bonding conditions for the above lamination. The smoothing treatment can be carried out by a commercially available laminator. Note that the lamination and the smoothing treatment may be continuously carried out using the above commercially available vacuum laminator.

[0149] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0150] In step (II), the resin composition layer is cured (e.g., thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions usually employed when forming an insulating layer of a printed wiring board may be used.

[0151] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition and the like. In one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0152] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0153] When manufacturing a printed wiring board, steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When removing the support after step (II), the removal of the support may be performed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeatedly performed to form a multilayer wiring board.

[0154] In another embodiment, the printed wiring board of the present invention can be manufactured using the above-described prepreg. The manufacturing method is basically the same as the case of using a resin sheet.

[0155] Step (III) is a step of drilling holes in the insulating layer, by which holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, a laser, a plasma, etc., according to the composition of the resin composition used for forming the insulating layer. The dimensions and shapes of the holes may be appropriately determined according to the design of the printed wiring board.

[0156] Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also carried out in this step (IV). The procedures and conditions for the roughening treatment are not particularly limited, and known procedures and conditions commonly used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0157] The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Security Gun P" and "Swelling Dip Security Gun SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0158] The oxidizing agent used for the roughening treatment is not particularly limited. For example, an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security Guard P" manufactured by Atotech Japan Co., Ltd.

[0159] In addition, as the neutralizing solution used for the roughening treatment, an acidic aqueous solution is preferable. Examples of commercially available products include "Reduction Solution Security Guard P" manufactured by Atotech Japan Co., Ltd.

[0160] The treatment with the neutralizing solution can be carried out by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0161] In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is not particularly limited, but is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, but can be preferably 0.5 nm or more, more preferably 1 nm or more, etc. Further, in one embodiment, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

[0162] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single-metal layer or an alloy layer. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, ease of patterning, etc. of forming the conductor layer, a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred, a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single-metal layer of copper is even more preferred.

[0163] The conductor layer may have a single-layer structure or a multilayer structure in which two or more single-metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0164] The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0165] In one embodiment, the conductor layer may be formed by plating. For example, by plating on the surface of the insulating layer by a conventionally known technique such as the semi-additive method or the full-additive method, a conductor layer having a desired wiring pattern can be formed. From the viewpoint of manufacturing simplicity, it is preferably formed by the semi-additive method. Hereinafter, an example of forming the conductor layer by the semi-additive method is shown.

[0166] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer by electroplating on the exposed plating seed layer, the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0167] In another embodiment, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, it is preferable to perform step (V) between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a conventional known technique such as a subtractive method or a modified semi-additive method.

[0168] The metal foil can be manufactured by known methods such as an electrolytic method or a rolling method. Examples of commercially available metal foils include HLP foil, JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, 3EC-III foil, TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd., and the like.

[0169] <Semiconductor device> The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0170] Examples of semiconductor devices include various semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft).

Example

[0171] Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "mass %", respectively, unless otherwise specified. The temperature conditions and pressure conditions in the case where the temperature and pressure are not specified are room temperature (23 ° C) and atmospheric pressure (1 atm).

[0172] <Example 1> 10 parts of a naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of about 145 g / eq.), 30 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC, active ester group equivalent of about 223 g / eq., toluene solution with a non-volatile component ratio of 65%), spherical silica surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m 2 / g) 90 parts, 2 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass), 2 parts of a triazine skeleton-containing phenolic curing agent ("LA-3018-50P" manufactured by DIC, active group equivalent of about 151 g / eq., 2-methoxypropanol solution with a non-volatile component ratio of 50%), 5 parts of a carbodiimide-based curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent of about 216 g / eq., toluene solution with a non-volatile component ratio of 50%), 0.1 part of an imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Chemicals Corporation, 1-benzyl-2-phenylimidazole), and 0.1 part of a phosphorus-containing curing catalyst ("TBP-DA" manufactured by Kitakyo Chemical Co., Ltd.) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin composition (resin varnish).

