Resin composition

Abstract

To provide a resin composition that enables obtaining a cured material having excellent flame retardancy and having a dielectric constant and dielectric loss tangent kept low.SOLUTION: A resin composition comprises (A) an epoxy resin, (B) an aromatic polyether-based resin, (C) an inorganic filler, and (E) a carbodiimide resin, where the (C) component includes porous silica.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition containing an epoxy resin, and further to a cured product, a sheet-like laminate material, a resin sheet, a circuit board, and a semiconductor device obtained by using the resin composition. [Background technology]

[0002] A build-up method in which insulating layers and conductor layers are alternately stacked is known as a manufacturing technique for circuit boards such as printed wiring boards and rewiring boards for semiconductor chip packages. In the build-up method, the insulating layer is generally formed by curing a resin composition containing an epoxy resin and an inorganic filler.

[0003] In recent years, with the trend toward finer and denser wiring on circuit boards and higher signal frequencies, there is a demand for further reduction in the relative dielectric constant and dielectric loss tangent of insulating layers. As one of the methods for achieving this, the application of hollow inorganic fillers has been attempted (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2020-83966 A [Patent Document 2] Patent No. 5864299 Summary of the Invention [Problem to be solved by the invention]

[0005] However, since hollow inorganic fillers contain air, which aids in combustion, the use of hollow inorganic fillers results in lower flame retardancy compared to the use of conventional solid inorganic fillers that are not hollow. In addition, if an excessive amount of flame retardant is used to compensate for the reduced flame retardancy, the dielectric loss tangent tends to increase. Therefore, there is a problem of how to simultaneously improve flame retardancy and reduce the relative dielectric constant and dielectric loss tangent.

[0006] An object of the present invention is to provide a resin composition which is capable of giving a cured product having excellent flame retardancy and low relative dielectric constant and dielectric loss tangent. [Means for solving the problem]

[0007] In order to achieve the object of the present invention, the present inventors have conducted extensive research and have unexpectedly found that by using an aromatic polyether resin (B) in a resin composition containing a hollow inorganic filler, a cured product having excellent flame retardancy and a low relative dielectric constant and dielectric dissipation factor can be obtained, and have completed the present invention. In particular, the present inventors have found that a resin composition containing an epoxy resin (A), an aromatic polyether resin (B), an inorganic filler (C), and a carbodiimide resin (E), in which the component (C) contains hollow silica, can provide a cured product having excellent flame retardancy and a low relative dielectric constant and dielectric dissipation factor, has an appropriately low minimum melt viscosity, and is even better in lamination properties and conductor embedding properties.

[0008] That is, the present invention includes the following. [1] A resin composition comprising (A) an epoxy resin, (B) an aromatic polyether resin, and (C) an inorganic filler, A resin composition, wherein the component (C) contains a hollow inorganic filler. [2] The component (B) is represented by the formula (1):

[0009] [ka]

[0010] [In the formula, R 11 and R 12 each independently represents an alkyl group; R 13 , R 14 , R 21 , R 22 , R 23 and R 24 each independently represents a hydrogen atom or an alkyl group; R a and R b each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkyl-carbonyl group, an optionally substituted alkenyl-carbonyl group, an optionally substituted aryl-carbonyl group, or an optionally substituted aralkyl-carbonyl group; A is a single bond, -C(R c )2-, -O-, -CO-, -S-, -SO-, or -SO2-; R c each independently represents a hydrogen atom or an alkyl group; s represents 0 or 1; t and u each independently represent an integer of 1 or more. The resin composition according to the above [1], comprising a resin represented by the formula: [3] The component (B) is represented by formula (2A) or (2B):

[0011] [ka]

[0012] [In the formula, W, X, Y and Z each independently represent N or CR; R represents a hydrogen atom or a substituent; R 1 and R 2 each independently represents a hydrogen atom or a substituent, or R 1 and R 2 are joined together to form a non-aromatic carbocyclic ring which may have a substituent and which may be fused to an aromatic carbocyclic ring; R 3 and R 4 each independently represents a substituent; a and b each independently represent 0, 1, 2, or 3. The resin composition according to the above [1] or [2], comprising a resin having a repeating unit represented by the following formula: [4] The resin composition according to any one of the above [1] to [3], wherein the content of the component (B) is 0.5% by mass to 10% by mass, relative to 100% by mass of non-volatile components in the resin composition excluding the component (C). [5] The resin composition according to any one of the above [1] to [4], wherein the content of the component (C) is 60 mass% or more, based on 100 mass% of the non-volatile components in the resin composition. [6] The resin composition according to any one of the above [1] to [5], wherein the hollow inorganic filler has an average porosity of 10 volume % or more. [7] The resin composition according to any one of the above [1] to [6], further comprising (D) a flame retardant. [8] The resin composition according to the above [7], wherein the component (D) contains a phosphorus-based flame retardant. [9] The resin composition according to [7] or [8] above, wherein the content of the (D) component is 5 mass% or less, based on 100 mass% of the non-volatile components in the resin composition excluding the (C) component.

[10] The resin composition according to any one of the above [7] to [9], wherein a mass ratio of the component (B) to the component (D) [component (B) / component (D)] is 0.5 or more.

[11] The resin composition according to any one of the above [1] to

[10] , having a phosphorus atom content of 0 to 5 mass%, relative to 100 mass% of non-volatile components in the resin composition excluding component (C).

[12] The resin composition according to any one of the above [1] to

[11] , further comprising (E) a carbodiimide resin.

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

[12] , further comprising (F) a curing agent.

[14] The resin composition according to the above

[13] , wherein the component (F) contains an active ester-based curing agent.

[15] The resin composition according to the above

[13] or

[14] , wherein the component (F) contains a phenol-based curing agent.

[16] The resin composition according to any one of the above [1] to

[15] , wherein a dielectric loss tangent (Df) of a cured product of the resin composition is 0.006 or less when measured at 5.8 GHz and 23°C.

[17] The resin composition according to any one of the above [1] to

[16] , wherein a cured product of the resin composition has a relative dielectric constant (Dk) of 3.0 or less when measured at 5.8 GHz and 23°C.

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

[17] above.

[19] A sheet-like laminate material comprising the resin composition according to any one of the above [1] to

[17] .

[20] A resin sheet comprising: a support; and a resin composition layer formed on the support, the resin composition being formed from the resin composition according to any one of [1] to

[17] above.

[21] A circuit board comprising an insulating layer made of a cured product of the resin composition according to any one of the above [1] to

[17] .

[22] A semiconductor device comprising the circuit board described in

[21] above. Effect of the Invention

[0013] According to the resin composition of the present invention, it is possible to obtain a cured product which is excellent in flame retardancy and has a low relative dielectric constant and dielectric loss tangent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present invention will be described in detail below with reference to preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be modified and implemented as desired without departing from the scope of the claims of the present invention and their equivalents.

[0015] <Resin composition> The resin composition of the present invention comprises (A) an epoxy resin, (B) an aromatic polyether resin, and (C) an inorganic filler, the (C) component comprising a hollow inorganic filler. With such a resin composition, a cured product having excellent flame retardancy and a low relative dielectric constant and dielectric loss tangent can be obtained. The present inventors have also confirmed that the resin composition of the present invention provides a cured product having an appropriately low minimum melt viscosity and a high glass transition temperature.

[0016] The resin composition of the present invention may further contain optional components in addition to (A) the epoxy resin, (B) the aromatic polyether resin, and (C) the inorganic filler, such as (D) a flame retardant, (E) a carbodiimide resin, (F) a curing agent, (G) a maleimide resin, and other additives.

[0017] Each component contained in the resin composition will be described in detail below.

[0018] <(A) Epoxy resin> The resin composition of the present invention contains an epoxy resin (A). The epoxy resin (A) is a curable resin having an epoxy group and an epoxy equivalent of 5,000 g / eq. or less.

[0019] Examples of the (A) epoxy resin include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, phenol ... Examples of the epoxy resin include 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, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, phosphorus-containing epoxy resin, glycirol type epoxy resin, alkyleneoxy skeleton-containing epoxy resin, fluorene structure-containing epoxy resin, etc. (A) Epoxy resin may be used alone or in combination of two or more kinds.

[0020] The resin composition of the present invention preferably contains, as the epoxy resin (A), 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 relative to 100 mass% of the epoxy resin (A) is preferably 50 mass% or more, more preferably 60 mass% or more, and particularly preferably 70 mass% or more.

[0021] (A) Epoxy resins include epoxy resins that are liquid at a temperature of 20° C. (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20° C. (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition of the present invention may contain only liquid epoxy resins as epoxy resins, or only solid epoxy resins, or both liquid and solid epoxy resins, but it is particularly preferable that the resin composition contains both liquid and solid epoxy resins.

[0022] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0023] Preferred liquid epoxy resins include glycirol type epoxy resins, 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 dimethanol type epoxy resins, cyclic aliphatic glycidyl ethers, epoxy resins having a butadiene structure, dicyclopentadiene type epoxy resins, alkyleneoxy skeleton-containing epoxy resins, and fluorene structure-containing epoxy resins.

[0024] Specific examples of liquid epoxy resins include "EX-992L" manufactured by Nagase ChemteX Corporation, "YX7400" manufactured by Mitsubishi Chemical Corporation, "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "828EL", "825", and "Epikote 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" manufactured by Mitsubishi Chemical Corporation. " (bisphenol F type epoxy resin); "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" (glycirol 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" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Corporation; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "EX-991L" (alkyleneoxy skeleton-containing epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Corporation; Examples of such epoxy resins include "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (epoxy resins having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resins) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EG-280" (fluorene structure-containing epoxy resin) manufactured by Osaka Gas Chemicals Co., Ltd.; and "EX-201" (cyclic aliphatic glycidyl ether) manufactured by Nagase ChemteX Corporation.

[0025] 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.

[0026] Preferred solid epoxy resins include bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, phenol aralkyl type epoxy resins, tetraphenylethane type epoxy resins, phenolphthalimidine type epoxy resins, phosphorus-containing flame-retardant epoxy resins, and fluorene structure-containing epoxy resins.

[0027] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy resins) manufactured by DIC Corporation; and "EXA-7311" manufactured by DIC Corporation. ", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN475V", "ES N4100V (naphthalene type epoxy resin); "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", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. "YX7700" (phenol aralkyl type epoxy resin) manufactured by Osaka Gas Chemicals; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene structure-containing epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical; "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku;Examples of such resins include "FX-289BEK75" (phosphorus-containing flame-retardant epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd. These resins may be used alone or in combination of two or more.

[0028] When a solid epoxy resin and a liquid epoxy resin are used in combination as the (A) epoxy resin, the mass ratio thereof (solid epoxy resin:liquid epoxy resin) is preferably 1:0.1 to 1:10, more preferably 1:0.2 to 1:5, and particularly preferably 1:0.5 to 1:10.

[0029] The epoxy equivalent of the (A) epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 50 g / eq. to 3,000 g / eq. or 60 g / eq. to 2,000 g / eq., even more preferably 70 g / eq. to 1,000 g / eq., even more preferably 80 g / eq. to 500 g / eq., and particularly preferably 110 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

[0030] The weight average molecular weight (Mw) of the epoxy resin (A) is preferably from 100 to 5,000, more preferably from 250 to 3,000, and further preferably from 400 to 1500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0031] The content of the epoxy resin (A) in the resin composition is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 65% ​​by mass or less, and particularly preferably 60% by mass or less, based on 100% by mass of the non-volatile components in the resin composition excluding the component (C), from the viewpoint of obtaining the effects of the present invention. The lower limit of the content of the epoxy resin (A) in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, based on 100% by mass of the non-volatile components in the resin composition excluding the component (C), from the viewpoint of obtaining the effects of the present invention.

[0032] <(B) Aromatic polyether resin> The resin composition of the present invention preferably contains (B) an aromatic polyether resin. The (B) aromatic polyether resin may be used alone or in combination of two or more kinds in any ratio.

[0033] (B) Aromatic polyether resin means a resin having a repeating unit having an ether bond that bonds two different aromatic rings together in the main chain and having no aliphatic chain (an alkylene group having two or more carbon atoms in the main chain). Examples of (B) aromatic polyether resin include polyphenylene ether resin, aromatic ether polymer of bisphenol, aromatic polyethersulfone resin, aromatic polyetherimide resin, aromatic polyetherketone resin, aromatic polyetheretherketone resin, aromatic polyetherketoneketone resin, etc. (B) Aromatic polyether resin preferably contains a resin selected from polyphenylene ether resin and aromatic ether polymer of bisphenol.

[0034] The polyphenylene ether resin, in one embodiment, preferably has the formula (1):

[0035] [ka]

[0036] [In the formula, R 11 and R 12 each independently represents an alkyl group; R 13 , R 14 , R 21 , R 22 , R 23 and R 24 each independently represents a hydrogen atom or an alkyl group; R a and R b each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkyl-carbonyl group, an optionally substituted alkenyl-carbonyl group, an optionally substituted aryl-carbonyl group, or an optionally substituted aralkyl-carbonyl group; A is a single bond, -C(R c )2-, -O-, -CO-, -S-, -SO-, or -SO2-; R c each independently represents a hydrogen atom or an alkyl group; s represents 0 or 1; t and u each independently represent an integer of 1 or more. The t units and the u units may be the same or different for each unit.

[0037] R 11 and R 12 R each independently represents an alkyl group, and in one embodiment, is preferably a methyl group. 13 and R 14 R each independently represents a hydrogen atom or an alkyl group, and in one embodiment, R is preferably a hydrogen atom. 21 and R 22R each independently represents a hydrogen atom or an alkyl group, and in one embodiment, R is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. 23 and R 24 each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group.

[0038] The alkyl group refers to a linear, branched and / or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, 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, an isopentyl group, a sec-pentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a tert-octyl group, a cyclopentyl group, and a cyclohexyl group.

[0039] R a and R b each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkyl-carbonyl group, an optionally substituted alkenyl-carbonyl group, an optionally substituted aryl-carbonyl group, or an optionally substituted aralkyl-carbonyl group.

[0040] The term "alkenyl group" refers to a linear, branched and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, the alkenyl group is preferably an alkenyl group having 2 to 14 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, and even more preferably an alkenyl group having 2 to 6 carbon atoms. Examples of alkenyl (groups) include vinyl groups, propenyl groups (allyl groups, 1-propenyl groups, isopropenyl groups), butenyl groups (1-butenyl groups, crotyl groups, methallyl groups, isocrotyl groups, etc.), pentenyl groups (1-pentenyl groups, etc.), hexenyl groups (1-hexenyl groups, etc.), heptenyl groups (1-heptenyl groups, etc.), octenyl groups (1-octenyl groups, etc.), cyclopentenyl groups (2-cyclopentenyl groups, etc.), and cyclohexenyl groups (3-cyclohexenyl groups, etc.).

[0041] The aryl group refers to a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbon ring. Unless otherwise specified, the aryl group is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0042] The aralkyl group refers to an alkyl group substituted with one or more (preferably one) aryl groups. Unless otherwise specified, the aralkyl group is preferably an aralkyl group having 7 to 15 carbon atoms, and more preferably an aralkyl group having 7 to 11 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, a hydrocinnamyl group, an α-methylbenzyl group, an α-cumyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group.

[0043] R a and R bIn the above, the substituents on the alkyl group, alkenyl group, alkyl-carbonyl group, and alkenyl-carbonyl group are not particularly limited, and examples thereof include a halogen atom, an aryl group, an alkyl-aryl group (an aryl group substituted with one or more alkyl groups), an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an aralkyl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an aralkyl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, an aralkyl-carbonyl-oxy group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, an aralkyl-carbonyl-oxy group, and the like.

