Resin composition

Abstract

To provide a resin composition that can give a cured product having excellent crack resistance.SOLUTION: A resin composition comprises (A) an epoxy resin, (B) a radical polymerizable group-containing compound, and (C) a curing accelerator, wherein the component (C) includes (C1) a compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition containing an epoxy resin, and further to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition. [Background technology]

[0002] A known manufacturing technique for printed wiring boards is a build-up method in which insulating layers and conductor layers are alternately stacked. In build-up manufacturing methods, the insulating layers are generally formed by curing a resin composition containing an epoxy resin (Patent Document 1).

[0003] In recent years, with the trend toward finer wiring, higher density, and higher signal frequencies on printed wiring boards, there has been a demand for further reductions in the relative permittivity and dielectric loss tangent of insulating layers. One method for achieving this is the combined use of epoxy resins and compounds containing radical polymerizable groups.

[0004] However, it has been known that the use of radical polymerizable group-containing compounds can sometimes result in a decrease in the glass transition temperature of the cured product. To prevent this, it is necessary to use a curing accelerator in addition to the radical polymerizable group-containing compound. However, when a curing accelerator is used, the degree of cure in the pre-cure state increases significantly, causing excessive internal stress to accumulate, and the induction of cracks by the radical polymerizable group-containing compound has become an issue. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2021-130780 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a resin composition that can give a cured product having excellent crack resistance. [Means for solving the problem]

[0007] In order to achieve the objects of the present invention, the present inventors have conducted extensive research and have unexpectedly found that by using, as the curing accelerator (C), a sterically hindered compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms, a cured product with excellent crack resistance can be obtained, leading to the completion of the present invention.

[0008] That is, the present invention includes the following. [1] A resin composition comprising (A) an epoxy resin, (B) a radically polymerizable group-containing compound, and (C) a curing accelerator, A resin composition in which the component (C) contains (C1) a compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms. [2] The component (C1) is a compound represented by the formula (C):

[0009] [ka]

[0010] [In the formula, R 1 represents an alkyl group having 7 or more carbon atoms or an alkenyl group having 7 or more carbon atoms; R 2 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group; R 3 and R 4 each independently represents a hydrogen atom or a substituent, or R 3 and R 4 are bonded together to form an optionally substituted aromatic ring or an optionally substituted non-aromatic ring; A double line (broken or solid) indicates a single or double bond. The resin composition according to [1] above, comprising a compound represented by the formula: [3] R 2 But, equation (R2):

[0011] [ka]

[0012] [In the formula, X represents an alkylene group having 1 to 6 carbon atoms: Y represents a single bond, -O-, -CO-, -S-, -SO-, -SO2-, -NH-, -COO-, -OCO-, -CONH-, or -NHCO-; * indicates the binding site.] The resin composition according to the above [2], wherein the group is represented by the formula: [4] The resin composition according to any one of the above [1] to [3], wherein the content of the component (C1) is 0.001% by mass to 1% by mass, where the total amount of non-volatile components in the resin composition is 100% by mass. [5] The resin composition according to any one of the above [1] to [4], wherein the content of the component (A) is 10% by mass to 30% by mass, where the total amount of non-volatile components in the resin composition is 100% by mass. [6] The resin composition according to any one of the above [1] to [5], further comprising (D) an inorganic filler. [7] The resin composition according to [6] above, wherein the material of component (D) comprises a material selected from silica, alumina, and aluminosilicate. [8] The resin composition according to [6] or [7] above, wherein the content of component (D) is 70% by mass or more, assuming that the total amount of non-volatile components in the resin composition is 100% by mass. [9] The resin composition according to any one of the above [1] to [8], further comprising (E) an epoxy resin curing agent.

[10] The resin composition according to the above [9], wherein the component (E) contains an active ester curing agent.

[11] The resin composition according to the above [9] or

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

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

[11] , wherein the cured product of the resin composition has a relative dielectric constant (Dk) of 3.5 or less when measured at 5.8 GHz and 23°C.

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

[12] , wherein the dielectric loss tangent (Df) of the cured product of the resin composition is 0.005 or less when measured at 5.8 GHz and 23°C.

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

[13] , wherein the coefficient of linear thermal expansion (CTE) of the cured product of the resin composition is 25 ppm / K or less in the temperature range of 25°C to 150°C.

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

[14] , wherein the glass transition temperature (Tg) of the cured product of the resin composition is 150°C or higher.

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

[15] above.

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

[15] .

[18] A resin sheet comprising a support and a resin composition layer formed on the support from the resin composition according to any one of [1] to

[15] above.

[19] A printed wiring board having an insulating layer made of a cured product of the resin composition according to any one of [1] to

[15] above.

[20] A semiconductor device comprising the printed wiring board according to

[19] above. [Effects of the Invention]

[0013] According to the resin composition of the present invention, a cured product having excellent crack resistance can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications within 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) a radically polymerizable group-containing compound, and (C) a curing accelerator, wherein the curing accelerator (C) comprises (C1) a compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms. Such a resin composition can provide a cured product with excellent crack resistance.

[0016] The resin composition of the present invention may further contain optional components in addition to (A) the epoxy resin, (B) the radically polymerizable group-containing compound, and (C) the curing accelerator, such as (D) an inorganic filler, (E) an epoxy resin curing agent, (F) a thermoplastic resin, (G) other additives, and (H) an organic solvent.