[0173] <Example 2> Instead of using 0.1 part of a phosphorus-containing curing catalyst (“TBP-DA” manufactured by Kitakyo Chemical Co., Ltd.), 0.1 part of a phosphorus-containing curing catalyst (“TBP-3PC” manufactured by Kitakyo Chemical Co., Ltd.) was used. Instead of using 30 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution with an active ester group equivalent of approximately 223 g / eq. and a non-volatile component ratio of 65%), 30 parts of an active ester compound (“HPC-8150-62T” manufactured by DIC Corporation, a toluene solution with an active ester group equivalent of approximately 220 g / eq. and a non-volatile component ratio of 62% by mass) were used. Otherwise, a resin composition (resin varnish) was prepared in the same manner as in Example 1.

[0174] <Example 3> Instead of using 0.1 part of a phosphorus-containing curing catalyst (“TBP-DA” manufactured by Kitakyo Chemical Co., Ltd.), 0.1 part of a phosphorus-containing curing catalyst (“TBP-3S” manufactured by Kitakyo Chemical Co., Ltd.) was used. Instead of using 10 parts of a naphthalene-type epoxy resin (“HP-4032-SS” manufactured by DIC Corporation, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of approximately 145 g / eq.), 10 parts of a biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of approximately 269 g / eq.) were used. Otherwise, a resin composition (resin varnish) was prepared in the same manner as in Example 1.

[0175] <Example 4> Instead of using 0.1 part of a phosphorus-containing curing catalyst (“TBP-DA” manufactured by Kitakyo Chemical Co., Ltd.), 0.1 part of a phosphorus-containing curing catalyst (“TPP-phthalic acid” manufactured by Kitakyo Chemical Co., Ltd.) was used. Instead of using 10 parts of a naphthalene-type epoxy resin (“HP-4032-SS” manufactured by DIC Corporation, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of approximately 145 g / eq.), 10 parts of a biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of approximately 269 g / eq.) were used. Otherwise, a resin composition (resin varnish) was prepared in the same manner as in Example 1.

[0176] <Example 5> The amount of spherical silica (manufactured by Admatechs Co., Ltd. "SO-C2") surface-treated with a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM-573") was changed from 90 parts to 92 parts. Instead of 30 parts of an active ester compound (manufactured by DIC Corporation "HPC-8000-65T", toluene solution with an active ester group equivalent of approximately 223 g / eq. and a non-volatile component ratio of 65%), 30 parts of an active ester compound (manufactured by DIC Corporation "HPC-8150-62T", toluene solution with an active ester group equivalent of approximately 220 g / eq. and a non-volatile component ratio of 62% by mass) was used. Further, a resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 2 parts of a biphenyl aralkyl novolac type maleimide (manufactured by Nippon Kayaku Co., Ltd. "MIR-3000-70MT", MEK / toluene mixed solution with a non-volatile component ratio of 70%) was used.

[0177] <Example 6> The amount of spherical silica (manufactured by Admatechs Co., Ltd. "SO-C2") surface-treated with a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM-573") was changed from 92 parts to 93 parts. The amount of an imidazole-based curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd. "1B2PZ") was changed from 0.1 part to 0.5 part. Further, a resin composition (resin varnish) was prepared in the same manner as in Example 5, except that 1 part of a maleimide-terminated polyimide compound (manufactured by DMI Co., Ltd. "BMI-1500") was used instead of 2 parts of a biphenyl aralkyl novolac type maleimide (manufactured by Nippon Kayaku Co., Ltd. "MIR-3000-70MT", MEK / toluene mixed solution with a non-volatile component ratio of 70%).

[0178] <Example 7> The amount of spherical silica (manufactured by Admatechs Co., Ltd. "SO-C2") surface-treated with a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM-573") was changed from 92 parts to 93 parts. Further, a resin composition (resin varnish) was prepared in the same manner as in Example 5, except that 2 parts of a methacryl-modified polyphenylene ether (manufactured by SABIC Innovative Plastics "SA9000-111") was used instead of 2 parts of a biphenyl aralkyl novolac type maleimide (manufactured by Nippon Kayaku Co., Ltd. "MIR-3000-70MT", MEK / toluene mixed solution with a non-volatile component ratio of 70%).