[0044] R a and R b In the above, the substituents of the aryl group, aralkyl group, aryl-carbonyl group, and aralkyl-carbonyl group are not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an aralkyl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an aralkyl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, an aralkyl-carbonyl-oxy group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, an aralkyl-carbonyl-oxy group, and the like.

[0045] The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom.

[0046] R a and R bIn one embodiment, each of them is preferably, independently, (1) a hydrogen atom, (2) an acryloyl group, (3) a methacryloyl group, (4) an allyl group, (5) a methallyl group, (6) a phenyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may be further substituted with an alkyl group, or (7) a benzyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may be further substituted with an alkyl group; more preferably, (1) an acryloyl group, (2) a methacryloyl group, (3) an allyl group, (4) a methallyl group, (5) a phenyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may be further substituted with an alkyl group, or (6) a benzyl group substituted with a group selected from a vinyl group and an isopropenyl group. and a benzyl group which may be substituted with an alkyl group; more preferably, (1) a phenyl group which is substituted with a group selected from a vinyl group and an isopropenyl group and which may be substituted with an alkyl group, or (2) a benzyl group which is substituted with a group selected from a vinyl group and an isopropenyl group and which may be substituted with an alkyl group; particularly preferably, a 4-vinylphenyl group, a 3-vinylphenyl group, a 2-vinylphenyl group, a 4-isopropenylphenyl group, a 3-isopropenylphenyl group, a 2-isopropenylphenyl group, a 4-vinylbenzyl group, a 3-vinylbenzyl group, a 2-vinylbenzyl group, a 4-isopropenylbenzyl group, a 3-isopropenylbenzyl group, or a 2-isopropenylbenzyl group.

[0047] A is a single bond, -C(R c )2-, -O-, -CO-, -S-, -SO-, or -SO2-, and in one embodiment, preferably a single bond, -C(R c )2- or -O-. "C" is the atomic symbol for carbon atom, "O" is the atomic symbol for oxygen atom, and "S" is the atomic symbol for sulfur atom. c each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group.

[0048] s represents 0 or 1, and in one embodiment, is preferably 1. t and u each independently represent an integer of 1 or more, and in one embodiment, is preferably an integer of 1 to 200, and more preferably an integer of 1 to 100.

[0049] The number average molecular weight of the polyphenylene ether resin is preferably 800 to 10000, and more preferably 900 to 5000. The number average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0050] Commercially available polyphenylene ether resins include, for example, "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Company, Inc.; and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether resins) manufactured by SABIC Corporation.

[0051] The aromatic ether polymer of bisphenol means a polymer having a structure in which a diphenylmethane structure or a substituted structure thereof and an aromatic ring not constituting said structure are alternately linked through ether bonds.

[0052] The aromatic ether polymer of bisphenol, in one embodiment, is preferably represented by formula (2A) or (2B):

[0053] [ka]

[0054] [In the formula, W, X, Y and Z each independently represent N or CR; R represents a hydrogen atom or a substituent; R 1 and R 2 each independently represents a hydrogen atom or a substituent, or R 1 and R 2are joined together to form a non-aromatic carbocyclic ring which may have a substituent and which may be fused to an aromatic carbocyclic ring; R 3 and R 4 each independently represents a substituent; a and b each independently represent 0, 1, 2, or 3. The resin includes a resin having a repeating unit represented by the formula:

[0055] W, X, Y and Z each independently represent N or CR; in one embodiment, preferably, W, X, Y and Z are N or CR and at least one of W, X, Y and Z is N; more preferably, W, X, Y and Z are N or CR and at least two of W, X, Y and Z are N; even more preferably, W, X, Y and Z are N or CR and two of W, X, Y and Z are N; particularly preferably, X and Z are CR and W and Y are N. In addition, "N" represents a nitrogen atom as an atomic symbol, and "C" represents a carbon atom as an atomic symbol.

[0056] R represents a hydrogen atom or a substituent. The substituent in R is "R a and R b Examples of the substituents include those exemplified as "the substituents of the aryl group, the aralkyl group, the aryl-carbonyl group, and the aralkyl-carbonyl group in the above formula (I)."

[0057] In one embodiment, R is preferably a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group; more preferably a hydrogen atom or an aryl group; and particularly preferably a hydrogen atom.

[0058] R 1 and R 2 each independently represents a hydrogen atom or a substituent, or R 1 and R 2 R are bonded together to form a non-aromatic carbocyclic ring which may have a substituent and which may be fused with an aromatic carbocyclic ring. 1 and R 2The substituents in the above and the non-aromatic carbocyclic ring which may be condensed with the aromatic carbocyclic ring include "R a and R b Examples of the substituents include those exemplified as "the substituents of the aryl group, the aralkyl group, the aryl-carbonyl group, and the aralkyl-carbonyl group in the above formula (I)."

[0059] A non-aromatic carbocycle means a carbocycle other than an aromatic carbocycle that has aromaticity in the entire ring. A non-aromatic carbocycle has only carbon atoms as ring constituent atoms. A non-aromatic carbocycle may be a saturated carbocycle consisting of only single bonds, or an unsaturated carbocycle having at least one of a double bond and a triple bond. A non-aromatic carbocycle is preferably a non-aromatic carbocycle having 4 to 20 carbon atoms, more preferably a non-aromatic carbocycle having 5 to 12 carbon atoms. Specific preferred examples of the non-aromatic carbocyclic ring include monocyclic saturated carbocyclic rings such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, and a cyclododecane ring; bicyclic saturated carbocyclic rings such as a bicyclo[2.2.1]heptane ring (norbornane ring), a bicyclo[4.4.0]decane ring (decalin ring), a bicyclo[5.3.0]decane ring, a bicyclo[4.3.0]nonane ring (hydrindane ring), a bicyclo[3.2.1]octane ring, a bicyclo[5.4.0]undecane ring, a bicyclo[3.3.0]octane ring, and a bicyclo[3.3.1]nonane ring; 2,6 ] Decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 3,7 ]Decane ring (adamantane ring), tricyclo[6.2.1.0 2,7 ]undecane ring and other tricyclic saturated carbocyclic rings; tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodecane ring and other saturated tetracyclic carbocyclic rings; pentacyclo[9.2.1.1 4,7 .0 2,1 .0 3,8 ]Pentadecane ring, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13]Pentadecane ring (tetrahydrotricyclopentadiene ring) and other saturated five-ring carbon rings are also included.

[0060] The aromatic carbocycle means a hydrocarbon ring according to the Huckel rule, in which the number of electrons contained in the π electron system on the ring is 4p+2 (p is a natural number). The aromatic carbocycle has only carbon atoms as ring-constituting atoms. In one embodiment, the aromatic carbocycle is preferably a 6- to 14-membered aromatic carbocycle, and more preferably a 6- to 10-membered aromatic carbocycle. Suitable specific examples of the aromatic carbocycle include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, and more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

[0061] Examples of non-aromatic carbocycles condensed with aromatic carbocycles include an indane ring, an indene ring, a tetralin ring, a 1,2-dihydronaphthalene ring, a 1,4-dihydronaphthalene ring, a fluorene ring, a 9,10-dihydroanthracene ring, and a 9,10-dihydrophenanthrene ring.

[0062] R 1 and R 2 In one embodiment, preferably, R 1 and R 2 are each independently a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, or R 1 and R 2 are bonded together to form a monocyclic saturated carbocyclic ring having 4 to 20 carbon atoms which may be substituted with a group selected from an alkyl group, an alkenyl group, and an aryl group and which may be condensed with a benzene ring; more preferably, R 1 and R 2 is a hydrogen atom, an alkyl group, or an aryl group, or R 1 and R 2 are bonded together to form a cyclohexane ring which may be substituted with a group selected from an alkyl group and an aryl group; particularly preferably, R 1 and R 2are joined together to form a cyclohexane ring which may be substituted with an alkyl group.

[0063] R 3 and R 4 R each independently represents a substituent. 3 and R 4 The substituents in the a and R b Examples of the substituents include those exemplified as "the substituents of the aryl group, the aralkyl group, the aryl-carbonyl group, and the aralkyl-carbonyl group in the above formula (I)."

[0064] R 3 and R 4 In one embodiment, each independently is preferably an alkyl group, an alkenyl group, or an aryl group; more preferably an alkyl group or an aryl group; further preferably an alkyl group; and particularly preferably a methyl group.

[0065] a and b each independently represent 0, 1, 2, or 3; in one embodiment, preferably 0, 1, or 2; more preferably 0 or 1; and particularly preferably 0.

[0066] In one embodiment, the aromatic ether polymer of bisphenol is more preferably represented by the formulas (2A-1) to (2B-6):

[0067] [ka]

[0068] [ka]

[0069] [In the formula, each symbol is as defined above.] The polymerizable composition preferably includes a resin having a repeating unit represented by formula (2A-1), more preferably includes a resin having repeating units represented by formula (2A-2) and (2B-3), and particularly preferably includes a resin having a repeating unit represented by formula (2A-4).

[0070] In the structural units represented by formulas (2A) and (2B), and in the structural units represented by formulas (2A-1) to (2B-6), the structural unit represented by formula (3):

[0071] [ka]

[0072] [In the formula, each symbol is as defined above.] Specific examples of the partial structure represented by the formula (3-1) to (3-36):

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] [In the formula, each symbol is as defined above.] Examples of the structure include those represented by the following formula:

[0077] The number of repeating units represented by formulae (2A) and (2B) and the number of repeating units represented by formulae (2A-1) to (2B-6) in one molecule is preferably 5 or more, more preferably 10 or more, even more preferably 30 or more, and particularly preferably 50 or more. The upper limit of the number of repeating units is not particularly limited, and may be, for example, 10,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, etc.

[0078] In one embodiment, the aromatic ether polymer of bisphenol may have a reactive group such as a phenolic hydroxyl group, a thiol group, an amino group, a carboxyl group, a sulfo group, etc., in the molecule, and preferably has a phenolic hydroxyl group. In one embodiment, it is preferable that one molecule has two or more reactive groups.

[0079] The weight average molecular weight (Mw) of the aromatic ether polymer of bisphenol is not particularly limited, but is preferably 1000 to 200000, more preferably 5000 to 150000, and further preferably 10000 to 120000. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0080] The glass transition temperature (Tg) of the aromatic ether polymer of bisphenol is not particularly limited, but may be preferably 100 to 300°C, more preferably 150 to 250°C.

[0081] The aromatic ether polymer of bisphenol can be synthesized, for example, by the method described in WO2019 / 054335 or WO2020 / 021827 or a method equivalent thereto.

[0082] The content of the aromatic polyether resin (B) in the resin composition is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, even more preferably 1% by mass or more, even more preferably 1.5% by mass or more, particularly preferably 1.7% by mass or more, 2% by mass or more, 2.5% by mass or more, 3% by mass or more, or 4% by mass or more, based on the non-volatile components excluding the component (C) in the resin composition being 100% by mass, from the viewpoint of obtaining a cured product having excellent flame retardancy and a low relative dielectric constant and dielectric dissipation factor when a resin composition containing a hollow inorganic filler is used. The upper limit of the content of the aromatic polyether resin (B) in the resin composition is preferably 10% by mass or less, more preferably 9% by mass or less, even more preferably 8% by mass or less, even more preferably 7% by mass or less, particularly preferably 6% by mass or less or 5% by mass or less, based on the non-volatile components excluding the component (C) in the resin composition being 100% by mass, from the viewpoint of obtaining a cured product having excellent flame retardancy and a low relative dielectric constant and dielectric dissipation factor when a resin composition containing a hollow inorganic filler is used. In particular, when the content of the aromatic polyether resin (B) in the resin composition is in the range of 1% by mass or more and 6% by mass or less, when the non-volatile components excluding the component (C) in the resin composition are taken as 100% by mass, even when the content of the hollow inorganic filler is high (for example, when the content of the hollow inorganic filler in the resin composition is 30% by mass or more, 35% by mass or more, or 40% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass), it is preferable because it is easy to achieve a cured product with excellent flame retardancy and low relative dielectric constant and dielectric loss tangent. The excellent effects of the aromatic polyether resin (B) can be enjoyed more significantly when the composition contains a flame retardant (D) described below.

[0083] <(C) Inorganic filler> The resin composition of the present invention contains an inorganic filler (C). The inorganic filler (C) is contained in the resin composition in the form of particles. The inorganic filler (C) includes a hollow inorganic filler.

[0084] (C) An inorganic compound is used as the material of the inorganic filler. (C) Examples of the material of the inorganic filler include silica, alumina, aluminosilicate, 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. Among these, silica, alumina, or aluminosilicate is preferred, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, spherical silica is preferred as the silica. The (C) inorganic filler may be used alone or in combination of two or more kinds in any ratio.

[0085] (C) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Company; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; "DAW-03" and "FB-105FD" manufactured by Denka Company; and "Cellspheres" and "MG-005" manufactured by Taiheiyo Cement Corporation.

[0086] The average particle size of the (C) inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 4 μm or less, even more preferably 3 μm or less, 2 μm or less, 1 μm or less, or 0.7 μm or less. The lower limit of the average particle size of the (C) inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. The average particle size of the (C) inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering particle size distribution measuring device, and the median diameter is taken as the average particle size. The measurement sample can be prepared by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device with blue and red light source wavelengths, and the particle size distribution of the inorganic filler on a volume basis was measured using a flow cell method, and the average particle size was calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction type particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

[0087] The specific surface area of ​​the (C) inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 The upper limit of the specific surface area of ​​the inorganic filler (C) is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 70m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 40m 2 The specific surface area of ​​the inorganic filler is obtained by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method.

[0088] As mentioned above, the (C) inorganic filler includes hollow inorganic filler. The material of hollow inorganic filler is as mentioned above about inorganic filler, among which hollow silica, hollow alumina or hollow aluminosilicate is preferred, and especially in combination with (B) aromatic polyether resin, from the viewpoint of obtaining a cured product with excellent flame retardancy and low relative dielectric constant and dielectric loss tangent, and even when the content of the hollow inorganic filler is high (for example, the content of the hollow inorganic filler in the resin composition is 30 mass% or more, 35 mass% or more, or 40 mass% or more when the non-volatile components in the resin composition are 100 mass%), hollow silica is more preferred from the viewpoint of easily achieving a cured product with excellent flame retardancy and low relative dielectric constant and dielectric loss tangent.

[0089] The (C) inorganic filler may further contain a solid inorganic filler so long as it contains a hollow inorganic filler. The material of the solid inorganic filler is as described above for the inorganic filler.

[0090] The content of the hollow inorganic filler is preferably 10% by mass or more, more preferably 30% by mass or more, and particularly preferably 50% by mass or more or more than 50% by mass (i.e., the content of the hollow inorganic filler is higher than the content of the solid inorganic filler), relative to 100% by mass of the (C) inorganic filler in the resin composition (the total of the hollow inorganic filler and the solid inorganic filler). The upper limit of the content can be, for example, 100% by mass or less, 90% by mass or less, 80% by mass or less, etc.

[0091] The average porosity of the hollow inorganic filler is preferably 90% by volume or less, more preferably 85% by volume or less. The lower limit of the average porosity of the hollow inorganic filler is not particularly limited, but is, for example, more than 0% by volume, 1% by volume or more, preferably 5% by volume or more, more preferably 10% by volume or more, even more preferably 15% by volume or more, 20% by volume or more, 25% by volume or more, or 30% by volume or more. The average porosity P (volume %) of the inorganic filler is defined as the volume-based ratio of the total volume of one or more voids present inside the particle to the total volume of the particle based on the outer surface of the particle (total volume of voids / volume of particle), and is, for example, the measured value D of the actual density (apparent density) of the inorganic filler. M (g / cm 3 ), and the theoretical value of the material density of the material forming the inorganic filler D T (g / cm 3 ) is used to calculate according to the following formula (I).