[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 (A) an epoxy resin. (A) An epoxy resin is a curable resin having an epoxy group and an epoxy equivalent of 5,000 g / eq. or less. The (A) epoxy resin described here is a component other than (B) a radically polymerizable group-containing compound and (F) a thermoplastic resin, both of which are described below.

[0019] Examples of (A) epoxy resins 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 aralkyl-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexane dimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, isocyanurate-type epoxy resins, and phenolphthalimidine-type epoxy resins. The (A) epoxy resin may be used alone or in combination of two or more.

[0020] The resin composition of the present invention preferably contains, as the (A) epoxy resin, an epoxy resin having two or more epoxy groups per molecule. The proportion of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the (A) epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by 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 preferred that the resin composition contain 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 glycerol-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, cyclohexanedimethanol-type epoxy resins, alicyclic glycidyl ethers, and epoxy resins having a butadiene structure.

[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" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", and "604" (glycidylamine-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirol-type epoxy resin) manufactured by ADEKA Corporation; and "EP-3950L" and "EP-3980S" (glycidylamine-type epoxy resins) manufactured by ADEKA Corporation. epoxy resin); ADEKA Corporation's "EP-4088S" (dicyclopentadiene type epoxy resin); Nippon Steel Chemical & Material Corporation's "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Corporation's "EX-721" (glycidyl ester type epoxy resin); Nagase ChemteX Corporation's "EX-991L" (an epoxy resin containing an alkyleneoxy skeleton and a butadiene skeleton); Daicel Corporation's "Celloxide 2021P" (an alicyclic epoxy resin having an ester skeleton); Nippon Steel Chemical & Material Corporation's "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin); Osaka Gas Chemicals Corporation's "EG-280" (an epoxy resin containing a fluorene structure); and Nagase ChemteX Corporation's "EX-201" (alicyclic glycidyl ether).

[0025] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[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, and phenolphthalimidine-type epoxy resins.

[0027] Specific examples of solid epoxy resins include DIC Corporation's "HP4032H" (naphthalene-type epoxy resin); DIC Corporation's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC Corporation's "N-690" (cresol novolac-type epoxy resin); DIC Corporation's "N-695" (cresol novolac-type epoxy resin); DIC Corporation's "HP-7200," "HP-7200HH," "HP-7200H," and "HP-7200L" (dicyclopentadiene-type epoxy resins); and DIC Corporation's "EXA-7311." "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 Kayaku Co., Ltd.; "ESN475V", "ESN4" manufactured by Nippon Steel Chemical & Material Co., Ltd. 100V" (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", and "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "Y" manufactured by Mitsubishi Chemical Corporation Examples include "X7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.These 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 10:1 to 1:50, more preferably 5:1 to 1:20, and particularly preferably 2:1 to 1:10.

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

[0030] The weight average molecular weight (Mw) of the (A) epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. 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 (A) epoxy resin in the resin composition is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of the (A) epoxy resin in the resin composition is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 15% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition.

[0032] <(B) Radical Polymerizable Group-Containing Compound> The resin composition of the present invention contains (B) a radically polymerizable group-containing compound. The (B) radically polymerizable group-containing compound is a compound containing one or more (preferably two or more) radically polymerizable groups in one molecule. The (B) radically polymerizable group-containing compound may be used alone or in combination of two or more.

[0033] The radically polymerizable group is a group having a radically polymerizable ethylenically unsaturated bond, and examples thereof include, but are not limited to, (1) an acryloyl group, (2) a methacryloyl group, (3) an allyl group, (4) a methallyl group, and (5) a phenyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group (for example, a vinylphenyl group (i.e., a 4-vinylphenyl group, a 3-vinylphenyl group, or a 2-vinylphenyl group), an isopropenylphenyl group (i.e., a 4-isopropenylphenyl group, a 3-isopropenylphenyl group, or a 2-isopropenylphenyl group), (6) a benzyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group (for example, a vinylbenzyl group (i.e., a 4-vinylbenzyl group, a 3-vinylbenzyl group, a 2-vinylbenzyl group), an isopropenylbenzyl group (i.e., a 4-isopropenylbenzyl group, a 3-isopropenylbenzyl group, a 2-isopropenylbenzyl group)), (7) a maleimide group (a 2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group), and the like.

[0034] In the first embodiment, the (B) radically polymerizable group-containing compound preferably contains a thermoplastic resin having two or more radically polymerizable groups (for example, a number average molecular weight of 800 or more). The thermoplastic resin is not particularly limited, but examples thereof include phenoxy resin, polyvinyl acetal resin, polystyrene resin, polyethylene resin, polypropylene resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, and polyester resin. In this embodiment, the (B) radically polymerizable group-containing compound contains a modified resin having two or more radically polymerizable groups of these resins.

[0035] In the first embodiment, the (B) radically polymerizable group-containing compound more preferably includes a resin selected from a modified polyphenylene ether resin having two or more radically polymerizable groups and a modified polystyrene resin having two or more radically polymerizable groups, and even more preferably includes a modified polyphenylene ether resin having two or more radically polymerizable groups. In one embodiment, the (B) radically polymerizable group-containing compound is particularly preferably a compound represented by the formula (B):

[0036] [ka]

[0037] [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 beach independently represent (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 further be substituted with an alkyl group, or (6) a benzyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl 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 u units may be the same or different for each unit.