[0179] <Example 8> The amount of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 92 parts to 93 parts. Further, instead of 2 parts of a biphenyl aralkyl novolac type maleimide (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., MEK / toluene mixed solution with a non-volatile component ratio of 70%), 2 parts of a vinylbenzyl-modified polyphenylene ether (“OPE-2St 2200” manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with a non-volatile component ratio of 65%) was used. Otherwise, in the same manner as in Example 5, a resin composition (resin varnish) was prepared.

[0180] <Example 9> Instead of 30 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, active ester group equivalent of about 223 g / eq., toluene solution with a non-volatile component ratio of 65%), 30 parts of an active ester compound (“HPC-8150-62T” manufactured by DIC Corporation, active ester group equivalent of about 220 g / eq., toluene solution with a non-volatile component ratio of 62% by mass) was used, and the amount of a phosphorus-containing curing catalyst (“TBP-DA” manufactured by Kitakyo Chemical Co., Ltd.) was changed from 0.1 part to 2 parts. Otherwise, in the same manner as in Example 1, a resin composition (resin varnish) was prepared.

[0181] <Comparative Example 1> A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that a phosphorus-containing curing catalyst (“TBP-DA” manufactured by Kitakyo Chemical Co., Ltd.) was not used, and the amount of an imidazole-based curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.) was changed from 0.1 part to 0.5 part.

[0182] <Comparative Example 2> Without using a phosphorus-containing curing catalyst ("TBP-DA" manufactured by Kitakyo Chemical Co., Ltd.), the amount of the imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Chemicals Corporation) was changed from 0.1 part to 0.5 part, and instead of 30 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, toluene solution with an active ester group equivalent of about 223 g / eq. and a non-volatile component ratio of 65%), 30 parts of an active ester compound ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with an active ester group equivalent of about 220 g / eq. and a non-volatile component ratio of 62% by mass) were used. Otherwise, in the same manner as in Example 1, a resin composition (resin varnish) was prepared.

[0183] <Comparative Example 3> The amount of spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd.) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 90 parts to 52 parts, and the amount of the active ester compound ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with an active ester group equivalent of about 220 g / eq. and a non-volatile component ratio of 62% by mass) was changed from 30 parts to 10 parts. Otherwise, in the same manner as in Comparative Example 2, a resin composition (resin varnish) was prepared.

[0184] <Comparative Example 4> The amount of spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd.) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 90 parts to 40 parts. Otherwise, in the same manner as in Comparative Example 2, a resin composition (resin varnish) was prepared.

[0185] <Test Example 1: Measurement of Dielectric Dissipation Factor> (1) Preparation of Resin Sheet A with a Resin Composition Layer Thickness of 40 μm As a support, a polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared. On the release layer of this support, the resin compositions obtained in the examples and comparative examples were uniformly coated so that the thickness of the resin composition layer after drying would be 40 μm. Then, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet A including the support and the resin composition layer.

[0186] (2) Preparation of the cured product B for evaluation The resin sheet A was cured in an oven at 190 °C for 90 minutes. By peeling off the support from the resin sheet A taken out of the oven, a cured product of the resin composition layer was obtained. The cured product was cut into pieces with a length of 80 mm and a width of 2 mm to obtain the cured product B for evaluation.

[0187] (3) Measurement of dielectric loss tangent Regarding the cured product B for evaluation, using the cavity resonator perturbation method dielectric constant measuring device "CP521" manufactured by Kanto Applied Electronics Development Co., Ltd. and "HP8362B" manufactured by Agilent Technologies, the value of the dielectric loss tangent (Df value) was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C by the cavity resonance perturbation method. The measurement was carried out with two test pieces, and the average was calculated.

[0188] <Test Example 2: Evaluation of unevenness after lamination> (1) Preparation of inner layer substrate Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic) with an inner layer circuit formed were etched with a micro-etching agent ("CZ8101" manufactured by Meck) by 1 μm to perform roughening treatment of the copper surface.

[0189] (2) Lamination of resin sheet A Using a batch type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nichco Materials Co., Ltd.), the resin sheet A obtained in Test Example 1(1) was laminated on both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. The lamination was carried out by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then pressure-bonding at 120 °C and a pressure of 0.74 MPa for 30 seconds. Subsequently, a hot press was performed at 100 °C and a pressure of 0.5 MPa for 60 seconds.