[0092]

number

[0093] The actual density (apparent density) of the inorganic filler can be measured, for example, by using a true density measuring device. Examples of the true density measuring device include ULTRAPYCNOMETER 1000 manufactured by QUANTACHROME. For example, nitrogen is used as the measurement gas.

[0094] (C) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane, an organosilazane compound, and a titanate coupling agent. The surface treatment agent may be used alone or in any combination of two or more.

[0095] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

[0096] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably 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 0.2% to 3% by mass, and even more preferably 0.3% to 2% by mass.

[0097] 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 set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, it is more preferable that the melt viscosity is 1.0 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0098] (C) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been 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, the "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used.

[0099] From the viewpoint of producing a cured product exhibiting good dielectric properties, the content (mass%) of the inorganic filler (C) in the resin composition is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 65% ​​by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass. The upper limit of the content (mass%) of the inorganic filler (C) in the resin composition is not particularly limited, but may be preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, even more preferably 75% by mass or less, and particularly preferably 70% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0100] From the viewpoint of producing a cured product exhibiting good dielectric properties, the content (volume %) of the inorganic filler (C) in the resin composition is preferably 20% by volume or more, more preferably 30% by volume or more, even more preferably 40% by volume or more, even more preferably 50% by volume or more, and particularly preferably 55% by volume or more, when the non-volatile components in the resin composition are taken as 100% by volume. The upper limit of the content (volume %) of the inorganic filler (C) in the resin composition is not particularly limited, but may be preferably 80% by volume or less, more preferably 75% by volume or less, even more preferably 70% by volume or less, even more preferably 65% ​​by volume or less, and particularly preferably 60% by volume or less, when the non-volatile components in the resin composition are taken as 100% by volume.

[0101] From the viewpoint of obtaining a cured product exhibiting good dielectric properties, the content of the hollow inorganic filler in the resin composition is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more, when the non-volatile components in the resin composition are 100% by mass. In conventional resin compositions, the content of the hollow inorganic filler tends to decrease in flame retardancy when the content of the hollow inorganic filler is increased. Although such a decrease in flame retardancy can be somewhat improved by using the flame retardant (D) described later, when the content of the flame retardant (D) is increased to a level that exhibits sufficient flame retardancy, the dielectric loss tangent of the obtained cured product increases, and the advantage of using the hollow inorganic filler is reduced. In contrast, according to the resin composition of the present invention using the aromatic polyether resin (B), the content of the hollow inorganic filler can be further increased while achieving good flame retardancy. For example, the content of the hollow inorganic filler in the resin composition may be increased to more than 30 mass%, 35 mass% or more, 40 mass% or more, or even more than 40 mass%, based on 100 mass% of the non-volatile components in the resin composition.

[0102] <(D) Flame retardant> The resin composition of the present invention may contain a flame retardant (D) as an optional component. The flame retardant (D) described here is a component different from the epoxy resin (A) and the inorganic filler (C) described above.

[0103] Examples of the (D) flame retardant include phosphorus-based flame retardants such as phosphazene compounds, phosphates, phosphoric acid esters, polyphosphates, phosphinates, phosphinic acid esters, phosphonates, and phosphonic acid esters; nitrogen-based flame retardants such as aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, and urea compounds; inorganic flame retardants such as metal hydroxides such as magnesium hydroxide and aluminum hydroxide, and antimony compounds such as antimony trioxide, antimony pentoxide, and sodium antimonate; and halogen-based flame retardants such as hexabromobenzene, chlorinated paraffin, brominated polycarbonate resins, brominated epoxy resins, brominated phenoxy resins, brominated polyphenylene ether resins, brominated polystyrene resins, and brominated benzyl polyacrylate resins. The (D) flame retardants may be used alone or in combination of two or more.

[0104] From the viewpoint of obtaining a cured product having excellent flame retardancy and low relative dielectric constant and dielectric dissipation factor in combination with the (B) aromatic polyether resin, and further from the viewpoint of easily achieving a cured product having excellent flame retardancy and low relative dielectric constant and dielectric dissipation factor even when the content of the hollow inorganic filler in the resin composition is high (for example, the content of the hollow inorganic filler in the resin composition is 30 mass % or more, 35 mass % or more, or 40 mass % or more, when the non-volatile components in the resin composition are taken as 100 mass %), the (D) flame retardant preferably includes a phosphorus-based flame retardant. The phosphorus-based flame retardant preferably includes a phosphorus-based flame retardant selected from the group consisting of phosphazenes, phosphates, phosphoric esters, polyphosphates, phosphinates, phosphinic esters, phosphonates, and phosphonic esters, more preferably includes a phosphorus-based flame retardant selected from the group consisting of phosphazenes, phosphoric esters, and phosphinic esters, even more preferably includes a phosphorus-based flame retardant selected from the group consisting of phosphazenes and phosphinic esters, and particularly preferably includes a phosphinic ester.

[0105] Examples of phosphazenes include phenoxycyclophosphazenes such as hexaphenoxycyclotriphosphazene, tris(4-hydroxyphenoxy)triphenoxycyclotriphosphazene, hexakis(4-hydroxyphenoxy)cyclotriphosphazene, tris(4-methylphenoxy)triphenoxycyclotriphosphazene, tris(4-cyanophenoxy)triphenoxycyclotriphosphazene, hexakis(4-aminophenoxy)cyclotriphosphazene, tris[4-(2-glycidyloxyethyl)phenoxy]triphenoxycyclotriphosphazene, and octaphenoxycyclotetraphosphazene.

[0106] Examples of phosphates include ammonium phosphate, melamine phosphate, and piperazine phosphate.

[0107] Examples of the phosphate ester include non-halogenated aliphatic phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and trioctyl phosphate; triphenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, tricresyl phosphate, tris(2,6-dimethylphenyl)phosphate, tris(4-isopropylphenyl)phosphate, tris(4-tert-butylphenyl)phosphate, and bis(4-tert-butylphenyl)phosphate. non-halogenated aromatic phosphate esters such as 1,3-phenylene bisphosphate, hydroxyphenyl diphenyl phosphate, octyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, and tetrakis(2,6-dimethylphenyl)-1,3-phenylene bisphosphate; and halogenated aliphatic phosphate esters such as tris(1-chloro-2-propyl)phosphate, tris(1,3-dichloro-2-propyl)phosphate, and tris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate.

[0108] Examples of polyphosphates include ammonium polyphosphate and melamine polyphosphate.

[0109] Examples of phosphinates include dialkylphosphinates such as aluminum tris(diethylphosphinate), zinc bis(diethylphosphinate), aluminum tris(methylethylphosphinate), zinc bis(methylethylphosphinate), and titanium tetrakis(diethylphosphinate); and diarylphosphinates such as zinc bis(diphenylphosphinate) and titanium tetrakis(diphenylphosphinate).

[0110] Examples of the phosphinic acid ester include dialkylphosphinic acid esters such as methyl dimethylphosphinate, ethyl dimethylphosphinate, ethyl diethylphosphinate, vinyl diethylphosphinate, and phenyl diethylphosphinate; non-cyclic diarylphosphinic acid esters such as phenyl diphenylphosphinate, methyl diphenylphosphinate, and ethyl diphenylphosphinate; 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphinic acid esters; 10-(1,4-dihydroxy-2-naphthyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxybiphenyl-4-yl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-[2,4-di(glycidyloxy)phenyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Cyclic diarylphosphinic acid esters of the above; cyclic monoarylphosphinic acid esters such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; 9,10-dihydro-10-benzyl-9-oxa-10-phosphaphenanthrene-10-oxide, 10-[2,3-bis(2-hydroxyethoxycarbonyl)propyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or polyether polycondensates thereof cyclic arylalkylphosphinic acid esters such as 10-(2-cyanoethyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-[2-(3,4-epoxycyclohexyl)ethyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(3-glycidyloxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0111] Examples of the phosphonate include zinc methanephosphonate, zinc ethylphosphonate, zinc butylphosphonate, and zinc phenylphosphonate.

[0112] Examples of phosphonate esters include aliphatic phosphonate esters such as diphenyl methylphosphonate, dibutyl butylphosphonate, diethyl ethylphosphonate, diethyl (methoxymethyl)phosphonate, and diethyl vinylphosphonate; and aromatic phosphonate esters such as diethyl phenylphosphonate, divinyl phenylphosphonate, and diallyl phenylphosphonate.

[0113] In combination with the (B) aromatic polyether resin, from the viewpoint of obtaining a cured product having excellent flame retardancy and low relative dielectric constant and dielectric loss tangent, and from the viewpoint of easily achieving a cured product having excellent flame retardancy and low relative dielectric constant and dielectric loss tangent even when the content of the hollow inorganic filler is high, and further from the viewpoint of easily achieving a cured product having a high glass transition temperature, it is more preferable that the (D) flame retardant contains a phosphinic acid ester, and particularly preferable that it contains a phenolic hydroxyl group-containing phosphinic acid ester. The phenolic hydroxyl group equivalent of the phenolic hydroxyl group-containing phosphorus-based flame retardant is not particularly limited, but is preferably 80 g / eq. to 1,000 g / eq., more preferably 100 g / eq. to 500 g / eq., even more preferably 110 g / eq. to 300 g / eq., even more preferably 120 g / eq. to 200 g / eq., and preferably 130 g / eq. to 180 g / eq. The phenolic hydroxyl group equivalent is the mass of the phosphorus-based flame retardant per equivalent of the phenolic hydroxyl group. Phosphinic acid esters containing phenolic hydroxyl groups may have the function of curing epoxy resin (A) like hardeners (F).

[0114] (D) Examples of commercially available flame retardants include "SPH-100", "SPS-100", "SPB-100", and "SPE-100" (phosphazenes) manufactured by Otsuka Chemical Co., Ltd.; "FP-100", "FP-110", "FP-300", and "FP-400" (phosphazenes) manufactured by Fushimi Pharmaceutical Co., Ltd.; "HCA-NQ", "HCA-HQ", and "HCA-HQ-HST" (phosphinic acid esters (containing phenolic hydroxyl groups)) manufactured by Sankosha; and "PX-200", "PX-201", "PX-202", "CR-733S", "CR-741", and "CR-747" (phosphate esters) manufactured by Daihachi Chemical Industry Co., Ltd.

[0115] The content of the flame retardant (D) in the resin composition is not particularly limited, but when the non-volatile components in the resin composition excluding the component (C) are taken as 100 mass%, from the viewpoint of suppressing the dielectric tangent lower, it is preferably 20 mass% or less, more preferably 10 mass% or less, even more preferably 8 mass% or less, even more preferably 6 mass% or less, and particularly preferably 5 mass% or less. The lower limit of the content of the flame retardant (D) in the resin composition is not particularly limited, but when the non-volatile components in the resin composition excluding the component (C) are taken as 100 mass%, it is, for example, 0 mass% or more, 0.01 mass% or more, or 0.05 mass% or more, and from the viewpoint of further improving the flame retardancy, it is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, even more preferably 1 mass% or more, and particularly preferably 2 mass% or more.

[0116] As described above, according to the resin composition of the present invention containing the aromatic polyether resin (B), even when a hollow inorganic filler is contained, and even when the content of the hollow inorganic filler is high, a cured product having excellent flame retardancy and low relative dielectric constant and dielectric loss tangent can be achieved, and the excellent effect of the aromatic polyether resin (B) can be more significantly enjoyed when a flame retardant (D) is contained. From the viewpoint of being able to enjoy the effects of the present invention even more, the mass ratio of the aromatic polyether resin (B) to the flame retardant (D) [(B) component / (D) component] is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 0.5 or more, 0.6 or more, 0.8 or more, or 1 or more, and even more preferably more than 1 (i.e., the content of the aromatic polyether resin (B) is higher than the content of the flame retardant (D)), 1.2 or more, 1.4 or more, or 1.5 or more. The upper limit of the mass ratio is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less, 10 or less, 8 or less, or 6 or less, from the viewpoint of achieving a cured product having excellent flame retardancy and low relative dielectric constant and dielectric tangent, when a hollow inorganic filler is contained, and even when the content of the hollow inorganic filler is high.

[0117] <(E) Carbodiimide resin> In the resin composition of the present invention, the component (E) is a carbodiimide resin.

[0118] The carbodiimide resin is a compound having one or more carbodiimide groups (-N=C=N-) in one molecule. By using the carbodiimide resin (E) in combination with the above components (A) to (C), it is easy to achieve a cured product having excellent flame retardancy and a further reduced relative dielectric constant and dielectric loss tangent, and it is also easy to achieve a resin composition having an appropriately low minimum melt viscosity and further improved lamination properties and conductor embedding properties, which is preferable.

[0119] The carbodiimide resin is preferably a compound having two or more carbodiimide groups in one molecule. The carbodiimide resin may be used alone or in combination of two or more.

[0120] In one embodiment, the (E) carbodiimide resin contains a structural unit represented by the following formula (E1):

[0121] [ka] (In the formula, X represents an alkylene group, a cycloalkylene group, or an arylene group, which may have a substituent. p represents an integer of 1 to 5. When there are multiple Xs, they may be the same or different. * represents a bond.)

[0122] The number of carbon atoms of the alkylene group represented by X is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms does not include the number of carbon atoms of the substituent. Suitable examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.

[0123] The number of carbon atoms of the cycloalkylene group represented by X is preferably 3 to 20, more preferably 3 to 12, and further preferably 3 to 6. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Suitable examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

[0124] The arylene group represented by X is a group in which two hydrogen atoms on an aromatic ring are removed from an aromatic hydrocarbon. The number of carbon atoms in the arylene group is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. The number of carbon atoms does not include the number of carbon atoms of the substituent. Suitable examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

[0125] In terms of facilitating the achievement of a cured product having excellent flame retardancy and an even lower relative dielectric constant and dielectric loss tangent in combination with the components (A) to (C), and facilitating the achievement of a resin composition having an appropriately low minimum melt viscosity and even better lamination properties and conductor embedding properties, X is preferably an alkylene group or a cycloalkylene group, which may have a substituent.

[0126] The alkylene group, cycloalkylene group or aryl group represented by X may have a substituent. The substituent is not particularly limited, but examples thereof include a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group and an acyloxy group. Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group and the alkoxy group used as a substituent may be either linear or branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms of the cycloalkyl group and the cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. The aryl group used as a substituent is a group obtained by removing one hydrogen atom on the aromatic ring from an aromatic hydrocarbon, and the number of carbon atoms is preferably 6 to 24, more preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. The number of carbon atoms in the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, and further preferably 6 to 10. The acyl group used as a substituent is represented by the formula: -C(=O)-R 1 (wherein R 1 represents an alkyl group or an aryl group. 1 The alkyl group represented by the formula (I) may be either linear or branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 6, 1 to 4, or 1 to 3 carbon atoms. 1The number of carbon atoms of the aryl group represented by the formula: is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, and further preferably 6 to 10. The acyloxy group used as a substituent is represented by the formula: -OC(=O)-R 1 (wherein R 1 has the same meaning as above.) Among them, as the substituent, an alkyl group, an alkoxy group, and an acyloxy group are preferable, and an alkyl group is more preferable.

[0127] In formula (E1), p represents an integer of 1 to 5. In combination with components (A) to (C), from the viewpoint of easily achieving a cured product having excellent flame retardancy and an even lower relative dielectric constant and dielectric loss tangent, and from the viewpoint of easily achieving a resin composition having an appropriately low minimum melt viscosity and even better lamination property and conductor embedding property, p is preferably 1 to 4, more preferably 2 to 4, and even more preferably 2 or 3.