[0038] 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, is preferably a hydrogen atom. 21 and R 22 R each independently represents a hydrogen atom or an alkyl group, and in one embodiment, 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.

[0039] 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.

[0040] R a and R b each independently represents (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 further be substituted with an alkyl group, or (6) a benzyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group.

[0041] R a and R b are each independently preferably (1) a phenyl group substituted with a group selected from a vinyl group and an isopropenyl group and optionally further substituted with an alkyl group, or (2) a benzyl group substituted with a group selected from a vinyl group and an isopropenyl group and optionally further substituted with an alkyl group; more 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; particularly preferably a 4-vinylbenzyl group, a 3-vinylbenzyl group, or a 2-vinylbenzyl group.

[0042] A is a single bond, -C(R c )2-, -O-, -CO-, -S-, -SO-, or -SO2-, and in one embodiment, preferably represents a single bond, -C(R c )2- or -O-. c each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group.

[0043] 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.

[0044] The radical polymerizable group equivalent of the (B) radical polymerizable group-containing compound in the first embodiment is preferably 300 g / eq. to 2500 g / eq., more preferably 400 g / eq. to 2000 g / eq. The radical polymerizable group equivalent represents the mass of the resin (compound) per equivalent of the radical polymerizable group.

[0045] The number average molecular weight of the radically polymerizable group-containing compound (B) in the first embodiment is preferably 800 to 10000, 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.

[0046] Commercially available products of the (B) radically polymerizable group-containing compound in the first embodiment 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 Innovative Plastics.

[0047] In the second embodiment, the (B) radically polymerizable group-containing compound includes a low-molecular-weight compound (e.g., a molecular weight of less than 800) having two or more radically polymerizable groups. Examples of such compounds include polyfunctional (meth)acryloyl group-containing compounds having a molecular weight of less than 800, polyfunctional vinylphenyl group-containing compounds having a molecular weight of less than 800, and polyfunctional allyl group-containing compounds having a molecular weight of less than 800.

[0048] A polyfunctional (meth)acryloyl group-containing compound having a molecular weight of less than 800 is a compound having two or more (meth)acryloyl groups. Examples of polyfunctional (meth)acryloyl group-containing compounds having a molecular weight of less than 800 include aliphatic (meth)acrylic acid ester compounds such as cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; dioxane Examples of the ether-containing (meth)acrylic acid ester compounds include ricol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, and propoxylated bisphenol A di(meth)acrylate; and isocyanurate-containing (meth)acrylic acid ester compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylate.Examples of commercially available polyfunctional (meth)acryloyl group-containing compounds having a molecular weight of less than 800 include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate) and "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., and "KAYARAD R-684" (tricyclodecane dimethanol diacrylate) and "KAYARAD R-604" (dioxane glycol diacrylate) manufactured by Nippon Kayaku Co., Ltd.

[0049] A polyfunctional vinylphenyl group-containing compound having a molecular weight of less than 800 is a compound having two or more vinylphenyl groups. Examples of polyfunctional vinylphenyl group-containing compounds having a molecular weight of less than 800 include 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether.

[0050] A polyfunctional allyl group-containing compound having a molecular weight of less than 800 is a compound having two or more allyl groups. Examples of polyfunctional allyl group-containing compounds having a molecular weight of less than 800 include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenecarboxylate; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; and allyl silane compounds such as diallyldiphenylsilane. Commercially available polyfunctional allyl group-containing compounds with a molecular weight of less than 800 include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Chemical Industry Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., "DAND" (2,3-diallyl naphthalenecarboxylate) manufactured by Nippon Distillation Industries Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Chemical Industry Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., and "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemical Industry Co., Ltd.

[0051] The radical polymerizable group equivalent of the radical polymerizable group-containing compound (B) in the second embodiment is preferably 30 g / eq. to 400 g / eq., more preferably 50 g / eq. to 300 g / eq., and even more preferably 75 g / eq. to 200 g / eq.

[0052] The molecular weight of the radically polymerizable group-containing compound (B) in the second embodiment is preferably 100-700, more preferably 200-400, and even more preferably 250-500.

[0053] The (B) radically polymerizable group-containing compound may contain either the preferred resin in the first embodiment or the preferred compound in the second embodiment, either alone, or may contain two or more of these in combination at any ratio.

[0054] The radical polymerizable group equivalent of the (B) radical polymerizable group-containing compound is preferably 30 g / eq. to 2500 g / eq., particularly preferably 75 g / eq. to 2000 g / eq.

[0055] The content of the (B) radical polymerizable group-containing compound in the resin composition is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 2% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of the (B) radical polymerizable group-containing compound in the resin composition is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition.

[0056] <(C) Curing accelerator> The resin composition of the present invention contains (C) a curing accelerator, which functions as a curing catalyst that accelerates the curing of (A) the epoxy resin.

[0057] In the resin composition of the present invention, the curing accelerator (C) contains a compound (C1) having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms.