[0190] (3) Evaluation of unevenness after lamination After lamination, those with resin depressions observed along the periphery of the inner layer substrate were evaluated as "present", and those without observed depressions were evaluated as "absent".

[0191] <Test Example 3: Measurement of Minimum Melting Viscosity> The resin composition layer of the resin sheet A obtained in Test Example 1(1) was stacked 25 sheets to a thickness of 1 mm, and a resin composition layer with a diameter of 20 mm was punched out to prepare a measurement sample. For the prepared measurement sample, using a dynamic viscoelasticity measuring device ("Rheogel-G3000" manufactured by UBM), the minimum melting viscosity (poise) was measured by measuring the dynamic viscoelastic modulus under the measurement conditions of a starting temperature of 60°C to 200°C, a heating rate of 5°C / min, a measurement temperature interval of 2.5°C, and a vibration frequency of 1 Hz.

[0192] The raw material usage amounts and the contents of non-volatile components of the resin compositions of the examples and comparative examples, and the measurement results and evaluation results of the test examples are shown in Table 1 below.

[0193]

Table 1

[0194] As shown in Table 1, in Comparative Example 3 with a low content of (C) active ester compound and Comparative Example 4 with a low content of (D) inorganic filler, the dielectric loss tangent is relatively high. In Comparative Examples 1 and 2 with high contents of (C) active ester compound and (D) inorganic filler, although the dielectric loss tangent is suppressed low, unevenness occurred after lamination. On the other hand, when the resin composition of the present invention containing (A) phosphorus-containing curing catalyst was used, the dielectric loss tangent was suppressed low, and furthermore, no unevenness occurred after lamination.

Claims

1. A resin composition comprising (A) a phosphorus-containing curing catalyst, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler, wherein component (A) contains a quaternary phosphonium salt, when the content of the non-volatile components in the resin composition is 100% by mass, the content of component (C) is 10% by mass or more and 20% by mass or less, when the content of the non-volatile components in the resin composition is 100% by mass, the content of component (D) is 60% by mass or more and 75% by mass or less, and the resin composition has a minimum melt viscosity of 5000 poise (500 Pa·s) or less.

2. The resin composition according to claim 1, wherein when the content of the non-volatile components in the resin composition is 100% by mass, the content of component (A) is 0.01% by mass or more and 3% by mass or less.

3. The resin composition according to claim 1 or 2, wherein when the content of the non-volatile components in the resin composition is 100% by mass, the content of component (B) is 1% by mass to 20% by mass.

4. The resin composition according to any one of claims 1 to 3, wherein the mass ratio of component (B) to component (A) ((B) component / (A) component) is 3 to 500.

5. The resin composition according to any one of claims 1 to 4, wherein the mass ratio of component (C) to component (A) ((C) component / (A) component) is 5 to 1000.

6. The resin composition according to any one of claims 1 to 5, wherein the mass ratio of component (D) to component (A) ((D) component / (A) component) is 30 to 5000.

7. The resin composition according to any one of claims 1 to 6, wherein component (D) is silica.

8. The resin composition according to any one of claims 1 to 7, wherein when the content of the non-volatile components in the resin composition is 100% by mass, the content of component (D) is 70% by mass or more and 75% by mass or less.

9. The resin composition according to any one of claims 1 to 8, further comprising an imidazole-based curing accelerator.

10. The resin composition according to any one of claims 1 to 9, further comprising a curing agent selected from the group consisting of a phenolic curing agent and a carbodiimide-based curing agent.

11. The resin composition according to any one of claims 1 to 10, wherein the dielectric tangent (Df) of the cured product of the resin composition, when measured at 5.8 GHz and 23 °C, is 0.0030 or less.

12. A cured product of the resin composition according to any one of claims 1 to 11.

13. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 11.

14. A resin sheet having a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 11 provided on the support.

15. A printed wiring board including an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 11.

16. A semiconductor device including the printed wiring board according to claim 15.

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