[0128] In formula (E1), when there are a plurality of X's, they may be the same or different. In a preferred embodiment, at least one X is an alkylene group or a cycloalkylene group, which may have a substituent.

[0129] In a preferred embodiment, the carbodiimide resin contains the structural unit represented by formula (E1) at preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more or 90% by mass or more, when the mass of the entire molecule of the carbodiimide resin is taken as 100% by mass. The carbodiimide resin may be substantially composed of the structural unit represented by formula (E1) except for the terminal structure. The terminal structure of the carbodiimide resin is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group, which may have a substituent. The alkyl group, cycloalkyl group, and aryl group used as the terminal structure may be the same as the alkyl group, cycloalkyl group, and aryl group described for the substituent that the group represented by X may have. In addition, the substituent that the group used as the terminal structure may have may be the same as the substituent that the group represented by X may have.

[0130] From the viewpoint of obtaining the above-mentioned effects more effectively, the weight average molecular weight of the carbodiimide resin is preferably 500 or more, more preferably 600 or more, even more preferably 700 or more, even more preferably 800 or more, and particularly preferably 900 or more or 1000 or more. From the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the carbodiimide resin is preferably 5000 or less, more preferably 4500 or less, even more preferably 4000 or less, even more preferably 3500 or less, and particularly preferably 3000 or less. The weight average molecular weight of the carbodiimide resin can be measured, for example, by gel permeation chromatography (GPC) method (polystyrene equivalent).

[0131] Commercially available carbodiimide resins may be used. Examples of commercially available carbodiimide resins include Carbodilite (registered trademark) V-02B, V-03, V-04K, V-07, and V-09 manufactured by Nisshinbo Chemical Co., Ltd., and Stavaxol (registered trademark) P, P400, and Hi-Kasil 510 manufactured by Lanxess AG.

[0132] The content of the carbodiimide resin (E) in the resin composition is, for example, 0% by mass or more, 0.01% by mass or more, or 0.05% by mass or more, when the nonvolatile components in the resin composition excluding the component (C) are taken as 100% by mass. In terms of facilitating the achievement of a cured product having excellent flame retardancy and a further reduced relative dielectric constant and dielectric loss tangent in combination with the components (A) to (C), and facilitating the achievement of a resin composition having a moderately low minimum melt viscosity and further improved lamination and conductor embedding properties, the content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more. The upper limit of the content of the carbodiimide resin (E) in the resin composition is not particularly limited, but is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, even more preferably 6% by mass or less, and particularly preferably 5% by mass or less, when the nonvolatile components in the resin composition excluding the component (C) are taken as 100% by mass.

[0133] <(F) Hardener> The resin composition of the present invention may contain a (F) curing agent as an optional component. The (F) curing agent may have a function of reacting with the (A) epoxy resin to cure it. The (F) curing agent may be used alone or in any combination of two or more types. The (F) curing agent described here is a component different from the above-mentioned (D) flame retardant and the thermoplastic resin described below.

[0134] The (F) curing agent is not particularly limited, and examples thereof include active ester curing agents, phenolic curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol curing agents. In one embodiment, the (F) curing agent preferably contains one or more epoxy resin curing agents selected from active ester curing agents, phenolic curing agents, and cyanate ester curing agents, and more preferably contains one or more epoxy resin curing agents selected from active ester curing agents and phenolic curing agents. In one embodiment, the (F) curing agent is particularly preferably contains an active ester curing agent from the viewpoint of further suppressing the dielectric tangent. In one embodiment, the (F) curing agent is particularly preferably contains a phenolic curing agent from the viewpoint of further improving the curability. Furthermore, in the combination with the components (A) to (C), when the curing agent (F) contains one or more selected from the group consisting of active ester-based curing agents and phenol-based curing agents, it is preferable because it is easy to achieve a cured product that has excellent flame retardancy and an even lower relative dielectric constant and dielectric loss tangent, and it is also easy to achieve a resin composition that has an appropriately low minimum melt viscosity and thus better lamination properties and conductor embeddability.

[0135] As the active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester curing agent, a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, is preferable. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent derived from a carboxylic acid compound is preferable, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is more preferable, and an active ester curing agent obtained from a carboxylic acid compound and an aromatic hydroxy compound is even more preferable.

[0136] The carboxylic acid compound may be either an aromatic carboxylic acid compound or an aliphatic carboxylic acid compound, and examples thereof include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and halides thereof.

[0137] Examples of aromatic hydroxy compounds include (i) polyaddition products of unsaturated aliphatic cyclic compounds containing two double bonds in one molecule and phenols, (ii) various bisphenol compounds, (iii) aromatic polyols having two or more hydroxyl groups bonded to the carbon atoms on the aromatic ring, and (iv) aromatic monools having one hydroxyl group bonded to the carbon atoms on the aromatic ring. Examples of polyaddition products of unsaturated aliphatic cyclic compounds and phenols include polyaddition products of unsaturated aliphatic cyclic compounds such as dicyclopentadiene, tetrahydroindene, norbornadiene, limonene, and vinylcyclohexene with phenols that may have a substituent (e.g., phenol, cresol, xylenol, ethylphenol, propylphenol, vinylphenol, allylphenol, phenylphenol, benzylphenol, halophenol, etc.), and specifically, for example, dicyclopentadiene-phenols polyaddition products. Examples of bisphenol compounds include bisphenol A, bisphenol F, bisphenol AF, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, and bisphenol M. Examples of aromatic polyols having two or more hydroxy groups bonded to carbon atoms on an aromatic ring include hydroquinone, resorcinol, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, and phenol novolak. Examples of aromatic monools having one hydroxy group bonded to a carbon atom on an aromatic ring include phenol, cresol, xylenol, ethylphenol, propylphenol, vinylphenol, allylphenol, phenylphenol, benzylphenol, halophenol, naphthol, methylnaphthol, dimethylnaphthol, ethylnaphthol, propylnaphthol, vinylnaphthol, allylnaphthol, phenylnaphthol, benzylnaphthol, and halonaphthol.

[0138] Specifically, the active ester curing agent is preferably 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 novolac, or an active ester compound containing a benzoylated product of phenol novolac, and more preferably at least one selected from a dicyclopentadiene type active ester compound and a naphthalene type active ester compound. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferable.

[0139] Commercially available active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", and "EXB-8000H" (manufactured by DIC Corporation); active ester compounds containing a naphthalene structure, such as "EXB-8100L-65T", "EXB-9416-70BK", "HPC-8150-62T", and "EXB-8" (manufactured by DIC Corporation); Examples of the active ester compound containing phosphorus include "EXB9401" (manufactured by DIC Corporation); an active ester compound which is an acetylated product of phenol novolac is "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds which are benzoylated products of phenol novolac are "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and an active ester compound containing a styryl group and a naphthalene structure is "PC1300-02-65MA" (manufactured by Air Water Inc.).

[0140] As the phenol-based curing agent, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure is preferable. Also, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a triazine skeleton-containing phenol novolac resin is preferable. Specific examples of phenol-based curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", and "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", and "KA-1160" manufactured by DIC Corporation.

[0141] Examples of the acid anhydride curing agent include a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule is preferable. Specific examples of the acid anhydride 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, and benzophenonetetracarboxylic dianhydride. Examples of acid anhydrides include anhydrides, 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 polymeric acid anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid. Commercially available acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by New Japan Chemical Co., Ltd., "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation, "HN-2200" and "HN-5500" manufactured by Resonaq, and "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Cray Valley Chemical Industries, Ltd.

[0142] 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, 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.

[0143] 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.

[0144] Examples of the cyanate ester curing agent 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'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester-based curing agents include Arcada's "PT30," "PT30S," and "PT60" (all of which are phenol novolac-type multifunctional cyanate ester resins), "BA230," and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been converted to triazine to form a trimer).

[0145] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0146] The reactive group equivalent of the (F) curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactive group equivalent is the mass of the (F) curing agent per equivalent of reactive group.

[0147] When an active ester curing agent is included as the curing agent (F), the content of the active ester curing agent in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, 16% by mass or more, 18% by mass or more, or 20% by mass or more, in terms of suppressing the dielectric tangent lower, when the non-volatile components in the resin composition excluding the component (C) are taken as 100% by mass. In particular, when the content of the active ester curing agent in the resin composition is 15% by mass or more, when the non-volatile components in the resin composition excluding the component (C) are taken as 100% by mass, even when the blending amount of the flame retardant (D) is high, the dielectric tangent can be suppressed further lower in combination with the aromatic polyether resin (B), and the minimum melt viscosity is appropriately low, making it easy to achieve a resin composition with better lamination properties and conductor embedding properties. Furthermore, the content of the active ester-based curing agent in the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, from the viewpoint of keeping the dielectric tangent lower, assuming that the content of the (F) curing agent in the resin composition is 100% by mass.

[0148] When a phenol-based curing agent is included as the (F) curing agent, the content of the phenol-based curing agent in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, 3% by mass or more, 4% by mass or more, or 5% by mass or more, from the viewpoint of further improving the curability, when the non-volatile components excluding the (C) component in the resin composition are taken as 100% by mass.

[0149] The content of the (F) curing agent in the resin composition is not particularly limited, but is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less, when the non-volatile components in the resin composition excluding the (C) component are taken as 100% by mass. The lower limit of the content of the (F) curing agent in the resin composition is not particularly limited, but may be, for example, 0% by mass or more, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more, when the non-volatile components in the resin composition excluding the (C) component are taken as 100% by mass.

[0150] In combination with the (B) aromatic polyether resin, from the viewpoint of obtaining a cured product having excellent flame retardancy and low dielectric constant and dielectric loss tangent, and further from the viewpoint of easily achieving a cured product having excellent flame retardancy and low dielectric constant and dielectric loss tangent even when the content of the hollow inorganic filler is high, the mass ratio of the (F) curing agent to the (A) epoxy resin in the resin composition [(F) component / (A) component] is preferably 0.3 or more, more preferably 0.4 or more, and even more preferably 0.5 or more, and the upper limit is preferably 2 or less, more preferably 1.5 or less, and even more preferably 1.4 or less, 1.2 or less, or 1 or less. From the viewpoint of obtaining a cured product exhibiting better dielectric properties, it has been reported that it is beneficial to increase the mass ratio, but it has also been reported that this may cause deterioration of insulation reliability under high temperature and high humidity conditions, or cause a decrease in smear removability during desmear treatment. In contrast, the resin composition of the present invention containing a combination of the components (A) to (C) can achieve good dielectric properties without significantly increasing the mass ratio of the curing agent (F) to the epoxy resin (A) (thus reducing the occurrence of problems due to the incorporation of a high amount of the component (F)). For example, good dielectric properties can be achieved even when the mass ratio [component (F) / component (A)] is 0.8 or less, 0.75 or less, 0.7 or less, 0.65 or less, or 0.6 or less.

[0151] <(G) Maleimide resin> The resin composition of the present invention may contain, as an optional component, a maleimide resin (G). By containing the component (G), a cured product exhibiting an even lower dielectric tangent can be obtained.

[0152] The component (G) is (G1) a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to a nitrogen atom of the maleimide; (G2) Maleimide compounds containing a trimethylindane skeleton, and (G3) a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide; It is preferable that the compound is one or more selected from the above.

[0153] The term "directly" used herein means that, in the case of component (G1), there is no other group between the nitrogen atom of the maleimide and the aliphatic group having 5 or more carbon atoms, and in the case of component (G3), there is no other group between the nitrogen atom of the maleimide and the aromatic ring.

[0154] The component (G), whether it is the component (G1), the component (G2), or the component (G3), preferably has two or more maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule.

[0155] The following describes the (G1), (G2), and (G3) components, which are suitable embodiments of the (G) component. In the following, the term "substituent" means, unless otherwise specified, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylthio group, a monovalent heterocyclic group, an alkylidene group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group. Examples of halogen atoms used as substituents include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 14, even more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a t-butyl group. The number of carbon atoms of the cycloalkyl group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. The alkoxy group used as a substituent may be either linear or branched. The number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The number of carbon atoms of the cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. Examples of the cycloalkyloxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group. The alkylthio group used as a substituent preferably has 1 to 20 carbon atoms, more preferably 1 to 14, even more preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms.The aryl group used as a substituent is a group in which one hydrogen atom on an aromatic ring is removed from an aromatic hydrocarbon. The number of carbon atoms in the aryl group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms in the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryloxy group used as a substituent include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. The number of carbon atoms in the arylalkyl group used as a substituent is preferably 7 to 25, more preferably 7 to 19, even more preferably 7 to 15, and even more preferably 7 to 11. Examples of the arylalkyl group include phenyl-C1-C. 12 Alkyl groups, naphthyl-C1-C 12 Alkyl groups and anthracenyl-C1-C 12 The number of carbon atoms in the arylalkoxy group used as a substituent is preferably 7 to 25, more preferably 7 to 19, further preferably 7 to 15, and further preferably 7 to 11. Examples of the arylalkoxy group include phenyl-C1-C 12 Alkoxy group, and naphthyl-C1-C 12Examples of the monovalent heterocyclic group include an alkoxy group. The number of carbon atoms of the arylthio group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. The monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom from a heterocyclic ring of a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably 3 to 21, more preferably 3 to 15, and even more preferably 3 to 9. The monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocyclic ring include a thienyl group, a pyrrolyl group, a furanyl group, a furyl group, a pyridyl group, a pyridazinyl group, a pyrimidyl group, a pyrazinyl group, a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group. The alkylidene group used as a substituent refers to a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms in the alkylidene group is preferably 1 to 20, more preferably 1 to 14, even more preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 3. The acyl group used as a substituent refers to a group represented by the formula: -C(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms in the acyl group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 7. The acyloxy group used as a substituent refers to a group represented by the formula: -OC(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms in the acyloxy group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 7. The above-mentioned substituents may further have a substituent (hereinafter, sometimes referred to as a "secondary substituent"). Unless otherwise specified, the secondary substituent may be the same as the above-mentioned substituent.

[0156] -(G1) Ingredients- The component (G1) is a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to a nitrogen atom of the maleimide. Such a maleimide compound can be obtained, for example, by subjecting a component containing an aliphatic amine compound (such as a dimer diamine compound), maleic anhydride, and, if necessary, tetracarboxylic dianhydride to an imidization reaction.

[0157] In one embodiment, the component (G1) includes a compound represented by the following formula (G1-1):

[0158] [ka]

[0159] In formula (G1-1), A 1 represents an aliphatic group having 5 or more carbon atoms which may have a substituent, L 1 represents a single bond or a divalent linking group, nB1 represents an integer from 0 to 20. 1 When there are multiple, they may be the same or different, and L 1 When there are multiple, they may be the same or different.

[0160] A 1 The number of carbon atoms in the aliphatic group represented by the formula (I) is 5 or more, and preferably 10 or more, 15 or more, or 20 or more. The upper limit of the number of carbon atoms is not particularly limited, and may be, for example, 100 or less, 80 or less, 60 or less, or 50 or less. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0161] In one embodiment, A 1 is a divalent group represented by the following formula (G1-2).

[0162] [ka]

[0163] In formula (G1-2), A 11 represents a single bond, an alkylene group, or an alkenylene group (preferably an alkylene group or an alkenylene group), Ring Z 1 represents a non-aromatic ring optionally having a group selected from an alkyl group and an alkenyl group (preferably a cycloalkane ring or cycloalkene ring optionally having a group selected from an alkyl group and an alkenyl group), nB11 represents an integer of 0 to 3 (preferably 0 or 1, more preferably 1); * indicates the binding site. 11 Or Z 1 Each of A may independently have a substituent. 11 When there are multiple rings, they may be the same or different. 1 When there are multiple, they may be the same or different.