[0058] The nitrogen-containing heterocycle refers to a heterocycle containing at least carbon and nitrogen atoms as ring-constituting atoms and optionally containing heteroatoms other than nitrogen atoms, such as oxygen and sulfur atoms, as ring-constituting atoms. The nitrogen-containing heterocycle may be a nitrogen-containing aromatic heterocycle conforming to Hückel's rule, in which the number of electrons contained in the π-electron system on the ring is 4p+2 (p is a natural number), or a nitrogen-containing non-aromatic heterocycle in which the entire ring is not aromatic. In one embodiment, a nitrogen-containing aromatic heterocycle is preferred. The nitrogen-containing heterocycle may be a monocyclic nitrogen-containing heterocycle, a bicyclic nitrogen-containing heterocycle, or a tricyclic nitrogen-containing heterocycle. In one embodiment, a monocyclic nitrogen-containing heterocycle is preferred. In one embodiment, the nitrogen-containing heterocycle is preferably 4- to 14-membered, and more preferably 5- to 10-membered. Specific preferred examples of the nitrogen-containing heterocycle include monocyclic nitrogen-containing aromatic heterocycles such as a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,2,3-triazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring; an indole ring, an isoindole ring, a benzimidazole ring, an indazo ring, and the like. Examples of the heterocyclic ring include a bicyclic nitrogen-containing aromatic heterocycle such as a pyrrolidine ring, an imidazolidine ring, an imidazoline ring, a pyrazolidine ring, a pyrazoline ring, an oxazolidine ring, an oxazoline ring, a thiazolidine ring, and a thiazoline ring; and a bicyclic nitrogen-containing non-aromatic heterocycle such as an indoline ring or a dihydrobenzimidazole ring. Of these, an imidazole ring or an imidazoline ring is preferred, and an imidazole ring is particularly preferred.

[0059] A hydrocarbon group is a monovalent group whose constituent atoms are only carbon atoms and hydrogen atoms, and may have a linear structure, a branched structure, and / or a cyclic structure, and may be a group that does not contain an aromatic ring or a group that contains an aromatic ring. Examples of hydrocarbon groups having 7 or more carbon atoms include alkyl groups having 7 or more carbon atoms and alkenyl groups having 7 or more carbon atoms.

[0060] An alkyl group having 7 or more carbon atoms refers to a linear, branched, and / or cyclic monovalent aliphatic saturated hydrocarbon group having 7 or more carbon atoms. The number of carbon atoms in the alkyl group having 7 or more carbon atoms is preferably 7 to 30, more preferably 7 to 20, even more preferably 8 to 15, and particularly preferably 9 to 13. The alkyl group having 7 or more carbon atoms is preferably a linear alkyl group having 7 or more carbon atoms. Examples of the alkyl group having 7 or more carbon atoms include a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group.

[0061] An alkenyl group having 7 or more carbon atoms refers to a linear, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having 7 or more carbon atoms and at least one carbon-carbon double bond. The number of carbon atoms in the alkenyl group having 7 or more carbon atoms is preferably 7 to 30, more preferably 7 to 20, even more preferably 8 to 15, and particularly preferably 9 to 13. The alkenyl group having 7 or more carbon atoms is preferably a linear alkenyl group having 7 or more carbon atoms. Examples of alkenyl groups having 7 or more carbon atoms include a heptenyl group (e.g., a 6-heptenyl group), an octenyl group (e.g., a 7-octenyl group), a nonenyl group (e.g., an 8-nonenyl group), a decenyl group (e.g., a 9-decenyl group), an undecenyl group (e.g., a 10-undecenyl group), a dodecenyl group, a tridecenyl group, a tetradecenyl group, and a pentadecenyl group.

[0062] In the component (C1), a carbon atom on the nitrogen-containing heterocycle is preferably substituted with a hydrocarbon group having 7 or more carbon atoms. The number of hydrocarbon groups having 7 or more carbon atoms on the nitrogen-containing heterocycle per molecule is preferably 1 or 2, and particularly preferably 1. The component (C1) may have any further substituent on the nitrogen-containing heterocycle other than the hydrocarbon group having 7 or more carbon atoms.

[0063] In one embodiment, the component (C1) is preferably represented by the formula (C):

[0064] [ka]

[0065] [In the formula, R 1 represents an alkyl group having 7 or more carbon atoms or an alkenyl group having 7 or more carbon atoms; R 2 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group; R 3 and R 4 each independently represents a hydrogen atom or a substituent, or R 3 and R 4 are bonded together to form an optionally substituted aromatic ring or an optionally substituted non-aromatic ring; A double line (broken or solid) indicates a single or double bond. The compound includes a compound represented by the formula:

[0066] R 1 represents an alkyl group having 7 or more carbon atoms or an alkenyl group having 7 or more carbon atoms; in one embodiment, it is preferably an alkyl group having 7 to 30 carbon atoms or an alkenyl group having 7 to 30 carbon atoms; more preferably an alkyl group having 7 to 20 carbon atoms or an alkenyl group having 7 to 20 carbon atoms; even more preferably an alkyl group having 8 to 15 carbon atoms or an alkenyl group having 8 to 15 carbon atoms; still more preferably an alkyl group having 9 to 13 carbon atoms or an alkenyl group having 9 to 13 carbon atoms; and particularly preferably an undecyl group.

[0067] R 2 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group.

[0068] 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.).

[0069] The term "aryl group" refers to a monovalent group formed by removing one hydrogen atom from an aromatic carbocyclic ring containing only carbon atoms as ring constituent atoms. Unless otherwise specified, the aryl group is preferably an aryl group having 6 to 14 carbon atoms, and particularly 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.