[0164] L 1 Examples of the divalent linking group represented by the formula (G1-3) include divalent organic groups (preferably divalent ring-containing organic groups (e.g., aromatic rings or non-aromatic rings)) consisting of two or more (e.g., 2 to 3000, 2 to 1000, 2 to 100, or 2 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, and among these, divalent groups represented by the formula (G1-3) below are preferred.

[0165] [ka]

[0166] In formula (G1-3), A 12 represents a single bond or a divalent group consisting of one or more (e.g., 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, R B1 and R B2 each independently represents a substituent, nB12 represents 0 or 1; nB13 and nB14 each independently represent an integer of 0 to 3 (preferably 0 or 1), * indicates the binding site. B1 When there are multiple, they may be the same or different, and R B2 When there are multiple, they may be the same or different.

[0167] When nB12 is 0, the divalent group represented by formula (G1-3) is a divalent group having a structure represented by the following formula (G1-4): B1 , nB13 and * are as explained in formula (G1-3).

[0168] [ka]

[0169] In the embodiment in which nB12 in formula (G1-3) is 1, A 12 The divalent group represented by the following formula (G1-5) is preferable.

[0170] [ka]

[0171] In formula (G1-5), Y 1 represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; Ring Z 2 represents an optionally substituted non-aromatic ring or an optionally substituted aromatic ring, nB15 represents an integer of 0 to 5 (preferably 0 to 3), * indicates the binding site. 1 Or Z 2 Each of Y may independently have a substituent. 1 When there are multiple rings, they may be the same or different. 2When there are multiple, they may be the same or different.

[0172] A 12 Specific examples of the divalent group represented by the formula (I) include, but are not limited to, -CH-, -CH(CH)-, -CH(CHCH)-, -C(CH)-, -C(CH)(CHCH)-, -C(CHCH)-, -O-, -CO-, -S-, -SO-, and -SO-, as well as divalent organic groups represented by the formula (I) below. [ka]

[0173] The weight average molecular weight (Mw) of the component (G1) is not particularly limited, but is preferably 150 to 50,000, more preferably 300 to 20,000, and more specifically, in an embodiment in which nB1 in formula (G1-1) is an integer of 1 or more, it is preferably 500 to 50,000, more preferably 1,000 to 20,000, and in an embodiment in which nB1 is 0, it is preferably 150 to 5,000, more preferably 300 to 1,000. The Mw of the component (G1) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0174] Furthermore, with regard to the component (G1), the functional group equivalent of the maleimide group is preferably 50 to 20,000 g / eq, more preferably 100 to 20,000 g / eq.; more specifically, in an embodiment in which nB1 in formula (G1-1) is an integer of 1 or more, it is preferably 300 g / eq. to 20,000 g / eq., more preferably 500 g / eq. to 10,000 g / eq.; and in an embodiment in which nB1 is 0, it is preferably 50 g / eq. to 2,000 g / eq., more preferably 100 g / eq. to 1,000 g / eq., even more preferably 200 g / eq. to 600 g / eq., and particularly preferably 300 g / eq. to 400 g / eq.

[0175] In particular, in combination with the aromatic polyether resin (B), from the viewpoint of obtaining a cured product having excellent flame retardancy and low dielectric constant and dielectric dissipation factor, and further from the viewpoint of easily achieving a cured product having excellent flame retardancy and low dielectric constant and dielectric dissipation factor even when the content of the hollow inorganic filler in the resin composition is high (for example, when the content of the hollow inorganic filler in the resin composition is 30 mass % or more, 35 mass % or more, or 40 mass % or more, assuming that the non-volatile components in the resin composition are 100 mass %), it is preferable that the component (G1) contains a maleimide compound having any of a structure represented by the following formula (G1-6), a structure represented by the following formula (G1-7), or a structure represented by the following formula (G1-8).

[0176] [ka]

[0177] In formula (G1-6), A 11 and ring Z 1 As explained above, A 11 -Ring Z 1 -A 11 The number of carbon atoms per block is preferably 20 to 100 (more preferably 30 to 60 or 30 to 50), and it is particularly preferably a so-called dimer acid skeleton (C36 skeleton; C36 alkylene skeleton derived from dimer diamine). nB16 represents an integer of 1 to 10.

[0178] [ka]

[0179] In formula (G1-7), A 11 , Y 1 , ring Z 1 , ring Z 2 and nB15 are as described above, and A 11 -Ring Z 1 -A 11The number of carbon atoms per block is preferably 20 to 100 (more preferably 30 to 60 or 30 to 50), and it is particularly preferably a so-called dimer acid skeleton (C36 skeleton; C36 alkylene skeleton derived from dimer diamine). In addition, the block consisting of nB15+1 Y1 and nB15 rings Z2 is preferably a divalent group A 12 Among them, a divalent group containing an oxygen atom is preferable. nB17 represents an integer of 1 to 10.

[0180] [ka]

[0181] In formula (G1-8), A 11 and ring Z 1 As explained above, A 11 -Ring Z 1 -A 11 The number of carbon atoms per block is preferably 20 to 100 (more preferably 30 to 60 or 30 to 50), and it is particularly preferably a so-called dimer acid skeleton (C36 skeleton; C36 alkylene skeleton derived from dimer diamine). nB11 represents an integer of 0 to 10.

[0182] Commercially available maleimide compounds having a structure represented by formula (G1-6) include, for example, "BMI-3000J" and "BMI-5000" manufactured by Designer Molecules. Commercially available maleimide compounds having a structure represented by formula (G1-7) include, for example, "BMI-1400", "BMI-1500", and "BMI-1700" manufactured by Designer Molecules, and "SLK-1500-T80" manufactured by Shin-Etsu Chemical Co., Ltd. Commercially available maleimide compounds having a structure represented by formula (G1-8) include, for example, "BMI-689" manufactured by Designer Molecules, and "SLK-6895-T90" manufactured by Shin-Etsu Chemical Co., Ltd.

[0183] -(G2) component- The component (G2) is a maleimide compound containing a trimethylindane skeleton, which is represented by the following formula (G2-1).

[0184] [ka]

[0185] The benzene ring in the trimethylindane skeleton may have a substituent. When the benzene ring in the trimethylindane skeleton has a substituent, the number of the substituent may be 1 or 2 or more. The upper limit of the number of the substituents that the benzene ring in the trimethylindane skeleton has is usually 3 or less. When the number of the substituents is 2 or more, they may be the same or different from each other. Among them, it is preferable that the benzene ring in the trimethylindane skeleton does not have a substituent.

[0186] The number of trimethylindane structures contained in one molecule of the component (G2) may be 1, or may be equal to or greater than 2. The upper limit can be, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

[0187] From the viewpoint of obtaining the effects of the present invention more effectively, the component (G2) preferably contains a structure represented by the following formula (G2-2): The entire component (G2) may have a structure represented by the formula (G2-2), or only a part of the component (G2) may have a structure represented by the formula (G2-2).

[0188] [ka]

[0189] In formula (G2-2), Ar a1 represents a divalent aromatic ring group which may have a substituent, R a1 and R a2 each independently represents a substituent, R a3 represents a divalent aliphatic hydrocarbon group, na1 represents a positive integer, n a2 each independently represents an integer of 0 to 4, n a3 R each independently represents an integer of 0 to 3. a1 When there are multiple, they may be the same or different, and R a2 If there are multiple R a3 may be the same or different from each other.

[0190] Ar a1 represents a divalent aromatic ring group which may have a substituent. The number of carbon atoms in the divalent aromatic ring group is preferably 6 or more, and preferably 20 or less, more preferably 16 or less, 14 or less, or 10 or less. Examples of the divalent aromatic ring group include a phenylene group and a naphthylene group. Examples of the substituent that the divalent aromatic ring group may have include the above-mentioned substituents, and among them, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, and a mercapto group are preferred. The hydrogen atom of each substituent may be further substituted with a halogen atom. When the divalent aromatic ring group has a substituent, the number of the substituent is preferably 1 to 4. When the divalent aromatic ring group has two or more substituents, the two or more substituents may be the same or different. a1 is preferably a divalent aromatic ring group having no substituent.

[0191] R a1 R represents a substituent. a1Examples of the substituent represented by the formula (I) include the above-mentioned substituents, and among them, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, and a mercapto group are preferred. The hydrogen atom of each of the substituents may be further substituted with a halogen atom. Among them, R a1 is more preferably one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and is further preferably an alkyl group having 1 to 4 carbon atoms.

[0192] R a2 R represents a substituent. a2 Examples of the substituent represented by the formula (I) include the above-mentioned substituents, and among them, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, and a mercapto group are preferred. The hydrogen atom of each of the substituents may be further substituted with a halogen atom. Among them, R a2 is more preferably one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0193] R a3 represents a divalent aliphatic hydrocarbon group. The preferred range of the divalent aliphatic hydrocarbon group is as described above.

[0194] n a1 represents a positive integer. a1 is preferably 1 or more, and preferably 10 or less, more preferably 8 or less.

[0195] na2 Each independently represents an integer of 0 to 4. a2 is preferably 2 or 3, more preferably 2. a2 may be different from each other, but are preferably the same. a2 If is 2 or more, multiple R a1 may be the same or different from each other.

[0196] n a3 represents an integer of 0 to 3. a3 When there are a plurality of n, they may be different from each other, but are preferably the same as each other. a3 is preferably 0.

[0197] From the viewpoint of obtaining the effects of the present invention more effectively, it is more preferable that the (G2) component contains a structure represented by the following formula (G2-3): The entire (G2) component may have a structure represented by the formula (G2-3), or only a part of the (G2) component may have a structure represented by the formula (G2-3).

[0198] [ka]

[0199] In formula (G2-3), R a1 , R a2 , n a1 , n a2 and n a3 is as explained in formula (G2-2).

[0200] The component (G2) may further contain a structure represented by the following formula (G2-4).

[0201] [ka]

[0202] In formula (G2-4), R a1 , R a2 , n a2 and n a3is as explained in formula (G2-2). c1 is the number of repeating units and represents an integer of 1 to 20. * represents a bond.

[0203] For example, the component (G2) is a compound represented by the formula (G2-2): a2 is 3 or less, and R is present at two or more of the ortho and para positions relative to the maleimide group bonding position of the benzene ring to which the maleimide group is bonded. a1 When is not bonded, the structure represented by formula (G2-2) may include a structure represented by formula (G2-4) in combination with the structure represented by formula (G2-2).

[0204] For example, the component (G2) is represented by the formula (G2-3), a2 is 3 or less, and R is present at two or more of the ortho and para positions relative to the maleimide group bonding position of the benzene ring to which the maleimide group is bonded. a1 When is not bonded, the structure represented by formula (G2-3) may include a structure represented by formula (G2-4) in combination with the structure represented by formula (G2-4).

[0205] The method for producing the component (G2) is not particularly limited, and may be produced, for example, by the method described in the Japan Institute of Invention and Innovation Disclosure Technical Bulletin No. 2020-500211. According to the production method described in this Japan Institute of Invention and Innovation Disclosure Technical Bulletin No. 2020-500211, it is possible to obtain a maleimide compound having a distribution in the number of repeating units of the trimethylindane skeleton.

[0206] The (G2) component preferably has a molecular weight distribution Mw / Mn calculated by gel permeation chromatography (GPC) measurement in a specific range. Specifically, the molecular weight distribution Mw / Mn of the maleimide compound containing the structure represented by formula (G2-5) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, even more preferably 1.2 to 3.6, and particularly preferably 1.3 to 3.4.

[0207] With respect to the component (G2), the functional group equivalent of the maleimide group is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, even more preferably 200 g / eq. or more, and is preferably 2000 g / eq. or less, more preferably 1000 g / eq. or less, even more preferably 800 g / eq. or less.

[0208] -(G3) component- The component (G3) is a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide. Such a maleimide compound can be obtained, for example, by imidization of a component containing an aromatic amine compound (such as an aromatic diamine compound) and maleic anhydride.

[0209] In one embodiment, the (G3) component includes a compound represented by the following formula (G3-1):

[0210] [ka]

[0211] In formula (G3-1), Ring Ar 1 represents an aromatic ring which may have a substituent, L 2 represents a single bond or a divalent linking group, nB2 represents an integer of 1 to 100. 1 may be the same or different, L 2 When there are multiple, they may be the same or different.

[0212] Ring Ar 1 The aromatic ring represented by the formula (I) may be either a carbocyclic ring or a heterocyclic ring, but is preferably a carbocyclic ring. 1 The number of carbon atoms in the aromatic ring represented by the following formula is preferably 3 to 20, and more preferably 5 to 14 or 6 to 10. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0213] L 2The divalent linking group represented by the formula (G1-3) is not particularly limited as long as it is a divalent group consisting of one or more (for example, 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. For example, A 12 Examples of the divalent group include the divalent group shown in

[0214] Among these, from the viewpoint of obtaining the effects of the present invention more effectively, the ring Ar 1 is preferably an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent (more preferably a benzene ring which may have a substituent), and L 2 (L 2 If there are multiple L, at least one 2 is preferably a divalent group having a biphenyl skeleton. Thus, in one embodiment, the (G3) component has a biphenyl skeleton.

[0215] In the (G3) component, the nitrogen atom of the maleimide is directly bonded to the aromatic ring. The bonding position of the maleimide and the aromatic ring is the same as that of the L bonded to the aromatic ring. 2 For example, when the aromatic ring is a benzene ring, the bonding position of the maleimide to the benzene ring may be any position based on the position of L bonded to the benzene ring. 2 Based on this standard, the bond may be at any of the ortho, meta, and para positions, but it is preferred that the bond be at the para position in order to obtain the effects of the present invention more effectively.

[0216] In a preferred embodiment, the component (G3) includes a compound represented by the following formula (G3-2):

[0217] [ka]

[0218] In formula (G3-2), R B3 , R B4 , R B5 and R B6each independently represents a substituent, nB21 represents an integer from 1 to 100, nB22 and nB23 each independently represent an integer of 1 to 10; nB24 and nB25 each independently represent an integer of 0 to 3; nB26 and nB27 each independently represent an integer of 0 to 4. B3 When there are multiple, they may be the same or different, which means that R B4 , R B5 and R B6 The same applies to.

[0219] nB21 is preferably 1-50, more preferably 1-20, and further preferably 1-5. nB22 and nB23 each independently represent preferably 1 to 6, more preferably 1 to 3, and further preferably 1 or 2. nB24 and nB25 are each independently preferably an integer of 0 to 2, more preferably 0 or 1. When nB24 and nB25 are 1 or more, R B3 and R B4 It is preferable that each of the substituents represented by the following formula (I) is independently an alkyl group or an aryl group. nB26 and nB27 are each independently preferably an integer of 0 to 2, more preferably 0 or 1. When nB26 and nB27 are 1 or more, R B5 and R B6 Each of the substituents represented by the following formula (1) is preferably an alkyl group or an aryl group.

[0220] When the component (G3) has a molecular weight distribution, the weight average molecular weight (Mw) is 500 or more, and preferably 550 or more. There are no particular limitations on the upper limit of the Mw, but it is preferably 5000 or less, and more preferably 2500 or less. The Mw of the component (G3) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0221] Furthermore, for the component (G3), the functional group equivalent of the maleimide group is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., even more preferably 150 g / eq. to 500 g / eq., and particularly preferably 200 g / eq. to 300 g / eq.

[0222] A commercially available product of the compound represented by (G3-2) is, for example, "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. As the compound represented by formula (G3-1), "BMI-4000" manufactured by Daiwa Kasei Co., Ltd., "BMI-80" manufactured by Keiai Kasei Co., Ltd., and the like may also be used as the component (G3).