[0070] The heteroaryl group refers to a monovalent group obtained by removing one hydrogen atom from an aromatic heterocycle having, in addition to carbon atoms, heteroatoms such as oxygen, nitrogen, and sulfur atoms as ring-constituting atoms. Unless otherwise specified, the heteroaryl group is preferably a 5- to 14-membered heteroaryl group, and particularly preferably a 5- to 10-membered heteroaryl group. Examples of heteroaryl groups include a furyl group, a thienyl group, a pyrrolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an imidazolyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, and a triazinyl group (e.g., 1,3,5-triazin-2-yl).

[0071] R 2The "substituents" of the alkyl and alkenyl groups in the formula (I) are not particularly limited, but examples thereof include halogen atoms, nitro groups, cyano groups, hydroxy groups, amino groups, -R', -OR, -COR, -SR, -SOR, -SOR, -SOR, -NHR, -NR, -COOR, -OCOR, -CONHR, -CONR, and -NHCOR. 2 The "substituents" of the aryl and heteroaryl groups in the formula (I) are not particularly limited, and examples thereof include a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, -R, -OR, -COR, -SR, -SOR, -SOR, -SOR, -NHR, -NR, -COOR, -OCOR, -CONHR, -CONR, -NHCOR, etc. R' is (1) an aryl group optionally substituted with a group selected from a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group (an alkyl group substituted with one or more aryl groups), an alkyl-aryl group (an aryl group substituted with one or more alkyl groups), an alkyl-oxy group, an alkenyl-oxy group, and an aryl-oxy group, or (2) a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, an alkyl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, and an aryl-oxy group. R represents (1) above for R', (2) above for R', (3) an alkyl group optionally substituted with a group selected from a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an aryl group, an alkyl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, and an aryl-oxy group, or (4) an alkenyl group optionally substituted with a group selected from a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an aryl group, an alkyl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, and an aryl-oxy group.

[0072] R 2In one embodiment, is preferably an alkyl group which may have a substituent or an alkenyl group which may have a substituent; more preferably an alkyl group which may have a substituent; and even more preferably a group represented by the formula (R2):

[0073] [ka]

[0074] [In the formula, X represents an alkylene group having 1 to 6 carbon atoms: Y represents a single bond, -O-, -CO-, -S-, -SO-, -SO2-, -NH-, -COO-, -OCO-, -CONH-, or -NHCO-; * indicates the binding site.] R 2 is a group represented by formula (R2), the pH of the resin composition can be increased, and the curing of the epoxy resin can be further accelerated.

[0075] X represents an alkylene group having 1 to 6 carbon atoms; in one embodiment, it is preferably an alkylene group having 1 to 3 carbon atoms; particularly preferably -CH2-CH2-.

[0076] The alkylene group refers to a linear, branched, and / or cyclic divalent aliphatic saturated hydrocarbon group. The alkylene group having 1 to 6 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include -CH2-, -CH2-CH2-, -CH(CH3)-, -CH2-CH2-CH2-, -CH2-CH(CH3)-, -CH(CH3)-CH2-, and -C(CH3)2-.

[0077] Y represents a single bond, -O-, -CO-, -S-, -SO-, -SO2-, -NH-, -COO-, -OCO-, -CONH-, or -NHCO-; in one embodiment, it is preferably a single bond.

[0078] R 3 and R4 each independently represents a hydrogen atom or a substituent, or R 3 and R 4 are bonded together to form an aromatic ring which may have a substituent, or a non-aromatic ring which may have a substituent.

[0079] The aromatic ring refers to a ring that conforms to Hückel's 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 ring may be an aromatic carbocyclic ring containing only carbon atoms as ring-constituting atoms, or an aromatic heterocyclic ring containing heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as ring-constituting atoms in addition to carbon atoms. In one embodiment, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 6- to 14-membered aromatic ring, and even more preferably a 6- to 10-membered aromatic ring. Specific examples of suitable aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. A benzene ring or a naphthalene ring is more preferred, and a benzene ring is particularly preferred.

[0080] A non-aromatic ring refers to a ring other than an aromatic ring that has aromaticity throughout the ring. The non-aromatic ring may be a non-aromatic carbocyclic ring having only carbon atoms as ring-constituting atoms, or a non-aromatic heterocyclic ring having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as ring-constituting atoms in addition to carbon atoms. The non-aromatic ring is preferably a 3- to 21-membered non-aromatic ring, more preferably a 4- to 17-membered non-aromatic ring, and even more preferably a 5- to 14-membered non-aromatic ring. Specific examples of suitable non-aromatic rings include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cyclopentadiene ring, a 1,3-cyclohexadiene ring, and a 1,4-cyclohexadiene ring.

[0081] R 3 and R 4 "Substituents" in and R 3 and R 4 The "substituents" in the aromatic and non-aromatic rings formed by R 2 Examples of the "substituents" include those similar to those of the aryl group and heteroaryl group in the above.

[0082] R3 and R 4 In one embodiment, each independently is preferably a hydrogen atom or a substituent; more preferably a hydrogen atom or an alkyl group; and particularly preferably a hydrogen atom.

[0083] A double line, dashed or solid, indicates a single bond or a double bond; in one embodiment, a double bond is preferred.

[0084] Specific examples of the component (C1) include 2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine.