[0223] The content of the maleimide resin (G) in the resin composition is, for example, 0% by mass or more, 0.01% by mass or more, or 0.05% by mass or more, when the nonvolatile components in the resin composition excluding the component (C) are taken as 100% by mass. In terms of facilitating the achievement of a cured product having excellent flame retardancy and a low relative dielectric constant and dielectric loss tangent in combination with the components (A) to (C), the content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, 2.5% by mass or more, or 3% by mass or more. In terms of being able to enjoy the effects of the present invention more effectively, the upper limit of the content of the maleimide resin (G) in the resin composition is, when the nonvolatile components in the resin composition excluding the component (C) are taken as 100% by mass, preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less, 8% by mass or less, 6% by mass or less, or 5% by mass or less.

[0224] In particular, in combination with the aromatic polyether resin (B), from the viewpoint of obtaining a cured product having excellent flame retardancy and low dielectric constant and dielectric loss tangent, and even when the content of the hollow inorganic filler is high (for example, when the content of the hollow inorganic filler in the resin composition is 30% by mass or more, 35% by mass or more, or 40% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass), from the viewpoint of easily achieving a cured product having excellent flame retardancy and low dielectric constant and dielectric loss tangent, the maleimide resin (G) preferably contains the component (G1). From the viewpoint of being able to enjoy the above-mentioned effect more significantly, when the content of the maleimide resin (G) in the resin composition of the present invention is taken as 100% by mass, the content of the component (G1) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, and the upper limit is not particularly limited and may be 100% by mass.

[0225] <Other additives> The resin composition of the present invention may further contain an optional additive, such as one or more additives selected from the group consisting of thermoplastic resins and curing accelerators.

[0226] -Thermoplastic resin- The thermoplastic resin is a component other than the epoxy resin (A) explained above.

[0227] Examples of the 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 thermoplastic resin preferably contains a thermoplastic resin selected from the group consisting of polyimide resin and phenoxy resin, and more preferably contains phenoxy resin. The thermoplastic resin may be used alone or in combination of two or more kinds.

[0228] Specific examples of polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., and "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd.

[0229] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0230] Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both of which are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "YX7200B35", "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482" manufactured by Mitsubishi Chemical Corporation.

[0231] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred.Specific examples of polyvinyl acetal resins include S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0232] Examples of polyolefin resins include ethylene-based copolymer resins such as low-density polyethylene, very low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0233] Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxy group-containing polybutadiene resins, phenolic hydroxy 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, and the like.

[0234] Specific examples of polyamide-imide resins include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins also include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Resonac Corporation.

[0235] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0236] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0237] A specific example of the polyphenylene ether resin is NORYL SA90 manufactured by SABIC Corp. A specific example of the polyetherimide resin is ULTEM manufactured by GE Corp.

[0238] Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include Mitsubishi Gas Chemical's "FPC0220," Asahi Kasei's "T6002" and "T6001" (polycarbonate diols), and Kuraray's "C-1090," "C-2090," and "C-3090" (polycarbonate diols). Specific examples of polyether ether ketone resins include Sumitomo Chemical's "Sumiploy K."

[0239] Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.

[0240] From the viewpoint of further improving film formability, the weight average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, even 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, even more preferably 60,000 or less, particularly preferably 50,000 or less.

[0241] The content of the thermoplastic resin in the resin composition is not particularly limited, but when the non-volatile components in the resin composition excluding the (C) component are taken as 100 mass%, it may be preferably 20 mass% or less, more preferably 15 mass% or less, and even more preferably 10 mass% or less. The lower limit of the content of the thermoplastic resin in the resin composition is not particularly limited, but when the non-volatile components in the resin composition excluding the (C) component are taken as 100 mass%, it is, for example, 0 mass% or more, 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 0.5 mass% or more, even more preferably 1 mass% or more, 1.5 mass% or more, or 2 mass% or more.

[0242] -Curing accelerator- The curing accelerator functions as a curing catalyst that accelerates the curing of the (A) epoxy resin. The curing accelerator is a component other than those that fall under the above (D) flame retardant.

[0243] Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. The curing accelerator preferably contains a curing accelerator selected from an imidazole-based curing accelerator and an amine-based curing accelerator, and more preferably contains an amine-based curing accelerator. The curing accelerator may be used alone or in combination of two or more.

[0244] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate ... aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;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 Examples of aromatic phosphines include 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, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0245] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. aromatic dimethylureas such as butylurea, 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), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0246] Examples of the guanidine curing accelerator 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, and 1-(o-tolyl)biguanide.

[0247] Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 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-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium 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- Examples of the imidazole compound include 4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds and epoxy resins.

[0248] As the imidazole-based curing accelerator, commercially available products may be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW", and "C11Z-A" manufactured by Shikoku Chemical Industry Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0249] Examples of metal-based curing 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.

[0250] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0251] As the amine-based curing accelerator, a commercially available product may be used, for example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0252] The content of the curing accelerator in the resin composition is not particularly limited, but is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, or 0.5% by mass, when the non-volatile components in the resin composition excluding the (C) component are taken as 100% by mass. The lower limit of the content of the curing accelerator in the resin composition is not particularly limited, but may 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, when the non-volatile components in the resin composition excluding the (C) component are taken as 100% by mass.

[0253] Other additives include, for example, radical polymerizable compounds having a vinylphenyl group, an acryloyl group, a methacryloyl group, or the like; 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, unsaturated polyester resins, melamine resins, and silicone resins; organic fillers such as rubber particles; organometallic 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; bentone , montmorillonite, and other thickeners; silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, vinyl resin-based defoamers, and other defoamers; ultraviolet absorbers, such as benzotriazole-based ultraviolet absorbers; adhesion improvers, such as urea silane; adhesion imparters, such as triazole-based adhesion imparters, tetrazole-based adhesion imparters, and triazine-based adhesion imparters; antioxidants, such as hindered phenol-based antioxidants; fluorescent brighteners, such as stilbene derivatives; surfactants, such as fluorine-based surfactants and silicone-based surfactants; 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. The other additives may be used alone or in combination of two or more in any ratio. The content of other additives can be appropriately determined by a person skilled in the art. In addition, the components (A) to (G) may have functions such as a radical polymerizable compound, a radical polymerization initiator, a thermosetting resin, an organic filler, an organometallic compound, a colorant, a polymerization inhibitor, a leveling agent, a thickener, an antifoaming agent, an ultraviolet absorber, an adhesion improver, an adhesion imparting agent, an antioxidant, a fluorescent brightener, a surfactant, a dispersant, and a stabilizer. In such a case, the component is regarded as each of the components (A) to (G) rather than as another additive.

[0254] <Organic solvent> The resin composition of the present invention may further contain an arbitrary organic solvent. As the organic solvent, known ones can be appropriately used, and the type is not particularly limited. Examples of the organic solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ester-based solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate. Examples of the organic solvent include ether ester solvents, 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, and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, and solvent naphtha. The organic solvent may be used alone or in combination of two or more in any ratio.

[0255] The content of the organic solvent in the varnish-like resin composition before drying is not particularly limited, but is, for example, 40% by mass or less, 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 6% by mass or less, when the total components in the resin composition are 100% by mass. The content of the organic solvent in the resin composition after drying to form the resin composition layer in the resin sheet is not particularly limited, but is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less, when the total components in the resin composition are 100% by mass.

[0256] The phosphorus atom content in the resin composition is, for example, 0% by mass or more, when the non-volatile components in the resin composition excluding the (C) component are taken as 100% by mass, and from the viewpoint of further improving flame retardancy, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. The upper limit of the phosphorus atom content in the resin composition is, when the non-volatile components in the resin composition excluding the (C) component are taken as 100% by mass, from the viewpoint of further suppressing the dielectric tangent, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

[0257] The resin composition of the invention contains at least the above-mentioned (A) epoxy resin, (B) aromatic polyether resin, and (C) inorganic filler. In this embodiment, the total content of the (A) component and the (B) component is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, more than 50% by mass, 52% by mass or more, 54% by mass or more, or 55% by mass or more, when the non-volatile components in the resin composition excluding the (C) component are taken as 100% by mass. The upper limit of the total content is not particularly limited, and may be, for example, 95% by mass or less, 90% by mass or less, etc. When the total content of the (A) component and the (B) component is in this range, it is preferable because the effects of the present invention can be further enjoyed in combination with the (C) component.

[0258] In one embodiment, the resin composition of the present invention includes the above-mentioned (A) epoxy resin, (B) aromatic polyether resin, (C) inorganic filler, and further includes at least (D) flame retardant. In such an embodiment, the total content of the (A), (B) and (D) components is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, more than 50% by mass, 52% by mass or more, 54% by mass or more, 56% by mass or more, 58% by mass or more, or 60% by mass or more, when the non-volatile components in the resin composition excluding the (C) component are taken as 100% by mass. The upper limit of the total content is not particularly limited, and may be, for example, 95% by mass or less, 90% by mass or less, etc. When the total content of the (A), (B) and (D) components is within such a range, it is preferable because the effects of the present invention can be further enjoyed in combination with the (C) component.

[0259] In one embodiment, the resin composition of the present invention includes the above-mentioned (A) epoxy resin, (B) aromatic polyether resin, (C) inorganic filler, and further includes at least (E) carbodiimide resin. In such an embodiment, the total content of the (A), (B) and (E) components is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, more than 50% by mass, 52% by mass or more, 54% by mass or more, 56% by mass or more, 58% by mass or more, or 60% by mass or more, when the non-volatile components in the resin composition excluding the (C) component are taken as 100% by mass. The upper limit of the total content is not particularly limited, and may be, for example, 95% by mass or less, 90% by mass or less, etc. When the total content of the (A), (B) and (E) components is within such a range, it is preferable because the effects of the present invention can be further enjoyed in combination with the (C) component.

[0260] <Method of producing resin composition> The resin composition of the present invention can be produced, for example, by adding (A) epoxy resin, (B) aromatic polyether resin, (C) inorganic filler, if necessary (D) flame retardant, if necessary (E) carbodiimide resin, if necessary (F) curing agent, if necessary (G) maleimide resin, if necessary other additives, and if necessary organic solvent to an arbitrary preparation vessel in any order and / or all or partly or entirely at the same time and mixing. In addition, the temperature can be appropriately set in the process of adding and mixing each component, and heating and / or cooling may be performed temporarily or throughout. In addition, during or after the process of adding and mixing, the resin composition may be stirred or shaken using a stirring device or shaking device such as a mixer to disperse uniformly. In addition, degassing may be performed under low pressure conditions such as under vacuum at the same time as stirring or shaking.

[0261] <Characteristics of resin composition> The resin composition of the present invention is a resin composition comprising (A) an epoxy resin, (B) an aromatic polyether resin, and (C) an inorganic filler, the component (C) comprising a hollow inorganic filler. With such a resin composition, a cured product having excellent flame retardancy and low relative dielectric constant and dielectric loss tangent can be obtained.

[0262] The cured product of the resin composition of the present invention may be characterized by a low dielectric loss tangent (Df). Thus, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition measured at 5.8 GHz and 23° C. as in Test Example 1 below is not particularly limited, but may be preferably 0.020 or less, more preferably 0.010 or less, even more preferably 0.008 or less, even more preferably 0.007 or less, and particularly preferably 0.006 or less.

[0263] The cured product of the resin composition of the present invention may be characterized by a low dielectric constant (Dk). Thus, in one embodiment, the dielectric constant (Dk) of the cured product of the resin composition measured at 5.8 GHz and 23° C. as in Test Example 1 below is not particularly limited, but may be preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.3 or less, 3.2 or less, 3.1 or less, or 3.0 or less.

[0264] In the case where a phosphinic acid ester is included as a flame retardant (D), the cured product of the resin composition according to a preferred embodiment of the present invention may be characterized by a high glass transition temperature (Tg). Thus, in one embodiment, the glass transition temperature (Tg) of the cured product of the resin composition measured using a thermomechanical analyzer as in the following Test Example 2 is not particularly limited, but may be preferably 130°C or higher or 140°C or higher, more preferably 145°C or higher or 150°C or higher, even more preferably 152°C or higher, 154°C or higher or 156°C or higher, and particularly preferably 158°C or higher, 160°C or higher or 162°C or higher. The upper limit is not particularly limited, but may be 400°C or lower, 300°C or lower, etc.

[0265] The cured product of the resin composition of the present invention has excellent flame retardancy. For example, when a UL94 vertical flame retardancy test is performed as in Test Example 3 below, the flammability classification can be preferably equivalent to V-0 or V-1, and particularly preferably equivalent to V-0.

[0266] In the case where the resin composition of the present invention contains a carbodiimide resin (E), the cured product of the resin composition of the present invention according to a preferred embodiment may have a feature of having a moderately low minimum melt viscosity. Thus, in one embodiment, when the dynamic viscoelastic modulus is measured as in the following Test Example 4, the minimum melt viscosity may be preferably 4000 poise or less, more preferably 3000 poise or less, further preferably 2500 poise or less, 2000 poise or less, 1500 poise or less, 1400 poise or less, or 1200 poise or less.

[0267] <Applications of resin composition> As described above, the resin composition of the present invention can provide a cured product having excellent flame retardancy and a low relative dielectric constant and dielectric loss tangent. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for insulating layer of printed wiring board), and can be more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for interlayer insulating layer of printed wiring board). The resin composition of the present invention can also be suitably used when the printed wiring board is a circuit board with built-in components. The resin composition of the present invention can also be suitably used as a resin composition for forming an insulating layer of a rewiring board of a semiconductor package (resin composition for insulating layer of rewiring board). In the present invention, the printed wiring board and the rewiring board are collectively referred to as "circuit board", and therefore the resin composition of the present invention can be suitably used for the insulating layer of a circuit board.

[0268] The resin composition of the present invention can further be used in a wide range of applications requiring a resin composition, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, hole filling resins, sealing resins, and component embedding resins.

[0269] <Sheet-type laminated material> The resin composition of the present invention can be used by coating in the form of a varnish, but from an industrial perspective, it is generally preferred to use the resin composition in the form of a sheet-like laminate material containing the resin composition.

[0270] As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

[0271] 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.

[0272] The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of making the printed wiring board thinner and being able to provide a cured product with excellent insulation even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, 10 μm or more, etc.

[0273] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0274] When a film made of a plastic material is used 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), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0275] When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0276] The surface of the support to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0277] In addition, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the support with a release layer may be, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation. In addition, the support with a release layer may be a commercially available product, for example, "Lumirror T60" and "Lumirror T6AM" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Ltd., and "Unipeel" manufactured by Unitika Ltd., which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

[0278] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the total thickness of the support with a release layer is in the above range.

[0279] When a metal foil is used as the support, a metal foil with a support substrate may be used, which is a thin metal foil with a peelable support substrate attached thereto. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer provided on the support substrate, and a metal foil provided on the release layer. When a metal foil with a support substrate is used as the support, the resin composition layer is provided on the metal foil.

[0280] In the metal foil with a supporting substrate, the material of the supporting substrate is not particularly limited, and examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, etc. When copper foil is used as the supporting substrate, it may be electrolytic copper foil or rolled copper foil. In addition, the release layer is not particularly limited as long as it can release the metal foil from the supporting substrate, and examples thereof include an alloy layer of an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic coating, etc.

[0281] In the metal foil with a supporting substrate, the material of the metal foil is preferably, for example, copper foil or copper alloy foil.

[0282] In the metal foil with a supporting substrate, the thickness of the supporting substrate is not particularly limited, but is preferably in the range of 10 μm to 150 μm, more preferably in the range of 10 μm to 100 μm, and the thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

[0283] In one embodiment, the resin sheet may further include an optional layer as necessary. For example, such an optional layer may be a protective film equivalent to the support provided on the surface of the resin composition layer that is not bonded to the support (i.e., 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 dirt and the like to the surface of the resin composition layer and scratches can be suppressed.