[0085] The content of component (C1) in the resin composition is not particularly limited, but is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.03% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The upper limit of the content of component (C1) in the resin composition is not particularly limited, but is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less, based on 100% by mass of the total amount of curing accelerator (C) in the resin composition. The content of component (C1) 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, based on 100% by mass of the total amount of curing accelerator (C) in the resin composition.

[0086] In the resin composition of the present invention, the curing accelerator (C) may contain a curing accelerator (C2) other than the component (C1).

[0087] Examples of component (C2) include imidazole-based curing accelerators other than component (C1), amine-based curing accelerators other than component (C1), phosphorus-based curing accelerators other than component (C1), urea-based curing accelerators other than component (C1), guanidine-based curing accelerators other than component (C1), and metal-based curing accelerators other than component (C1). The (C) curing accelerator preferably contains a curing accelerator selected from imidazole-based curing accelerators other than component (C1) and amine-based curing accelerators other than component (C1), and particularly preferably contains an amine-based curing accelerator other than component (C1). The (C) curing accelerators may be used alone or in combination of two or more.

[0088] Examples of imidazole-based curing accelerators other than component (C1) include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-methylimidazole. 1-cyanoethyl-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'-methylimidazole] 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 with isocyanuric acid Examples of imidazole compounds include adducts of imidazole compounds with epoxy resins, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline.

[0089] As the imidazole-based curing accelerator other than component (C1), commercially available products may be used, such as "1B2PZ," "2MZA-PW," and "2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0090] Examples of amine-based curing accelerators other than component (C1) include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0091] As the amine-based curing accelerator other than the component (C1), a commercially available product may be used, for example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc.

[0092] Examples of phosphorus-based curing accelerators other than component (C1) 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, and tetraphenylphosphonium bromide. Aromatic phosphonium salts such as tris(3-methylphenyl)ethylphosphonium 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 addition products such as triphenylphosphine-p-benzoquinone addition product; 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 aromatic phosphines such as benzene, 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;

[0093] Examples of urea-based curing accelerators other than component (C1) include aliphatic dimethylureas such as 1,1-dimethylurea, 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, Examples of aromatic dimethylureas include 1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0094] Examples of guanidine-based curing accelerators other than component (C1) include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, and 1,5,7-triazabicyclo[4.4.0]de. Examples of such compounds include 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.

[0095] Examples of metal-based curing accelerators other than component (C1) include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0096] The content of (C) curing accelerator in the resin composition is not particularly limited, but is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more, when the nonvolatile components in the resin composition are taken as 100% by mass. The upper limit of the content of (C) curing accelerator in the resin composition is not particularly limited, but is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.2% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0097] <(D) Inorganic filler> The resin composition of the present invention may contain (D) an inorganic filler as an optional component. (D) The inorganic filler is contained in the resin composition in the form of particles.

[0098] (D) Inorganic fillers are inorganic compounds. Examples of (D) inorganic filler materials 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 titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. (D) Inorganic filler materials preferably include a material selected from silica, alumina, and aluminosilicate, and particularly preferably include silica. The inorganic filler (D) may be one type alone or a combination of two or more types in any ratio.

[0099] The (D) inorganic filler may be composed only of the (D1) hollow inorganic filler, or may be composed only of the (D2) solid inorganic filler, or may be composed of both the (D1) hollow inorganic filler and the (D2) solid inorganic filler. The (D) inorganic filler is preferably composed of both the (D1) hollow inorganic filler and the (D2) solid inorganic filler.

[0100] The hollow inorganic filler (D1) may contain an inorganic filler of monohollow particles having only one void inside the particle, or may contain an inorganic filler of polyhollow particles having multiple voids inside the particle, or may contain both.

[0101] The hollow inorganic filler (D1) has an average porosity of more than 0% by volume, preferably 1% by volume or more, more preferably 5% by volume or more, even more preferably 10% by volume or more, and particularly preferably 15% by volume or more. The upper limit of the average porosity of the hollow inorganic filler (D1) is not particularly limited, but is preferably 90% by volume or less, and more preferably 85% by volume or less.

[0102] The average porosity P (vol %) of an inorganic filler is defined as the volume-based ratio of the total volume of one or more pores present inside the particle to the total volume of the particle based on the outer surface of the particle (total volume of pores / volume of particle). For example, the actual density measurement value D of the inorganic filler M (g / cm 3 ), and the theoretical value of the material density D of the material that forms the inorganic filler T (g / cm 3 ) is used to calculate the value according to the following formula (I).

[0103]

number

[0104] The actual density of the inorganic filler can be measured using, for example, a true density measuring device. Examples of true density measuring devices include the Ultrapycnometer 1000 manufactured by Quantachrome. Nitrogen, for example, is used as the measurement gas.

[0105] The hollow inorganic filler (D1) is preferably a hollow inorganic filler selected from spherical hollow silica, spherical hollow alumina, and spherical hollow aluminosilicate. The hollow inorganic filler (D1) may be used alone or in combination of two or more kinds in any ratio.

[0106] The average particle size of the hollow inorganic filler (D1) is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The lower limit of the average particle size of the hollow inorganic filler (D1) 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.

[0107] The average particle size of inorganic fillers can be measured using a laser diffraction / scattering method based on Mie scattering theory. Specifically, a volumetric particle size distribution of the inorganic filler is created using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture ultrasonically for 10 minutes. The volumetric particle size distribution of the inorganic filler was measured using a laser diffraction particle size distribution analyzer with blue and red wavelength light sources using a flow cell system, and the average particle size was calculated as the median diameter from the particle size distribution obtained. Examples of laser diffraction particle size distribution analyzers include the LA-960 manufactured by Horiba, Ltd.

[0108] The specific surface area of the hollow inorganic filler (D1) 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 hollow inorganic filler (D1) 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 then calculating the specific surface area using the BET multipoint method.

[0109] (D1) Commercially available hollow inorganic fillers include, for example, 、Yu Examples include "LHP-208" (average particle size 0.5 μm, porosity 50% by volume) manufactured by Hexsymo Co., Ltd., "DLSB-001" (average particle size 0.23 μm, porosity 20% by volume) manufactured by Daiken Chemical Co., Ltd., and "MG-005" (average particle size 1.6 μm, porosity 80% by volume) manufactured by Taiheiyo Cement Corporation.

[0110] The hollow inorganic filler (D1) is preferably treated with a surface treatment agent to improve moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. The surface treatment agents may be used alone or in any combination of two or more.

[0111] 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).

[0112] The degree of surface treatment with the surface treatment agent preferably falls within a predetermined range from the viewpoint of improving the dispersibility of the hollow inorganic filler (D1). Specifically, 100% by mass of the hollow inorganic filler (D1) 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.

[0113] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (D1) hollow inorganic filler. From the viewpoint of improving the dispersibility of the (D1) hollow inorganic filler, the amount of carbon per unit surface area of the (D1) hollow 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:

[0114] The content (mass%) of the (D1) hollow inorganic filler in the (D) inorganic filler is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, when the nonvolatile components in the resin composition are taken as 100% by mass, from the viewpoint of further reducing the dielectric constant. The upper limit of the content (mass%) of the (D1) hollow inorganic filler in the (D) inorganic filler is not particularly limited, but is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0115] (D2) The solid inorganic filler has an average porosity of 0% by volume.

[0116] The (D2) solid inorganic filler is preferably a solid inorganic filler selected from spherical solid silica, spherical solid alumina, and spherical solid aluminosilicate. The (D2) solid inorganic filler may be used alone or in combination of two or more kinds in any ratio.

[0117] The average particle size of the (D2) solid inorganic filler is preferably 5 μm or less, more preferably 3 μm or less, even more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.6 μm or less. The lower limit of the average particle size of the (D2) solid 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.

[0118] The specific surface area of the (D2) solid 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 (D2) solid inorganic filler 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 / g or less.

[0119] (D2) Commercially available solid 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 Limited; "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.; and "DAW-03" and "FB-105FD" manufactured by Denka Company Limited.

[0120] The (D2) solid inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility.

[0121] The degree of surface treatment with the surface treatment agent preferably falls within a predetermined range from the viewpoint of improving the dispersibility of the (D2) solid inorganic filler. Specifically, 100% by mass of the (D2) solid 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.

[0122] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (D2) solid inorganic filler. From the viewpoint of improving the dispersibility of the (D2) solid inorganic filler, the amount of carbon per unit surface area of the (D2) solid 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:

[0123] The content (mass%) of the (D) inorganic filler in the resin composition is, for example, 0 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, preferably 40 mass% or more, more preferably 50 mass% or more, even more preferably 60 mass% or more, still more preferably 65 mass% or more, and particularly preferably 70 mass% or more, when the nonvolatile components in the resin composition are taken as 100 mass%. The upper limit of the content (mass%) of the (D) inorganic filler in the resin composition is not particularly limited, but is preferably 90 mass% or less, more preferably 85 mass% or less, and even more preferably 80 mass% or less, when the nonvolatile components in the resin composition are taken as 100 mass%.

[0124] The content (vol %) of the (D) inorganic filler in the resin composition is, for example, 0% by mass or more, 10% by mass or more, 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 60% by volume or more, when the nonvolatile components in the resin composition are taken as 100% by volume. The upper limit of the content (vol %) of the (D) inorganic filler in the resin composition is not particularly limited, but may be preferably 80% by volume or less, more preferably 75% by volume or less, and even more preferably 70% by volume or less, when the nonvolatile components in the resin composition are taken as 100% by volume.

[0125] <(E) Epoxy resin curing agent> The resin composition of the present invention may contain an optional component, an epoxy resin curing agent (E). The epoxy resin curing agent (E) may have the function of reacting with the epoxy resin (A) to cure it. The epoxy resin curing agent (E) may be used alone or in any combination of two or more. The epoxy resin curing agent (E) described here is a component other than the thermoplastic resin (F) described below.

[0126] The (E) epoxy resin curing agent is not particularly limited, but examples thereof include active ester curing agents, phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol curing agents. In one embodiment, the (E) epoxy resin 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 (E) epoxy resin curing agent particularly preferably contains an active ester curing agent from the viewpoint of further reducing the dielectric loss tangent. In one embodiment, the (E) epoxy resin curing agent particularly preferably contains a phenolic curing agent from the viewpoint of further improving curability.

[0127] As the active ester curing agent, compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. The active ester compound is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. From the viewpoint of improving heat resistance in particular, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0128] Specific examples of the active ester curing agent include dicyclopentadiene-type active ester compounds, naphthalene-type active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, and active ester compounds containing a benzoylated product of phenol novolac, and among these, at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred.