[0284] The resin sheet can be produced, for example, by preparing a liquid (varnish-like) resin composition as is or by dissolving the resin composition in an organic solvent to prepare a liquid (varnish-like) resin composition, applying this onto a support using a die coater or the like, and then drying to form a resin composition layer.

[0285] The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of two or more kinds.

[0286] Drying may be performed by a known method such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer becomes 10 mass % or less, preferably 5 mass % or less. Although it varies depending on the boiling point of the organic solvent in the resin composition, for example, when a resin composition containing 30 mass % to 60 mass % of the organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0287] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0288] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

[0289] The sheet-like fiber substrate used for the prepreg is not particularly limited, and can be a substrate commonly used for prepreg, such as glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, etc. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber substrate is not particularly limited. It is usually 10 μm or more.

[0290] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0291] The thickness of the prepreg may be in the same range as that of the resin composition layer in the above-mentioned resin sheet.

[0292] The sheet-like laminate material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an 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 an interlayer insulating layer of a printed wiring board).

[0293] [Circuit board] The resin composition of the present invention can be used to form an insulating layer for a circuit board. The present invention also provides such a circuit board, i.e., a circuit board including an insulating layer made of a cured product of the resin composition of the present invention.

[0294] <Printed wiring board> In one embodiment, the circuit board of the present invention is a printed wiring board.

[0295] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet, by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate such that a resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., heat curing) the resin composition layer to form an insulating layer.

[0296] The "inner layer substrate" used in step (I) is a member that becomes the substrate of the printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be called an "inner layer circuit substrate". In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be formed during the manufacture of a printed wiring board is also included in the "inner layer substrate" of 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.

[0297] 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. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). The thermocompression bonding member may be pressed directly onto the resin sheet, or may be pressed via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the inner layer substrate.

[0298] The lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression 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 pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the thermocompression 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 may be performed under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0299] The lamination can be performed by a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch type vacuum pressure laminator.

[0300] After lamination, the laminated resin sheet may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. The lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0301] The support may be removed between step (I) and step (II), or after step (II). When a metal foil is used as the support, the conductor layer may be formed using the metal foil without peeling off the support. When a metal foil with a support substrate is used as the support, the support substrate (and the peel layer) may be peeled off. Then, the conductor layer can be formed using the metal foil.

[0302] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions that are usually adopted when forming an insulating layer for a printed wiring board may be used.

[0303] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, etc., but in one embodiment, the curing temperature is preferably 140° C. to 250° C., more preferably 150° C. to 240° C., and even more preferably 160° C. to 230° C. The curing time is preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and even more preferably 15 minutes to 120 minutes.

[0304] Before the resin composition layer is thermally cured, 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 140° C., preferably 60° C. to 135° C., more preferably 70° C. to 130° 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.

[0305] In manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in manufacturing printed wiring boards. When the support is removed after step (II), the removal of the support may be carried out between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0306] In another embodiment, the printed wiring board of the present invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as when a resin sheet is used.

[0307] Step (III) is a step of drilling holes in the insulating layer, which allows holes such as via holes and through holes to be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined depending on the design of the printed wiring board.

[0308] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear removal (desmear) is also performed. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an 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.

[0309] The swelling liquid used in the roughening treatment is not particularly limited, but includes an alkaline solution, a surfactant solution, etc., and is preferably an alkaline solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, but can be performed by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes, for example. 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 to 15 minutes.

[0310] The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. The concentration of 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", "Concentrate Compact P", and "Dosing Solution Securigans P" manufactured by Atotech Japan.

[0311] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be mentioned.

[0312] The treatment with the neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method in which the object that has been roughened with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferred.

[0313] 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, and examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a 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 a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0314] The conductor layer may be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a multi-layer 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 a nickel-chromium alloy.

[0315] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.

[0316] In one embodiment, the conductor layer may be formed by plating. From the viewpoint of facilitating the formation of fine wiring, it is preferable to form the conductor layer by a semi-additive method. An example of forming the conductor layer by the semi-additive method will be described below.

[0317] First, a plating seed layer is formed on the surface of an 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 a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0318] In another embodiment, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, it is preferable to carry out the step (V) between the steps (I) and (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for the step (I). Then, the step (II) is carried out to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a modified semi-additive method, using the metal foil on the insulating layer.

[0319] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0320] Alternatively, when a metal foil or a metal foil with a supporting substrate is used as the support for the resin sheet, the conductor layer may be formed using the metal foil, as described above.

[0321] <Rewiring substrate for semiconductor packages> In one embodiment, the circuit board of the present invention is a rewiring board (rewiring layer) of a semiconductor package. Hereinafter, a method for manufacturing a semiconductor package will be described.

[0322] The semiconductor package includes an insulating layer made of the cured product of the resin composition of the present invention as an insulating layer of a rewiring board. The semiconductor package may also include a sealing layer made of the cured product of the resin composition of the present invention.

[0323] A semiconductor package can be manufactured, for example, by a method including the following steps (1) to (6) using the resin composition and resin sheet of the present invention. The resin composition and resin sheet of the present invention may be used to form a rewiring formation layer (insulating layer for forming a rewiring board) in step (5) or a sealing layer in step (3). An example of forming a rewiring formation layer or a sealing layer using a resin composition or a resin sheet will be shown below, but the technology for forming a rewiring formation layer or a sealing layer of a semiconductor package is publicly known, and a person skilled in the art can manufacture a semiconductor package using the resin composition and resin sheet of the present invention according to a publicly known technology. (1) A step of laminating a temporary fixing film onto a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) 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 off; and (6) A process of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0324] -Process (1)- The material used for the substrate is not particularly limited. Examples of the substrate include semiconductor wafers such as silicon wafers, glass wafers, glass substrates, metal substrates such as copper, titanium, stainless steel, and cold-rolled steel (SPCC), substrates in which glass fibers are impregnated with epoxy resin or the like and subjected to a heat curing treatment (e.g., FR-4 substrates), and substrates made of bismaleimide triazine resin (BT resin).

[0325] The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in step (4) and can temporarily fix the semiconductor chip. A commercially available product can be used as the temporary fixing film. An example of the commercially available product is Riva Alpha manufactured by Nitto Denko Corporation.

[0326] -Process (2)- The semiconductor chips can be temporarily fixed using known devices such as a flip chip bonder, a die bonder, etc. The layout and number of semiconductor chips can be appropriately set depending on the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, etc., and for example, the semiconductor chips can be temporarily fixed by arranging them in a matrix shape of multiple rows and multiple columns.

[0327] -Process (3)- A resin composition layer of the resin sheet of the present invention is laminated on a semiconductor chip, or the resin composition of the present invention is applied onto a semiconductor chip and cured (for example, thermally cured) to form an encapsulating layer.

[0328] For example, the semiconductor chip and the resin sheet can be laminated by removing the protective film of the resin sheet and then heat-pressing the resin sheet to the semiconductor chip from the support side. Examples of the member for heat-pressing the resin sheet to the semiconductor chip (hereinafter also referred to as the "heat-pressing member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). It is preferable to press the heat-pressing member not directly onto the resin sheet but via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the semiconductor chip. The semiconductor chip and the resin sheet may be laminated by a vacuum lamination method, and the lamination conditions are the same as those described in relation to the manufacturing method of the printed wiring board, and the preferred ranges are also the same.

[0329] After lamination, the resin composition is thermally cured to form the encapsulating layer under the same conditions as those described in relation to the method for producing a printed wiring board.

[0330] The support of the resin sheet may be peeled off after the resin sheet is laminated on the semiconductor chip and thermally cured, or the support may be peeled off before the resin sheet is laminated on the semiconductor chip.

[0331] When the resin composition of the present invention is applied to form a sealing layer, the application conditions are the same as the application conditions when forming the resin composition layer described in relation to the resin sheet of the present invention, and the preferred ranges are also the same.

[0332] -Process (4)- The method for peeling off the substrate and the temporary fixing film can be appropriately changed depending on the material of the temporary fixing film, and examples of the method include a method in which the temporary fixing film is heated and foamed (or expanded) to peel it off, and a method in which ultraviolet light is irradiated from the substrate side to reduce the adhesive strength of the temporary fixing film and then peeled off.

[0333] In the method of heating and foaming (or expanding) the temporary fixing film to peel it off, the heating conditions are usually 100 to 250° C. for 1 to 90 seconds or 5 to 15 minutes. In the method of irradiating ultraviolet light from the substrate side to reduce the adhesive strength of the temporary fixing film to peel it off, the irradiation dose of ultraviolet light is usually 10 mJ / cm. 2 ~1000mJ / cm 2 It is.

[0334] -Process (5)- The resin composition and resin sheet of the present invention are used to form a rewiring formation layer (insulating layer of a rewiring board).

[0335] After forming the redistribution layer, a via hole may be formed in the redistribution layer to connect the semiconductor chip to a conductor layer described later. The via hole may be formed by a known method depending on the material of the redistribution layer.

[0336] -Process (6)- The formation of the conductor layer on the rewiring formation layer may be carried out in the same manner as in step (V) described in relation to the method for producing a printed wiring board. Note that steps (5) and (6) may be repeated to alternately stack (build up) the conductor layer (rewiring layer) and the rewiring formation layer (insulating layer).

[0337] In manufacturing the semiconductor package, the steps of (7) forming a solder resist layer on the conductor layer (rewiring layer), (8) forming bumps, and (9) dicing a plurality of semiconductor packages into individual semiconductor packages may be further carried out. These steps may be carried out according to various methods used in manufacturing semiconductor packages and known to those skilled in the art.

[0338] By forming a rewiring formation layer (insulating layer) using the resin composition and resin sheet of the present invention, which can provide a cured product having excellent flame retardancy and a low relative dielectric constant and dielectric loss tangent, a semiconductor package with extremely low transmission loss can be realized without concern for burnout, regardless of whether the semiconductor package is a fan-in (Fan-In) type package or a fan-out (Fan-Out) type package. In one embodiment, the semiconductor package of the present invention is a fan-out (Fan-Out) type package. The resin composition and resin sheet of the present invention can be applied to any type of package, regardless of whether it is a fan-out type panel level package (FOPLP) or a fan-out type wafer level package (FOWLP). In one embodiment, the semiconductor package of the present invention is a fan-out type panel level package (FOPLP) or a fan-out type wafer level package (FOWLP).

[0339] [Semiconductor Devices] The semiconductor device of the present invention includes a layer made of a cured product of the resin composition layer of the present invention. The semiconductor device of the present invention can be produced by using the circuit board of the present invention.

[0340] Examples of the semiconductor device include various semiconductor devices used in electric appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). EXAMPLES

[0341] The present invention will be specifically described below 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 "% by mass", respectively, unless otherwise specified. Unless otherwise specified, the temperature conditions are room temperature (23°C), and unless otherwise specified, the pressure conditions are atmospheric pressure (1 atm).

[0342] (Method for measuring the average particle size of inorganic fillers) 100 mg of inorganic filler and 10 g of methyl ethyl ketone were weighed into a vial and dispersed by ultrasonic waves for 10 minutes. Using a laser diffraction particle size distribution measuring device (HORIBA, Ltd.'s "LA-960"), the particle size distribution of the inorganic filler was measured on a volume basis using a flow cell method with blue and red light source wavelengths. From the particle size distribution obtained, the average particle size of the inorganic filler was calculated as the median diameter.

[0343] (Method for measuring average porosity of inorganic filler) The apparent density of the inorganic filler was measured using a true density measuring device (QUANTACHROME's "ULTRAPYCNOMETER 1000"). In this measurement, nitrogen was used as the measurement gas. The measured apparent density (measured value) D M (g / cm 3 ) and the material density (theoretical value) D of the inorganic material (silica) that forms the inorganic filler T (g / cm 3 ) was used to measure the average porosity of the inorganic filler according to the above formula (I). In the above formula (I), the material density (theoretical value) of silica as an inorganic material is 2.2 g / cm 3 It was decided.

[0344] <Synthesis Example 1: Production of Polyether Resin 1> Into a four-neck flask, 894.96 mmol of 4,6-dichloropyrimidine, 900.00 mmol of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1.2 mol of potassium carbonate, and N-methyl-2-pyrrolidone (450 g) were placed. After replacing the atmosphere in the flask with nitrogen, the contents of the flask were heated at 130°C for 6 hours, and water generated during heating was removed from the Dean-Stark tube at regular intervals. After cooling the contents of the flask to room temperature, the precipitated solid was filtered off, methanol was added to the filtrate, the precipitated solid was washed with methanol, and these solids were dried to obtain polyether resin 1 represented by the following formula (2) (weight average molecular weight (Mw); 87,000 (polystyrene equivalent value), n indicates the number of repeating units). The obtained compound was 13 The product was confirmed by C-NMR measurement.

[0345] [ka]

[0346] <Example 1> Thirty parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: approximately 180 g / eq.) and 30 parts of biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: approximately 269 g / eq.) were heated and dissolved in 55 parts of solvent naphtha with stirring, and then cooled to room temperature. To the mixed solution, 144 parts of hollow silica particles 2 (average particle size 2.0 μm, average porosity 20% by volume) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), 80 parts of spherical silica (solid silica) ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), and 3 parts of a flame retardant ("HCA-HQ-HST" manufactured by Sankosha Co., Ltd., 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 1.5 μm, phenolic hydroxyl group equivalent of about 162 g / eq.) were added, and the mixture was kneaded with a three-roll mill to uniformly disperse the mixture. The roll dispersion was mixed with 14 parts of a triazine skeleton-containing phenolic hardener (DIC Corporation's "LA-3018-50P", hydroxyl equivalent of about 151, 2-methoxypropanol solution with a solid content of 50%) and 1 part of an oligophenylene ether-styrene resin (Mitsubishi Gas Chemical Company's "OPE-2St A resin varnish was prepared by mixing 7.7 parts of an active ester compound (DIC Corporation's "HPC-8000-65T", active group equivalent of approximately 223 g / eq., toluene solution with 65% nonvolatile content), 40 parts of an active ester compound (DIC Corporation's "HPC-8000-65T", active group equivalent of approximately 223 g / eq., toluene solution with 65% nonvolatile content), 20 parts of a phenoxy resin (Mitsubishi Chemical Corporation's "YX6954BH30", a 1:1 mixed solvent of MEK and cyclohexanone, nonvolatile content rate of 30% by mass), 6 parts of a carbodiimide resin (Nisshinbo Chemical Inc.'s "V-03", toluene solution with 50% nonvolatile content), and 6 parts of a curing accelerator ("DMAP", 4-dimethylaminopyridine, MEK solution with 5% solid content by mass). The mixture was uniformly dispersed in a high-speed rotating mixer to prepare a resin varnish.

[0347] <Example 2> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 3 parts of a flame retardant ("FP-100" manufactured by Fushimi Seisakusho, hexaphenoxycyclotriphosphazene) was used instead of 3 parts of the flame retardant ("HCA-HQ-HST" manufactured by Sankosha).

[0348] <Example 3> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 3 parts of a flame retardant ("PX-200" manufactured by Daihachi Chemical Industry Co., Ltd., tetrakis(2,6-dimethylphenyl)1,3-phenylene bisphosphate) was used instead of 3 parts of the flame retardant ("HCA-HQ-HST" manufactured by Sankosha).

[0349] <Example 4> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 5 parts of a maleimide resin ("SLK-6895-T90" manufactured by Shin-Etsu Chemical Co., Ltd., a toluene solution with a non-volatile content of 90%) was added to the roll dispersion, and the oligophenylene ether-styrene resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Inc., a toluene solution with a non-volatile content of 65%) was changed from 7.7 parts to 3.1 parts.

[0350] <Example 5> A varnish-like resin composition was prepared in the same manner as in Example 4, except that 5 parts of maleimide resin ("SLK-6895-T90" manufactured by Shin-Etsu Chemical Co., Ltd., a toluene solution with a non-volatile content of 90%) was replaced with 5 parts of maleimide resin ("SLK-1500-T80" manufactured by Shin-Etsu Chemical Co., Ltd., a toluene solution with a non-volatile content of 80%).

[0351] <Example 6> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 144 parts of hollow silica particles 2 (average particle size: 2.0 μm, average porosity: 20 volume%) were replaced with 90 parts of hollow silica particles 1 (average particle size: 1.6 μm, average porosity: 50 volume%).

[0352] <Example 7> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 7.7 parts of oligophenylene ether-styrene resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Inc., a toluene solution with a non-volatile content of 65%) was replaced with 25 parts of polyether resin 1 (a cyclohexanone solution with a solid content of 20% by mass) of Synthesis Example 1.

[0353] <Example 8> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 30 parts of a naphthol-type epoxy resin ("ESN475V" manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent: 332 g / eq.) was used instead of 30 parts of a biphenyl-type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: approximately 269 g / eq.).

[0354] <Example 9> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 30 parts of a bixylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: approximately 185 g / eq.) was used instead of 30 parts of a biphenyl-type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: approximately 269 g / eq.).

[0355] <Example 10> A varnish-like resin composition was prepared in the same manner as in Example 1, except that the amount of the flame retardant ("HCA-HQ-HST" manufactured by Sankosha, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 1.5 μm, phenolic hydroxyl group equivalent approximately 162 g / eq.) used was changed from 3 parts to 1 part.

[0356] <Example 11> A varnish-like resin composition was prepared in the same manner as in Example 1, except that the amount of oligophenylene ether-styrene resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Inc., a toluene solution with a non-volatile content of 65%) used was changed from 7.7 parts to 3.1 parts.

[0357] <Comparative Example 1> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 144 parts of hollow silica particles 2 (average particle size 2.0 μm, average porosity 20% by volume) were not used, and the amount of spherical silica (solid silica) ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 80 parts to 260 parts.

[0358] <Comparative Example 2> A varnish-like resin composition was prepared in the same manner as in Example 1, except that the oligophenylene ether-styrene resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Inc., a toluene solution with a non-volatile content of 65%) was changed from 7.7 parts to 0 parts, and the flame retardant ("HCA-HQ-HST" manufactured by Sanko Co., Ltd.) was changed from 3 parts to 0 parts.

[0359] <Comparative Example 3> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 7.7 parts of an oligophenylene ether-styrene resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Inc., a toluene solution with a non-volatile content of 65%) was not used.

[0360] <Reference example 1> Thirty parts of bisphenol A type epoxy resin (Mitsubishi Chemical's "828US", epoxy equivalent approximately 180g / eq.) and 30 parts of biphenyl type epoxy resin (Nippon Kayaku's "NC3000H", epoxy equivalent approximately 269g / eq.) were dissolved in 55 parts of solvent naphtha with stirring, and then cooled to room temperature. To the mixed solution, 144 parts of hollow silica particles 2 (average particle size 2.0μm, average porosity 20% by volume) surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical's "KBM573") and 80 parts of spherical silica (solid silica) (Admatechs' "SO-C2", average particle size 0.5μm) surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical's "KBM573") were added, and the mixture was kneaded with a three-roll mill to uniformly disperse the mixture. The roll dispersion was mixed with 7.7 parts of oligophenylene ether-styrene resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a non-volatile content of 65%), 21 parts of bisphenol A dicyanate prepolymer ("BA230S75" manufactured by Arcsada, a MEK solution with a cyanate equivalent of approximately 232 g / eq. and a non-volatile content of 75%), 5 parts of phenol novolac type multifunctional cyanate ester resin ("PT30S" manufactured by Arcsada, a MEK solution with a cyanate equivalent of 124 g / eq. and a non-volatile content of 80%), and 10 parts of flame retardant ("FP-100" manufactured by Fushimi Seisakusho Co., Ltd., a hexaphenoxysilane solution). A resin varnish was prepared by mixing 2 parts of a phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 mixed solvent of MEK and cyclohexanone, non-volatile content of 30% by mass), 20 parts of a curing accelerator ("DMAP", 4-dimethylaminopyridine, MEK solution with 5% by mass of non-volatile content), and 3 parts of a curing accelerator (cobalt (III) acetylacetonate, MEK solution with 1% by mass of non-volatile content manufactured by Tokyo Chemical Industry Co., Ltd.) and dispersing the mixture uniformly using a high-speed rotating mixer.

[0361] <Preparation Example 1: Preparation of resin sheet> A PET film (Toray Industries, Inc., "Lumirror T6AM", thickness 38 μm) that had been release-treated with an alkyd resin-based release agent (Lintec Corporation, "AL-5") was prepared as a support. On the release layer of the support, the varnish-like resin compositions prepared in the Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying was 40 μm, and the resulting mixture was dried at 80 to 120° C. (average 100° C.) for 5 minutes to produce a resin sheet.

[0362] <Test Example 1: Measurement of relative dielectric constant and dielectric loss tangent> The resin sheet (resin composition layer thickness 40 μm) produced in Production Example 1 was heated at 200° C. for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The obtained cured product is referred to as the “cured product for evaluation”. The cured product for evaluation was cut into a test piece having a width of 2 mm and a length of 80 mm. The relative dielectric constant and dielectric loss tangent of the test piece were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity resonance perturbation method using an “HP8362B” manufactured by Agilent Technologies. The measurements were performed on two test pieces, and the average values ​​were calculated.

[0363] <Test Example 2: Evaluation of Glass Transition Temperature> The cured product for evaluation was cut into a test piece with a width of about 5 mm and a length of about 15 mm, and a thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer (Rigaku Corporation, "Thermo Plus TMA8310"). In detail, the test piece was mounted on the thermomechanical analyzer, and then measured twice consecutively under the measurement conditions of a load of 1 g and a temperature rise rate of 5°C / min (the first time the temperature was raised to 200°C, and the second time the temperature was raised to 260°C). Then, in the second measurement, the glass transition temperature (Tg, unit: °C) was calculated.

[0364] <Test Example 3: Evaluation of flame retardancy> The resin sheet prepared in Preparation Example 1 was laminated on both sides of a substrate obtained by etching away the copper foil of a copper-clad laminate ("MCL-E-700G" manufactured by Resonac Co., Ltd.) having a substrate thickness of 0.2 mm, using a batch-type vacuum pressure laminator MVLP-500 (trade name manufactured by Japan Steel Works, Ltd.) so that the resin composition layer was bonded to the substrate. The lamination was performed by reducing the pressure for 30 seconds to 13 hPa or less, and then pressing for 30 seconds at 100°C and a pressure of 0.74 MPa. After peeling off the PET film of the support, the resin sheet prepared in Preparation Example 1 was laminated again on both sides under the same conditions. Thereafter, the PET film of the support was peeled off and heat cured at 200°C for 90 minutes to obtain a sample for flame retardancy test. The sample was cut to a width of 12.7 mm and a length of 127 mm, and the cut surface was polished with a polisher (RotoPol-22 manufactured by Struers Co., Ltd.). The above five samples were grouped into a set and a flame retardancy test was carried out according to the UL94 vertical flame retardancy test. Those with evaluation results equivalent to V-0 were rated "○", those equivalent to V-1 were rated "△", and all other results were rated "×". The results are shown in Table 1 below.

[0365] <Test Example 4: Evaluation of minimum melt viscosity> The PET film support was peeled off from the resin sheet produced in Production Example 1, and the resulting resin composition layer was compressed in a mold to produce pellets for measurement (diameter 18 mm, 1.2 to 1.3 g).

[0366] Using a dynamic viscoelasticity measuring device (UBM's "Rheosol-G3000") and a parallel plate with a diameter of 18 mm, the temperature was raised from the starting temperature of 60°C to 200°C at a heating rate of 5°C / min, and the dynamic viscoelasticity was measured under the measurement conditions of a measurement temperature interval of 2.5°C, a vibration frequency of 1 Hz, and a strain of 1 deg, and the minimum melt viscosity (poise) was calculated.

[0367] The non-volatile component contents of the resin compositions of the Examples and Comparative Examples, and the measurement results and evaluation results of the Test Examples are summarized in Table 1 below.

[0368] [Table 1]

[0369] From the results shown in Table 1, it can be seen that by using a resin composition containing (A) an epoxy resin, (B) an aromatic polyether resin, and (C) an inorganic filler, in which the (C) component contains a hollow inorganic filler, it is possible to obtain a cured product having excellent flame retardancy and low relative dielectric constant and dielectric loss tangent (Examples 1 to 11 and Reference Example 1). In addition, it was confirmed that, in addition to the above (A) to (C) components, a resin composition containing (E) a carbodiimide resin and containing hollow silica in the (C) component can achieve a cured product having excellent flame retardancy and low relative dielectric constant and dielectric loss tangent, and can achieve a resin composition having a moderately low minimum melt viscosity and even better lamination properties and conductor embedding properties (Examples 1 to 11).

[0370] In addition, it was confirmed in Reference Example 1 that the absence of the aromatic polyether resin (B) resulted in poor flame retardancy. In this case (not containing the component (B)), the content of the hollow inorganic filler was changed, and it was confirmed that, although the higher the content of the hollow inorganic filler, the lower the relative dielectric constant and the dielectric loss tangent, the decrease in flame retardancy became evident especially when the content of the hollow inorganic filler exceeded 20 mass%, and the flame retardancy decreased as the content of the hollow inorganic filler increased. Even when hollow inorganic fillers made of other inorganic oxides such as hollow alumina or hollow inorganic fillers made of composite inorganic oxides such as hollow aluminosilicate are used instead of hollow silica particles, the above problem of reduced flame retardancy occurs similarly, and it has been confirmed that adding (B) aromatic polyether resin is beneficial in solving such a problem. For example, in Reference Example 1, it has been confirmed that a resin composition using hollow alumina or hollow aluminosilicate instead of hollow silica particles 2 (referred to as Reference Example 1-1) exhibits better results in terms of flame retardancy and dielectric loss tangent than a resin composition in Reference Example 1-1 that does not use component (B) (referred to as Comparative Reference Example 1-1').

[0371] In addition, in Reference Example 1, it was confirmed that although the dielectric loss tangent tends to increase when the content of the flame retardant (D) is increased, the increase in the dielectric loss tangent can be significantly suppressed compared to a conventional resin composition that does not contain the aromatic polyether resin (B). It was confirmed that the effect of suppressing the increase in the dielectric loss tangent can be achieved more remarkably when the active ester curing agent (F) is contained as the curing agent.

[0372] In Reference Example 1, the content of the aromatic polyether resin (B) was changed, and it was confirmed that, particularly when the content of the aromatic polyether resin (B) in the resin composition is in the range of 1% by mass to 6% by mass, where the non-volatile components excluding the component (C) in the resin composition are taken as 100% by mass, a cured product having excellent flame retardancy and low relative dielectric constant and dielectric loss tangent can be easily achieved even when the content of the hollow inorganic filler is high. In addition, the content of the flame retardant (D) was changed, and it was confirmed that the excellent effect of the aromatic polyether resin (B) can be more significantly exhibited, particularly when the flame retardant (D) is contained such that the mass ratio of the aromatic polyether resin (B) to the flame retardant (D) [component (B) / component (D)] is 0.5 or more.

[0373] In Reference Example 1, it was confirmed that a cured product having excellent flame retardancy and low dielectric constant and dielectric loss tangent could be achieved even without using solid inorganic particles. In this regard, it was confirmed that it is preferable to use solid inorganic particles in combination with hollow inorganic particles in order to simultaneously achieve good flame retardancy and a lower dielectric loss tangent (while ensuring the design freedom of the resin composition).

[0374] In Reference Example 1, it has been confirmed that the further addition of a maleimide resin (G) tends to result in a cured product with an even lower dielectric loss tangent. As the maleimide resin (G), any of the aforementioned components (G1), (G2), and (G3) may be used, but it has been confirmed that it is preferable to use component (G1), i.e., a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of the maleimide, from the viewpoint of easily achieving a cured product with excellent flame retardancy and low relative dielectric constant and dielectric loss tangent, even when the content of hollow inorganic filler is high, particularly in combination with the aromatic polyether resin (B).

Claims

1. A resin composition comprising (A) an epoxy resin, (B) an aromatic polyether resin, (C) an inorganic filler, and (E) a carbodiimide resin, A resin composition, wherein the component (C) contains hollow silica.

2. The component (B) is represented by the formula (1): 【Chemistry 1】 [In the formula, R １１ and R １２ each independently represents an alkyl group; R １３ , R １４ , R ２１ , R ２２ , R ２３ and R ２４ each independently represents a hydrogen atom or an alkyl group; R ａ and R ｂ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkyl-carbonyl group, an optionally substituted alkenyl-carbonyl group, an optionally substituted aryl-carbonyl group, or an optionally substituted aralkyl-carbonyl group; A is a single bond, -C(R ｃ ) ２ -, -O-, -CO-, -S-, -SO-, or -SO ２ - indicates; R ｃ each independently represents a hydrogen atom or an alkyl group; s represents 0 or 1; t and u each independently represent an integer of 1 or more. The resin composition according to claim 1 , comprising a resin represented by the formula:

3. The component (B) is represented by formula (2A) or (2B): 【Chemistry 2】 [In the formula, W, X, Y and Z each independently represent N or CR; R represents a hydrogen atom or a substituent; R １ and R ２ each independently represents a hydrogen atom or a substituent, or R １ and R ２ are joined together to form a non-aromatic carbocyclic ring which may have a substituent and which may be fused with an aromatic carbocyclic ring; R ３ and R ４ each independently represents a substituent; a and b each independently represent 0, 1, 2, or 3. The resin composition according to claim 1 , comprising a resin having a repeating unit represented by the formula:

4. The resin composition according to claim 1, wherein the content of the component (B) is 0.5% by mass to 10% by mass, based on 100% by mass of non-volatile components in the resin composition excluding the component (C).

5. The resin composition according to claim 1 , wherein the content of the component (C) is 60% by mass or more, based on 100% by mass of non-volatile components in the resin composition.

6. The resin composition according to claim 1 , wherein the hollow silica has an average porosity of 10% by volume or more.

7. The resin composition according to claim 1 , further comprising (D) a flame retardant.

8. The resin composition according to claim 7 , wherein the component (D) comprises a phosphorus-based flame retardant.

9. The resin composition according to claim 7, wherein a mass ratio of the component (B) to the component (D) [component (B) / component (D)] is 0.5 or more.

10. The resin composition according to claim 1, wherein the phosphorus atom content is 0% by mass to 5% by mass, where the total amount of non-volatile components in the resin composition excluding the component (C) is taken as 100% by mass.

11. The resin composition according to claim 1 , further comprising (F) a curing agent.

12. The resin composition according to claim 11, wherein the component (F) comprises an active ester-based curing agent.

13. The resin composition according to claim 11, wherein component (F) comprises a phenol-based curing agent.

14. The resin composition according to claim 1, wherein the dielectric loss tangent (Df) of a cured product of the resin composition is 0.006 or less when measured at 5.8 GHz and 23°C.

15. The resin composition according to claim 1, wherein the cured product of the resin composition has a relative dielectric constant (Dk) of 3.0 or less when measured at 5.8 GHz and 23°C.

16. A cured product of the resin composition according to any one of claims 1 to 15.

17. A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 15.

18. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 15 provided on the support.

19. A circuit board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 15.

20. A semiconductor device comprising the circuit board according to claim 19.

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