[0129] Commercially available active ester curing agents include "EXB9451," "EXB9460," "EXB9460S," "HPC-8000L-65TM," "HPC-8000-65T," "HPC-8000H," and "HPC-8000H-65TM" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure; and "HP-B-8151-62T," "EXB-8100L-65T," "EXB-9416-70BK," and "HPC-8150-62T" as active ester compounds containing a naphthalene structure. and "EXB-8" (manufactured by DIC Corporation); a phosphorus-containing active ester compound, "EXB9401" (manufactured by DIC Corporation); an active ester compound which is an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds which are benzoylated products of phenol novolac, "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); an active ester compound containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Inc.), and the like.

[0130] As the phenolic curing agent, a phenolic curing agent having a novolac structure is preferred from the viewpoint of heat resistance and water resistance. Also, from the viewpoint of adhesion to an adherend, a nitrogen-containing phenolic curing agent is preferred, and a triazine skeleton-containing phenolic curing agent is more preferred. Among them, a triazine skeleton-containing phenolic novolac resin is preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of phenolic curing agents include "MEH-7700," "MEH-7810," and "MEH-7851" manufactured by Meiwa Chemical Industry 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.

[0131] Examples of carbodiimide curing agents include curing agents having one or more, preferably two or more, carbodiimide structures in one molecule, such as aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane-bis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); and aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide). ; aromatic polycarbodiimides such as poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide].

[0132] Commercially available carbodiimide curing agents include, for example, "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-07," and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; and "Stavaxol P," "Stavaxol P400," and "Hykasil 510" manufactured by Rhein Chemie.

[0133] The acid anhydride curing agent may be 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 preferred. 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 suitable 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 anhydrides such as styrene-maleic acid resins, which are copolymers 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 Hitachi Chemical Co., Ltd.; and "EF-30," "EF-40," "EF-60," and "EF-80" manufactured by Clay Valley.

[0134] Examples of the amine curing agent include curing agents having one or more, preferably two or more, amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, among which aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propane. propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine-based curing agents 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.

[0135] Specific examples of benzoxazine 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 Chemicals Corporation.

[0136] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; multifunctional 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 curing agents include "PT30" and "PT60" (both phenol novolac type multifunctional cyanate ester resins) manufactured by Lonza Japan Co., Ltd., "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine converted to a trimer).

[0137] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0138] The reactive group equivalent of the (E) epoxy resin curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., even more 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 (E) epoxy resin curing agent per equivalent of reactive group.

[0139] When an active ester curing agent is included as the (E) epoxy resin curing agent, the content of the active ester curing agent in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 8% by mass or more, from the viewpoint of further reducing the dielectric loss tangent, when the total amount of the (E) epoxy resin curing agent in the resin composition is taken as 100% by mass. Furthermore, the content of the active ester curing agent in the (E) epoxy resin curing agent 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 further reducing the dielectric loss tangent, when the total amount of the (E) epoxy resin curing agent in the resin composition is taken as 100% by mass.

[0140] When a phenolic curing agent is included as the (E) epoxy resin curing agent, the content of the phenolic curing agent in the resin composition is, from the viewpoint of further improving curability, preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, and particularly preferably 1.7% by mass or more, where the total amount of non-volatile components in the resin composition is 100% by mass.

[0141] The content of (E) epoxy resin curing agent in the resin composition is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 13% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of (E) epoxy resin curing agent in the resin composition is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, even more preferably 8% by mass or more, and particularly preferably 10% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition.

[0142] <(F)Thermoplastic resin> The resin composition of the present invention may contain, as an optional component, a thermoplastic resin (F). The thermoplastic resin (F) is a component that does not fall under the category of the epoxy resin (A) described above.

[0143] Examples of (F) thermoplastic resins include polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. In one embodiment, the (F) thermoplastic resin preferably contains a thermoplastic resin selected from the group consisting of polyimide resins and phenoxy resins, and more preferably contains a phenoxy resin. One type of (F) thermoplastic resin may be used alone, or two or more types may be used in combination.

[0144] 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.

[0145] Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, bisphenolacetophenone, novolac, biphenyl, fluorene, dicyclopentadiene, norbornene, naphthalene, anthracene, adamantane, terpene, and trimethylcyclohexane. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0146] 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.

[0147] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, with polyvinyl butyral resins being preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-EP, manufactured by Denki Kagaku Kogyo Co., Ltd.; and 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.

[0148] Examples of polyolefin resins include ethylene 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.

[0149] 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, and polyphenylene ether-polybutadiene resins.

[0150] Specific examples of polyamide-imide resins include "Vylomax HR11NN" and "Vylomax 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-imides) manufactured by Hitachi Chemical Co., Ltd.

[0151] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0152] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0153] A specific example of the polyphenylene ether resin is NORYL SA90 manufactured by SABIC, etc. A specific example of the polyetherimide resin is ULTEM manufactured by GE, etc.

[0154] 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 "FPC0220" manufactured by Mitsubishi Gas Chemical Company, Inc., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090," "C-2090," and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. Specific examples of polyether ether ketone resins include "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd.

[0155] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.

[0156] From the viewpoint of further improving film formability, the weight average molecular weight (Mw) of the (F) 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.

[0157] The content of the thermoplastic resin (F) in the resin composition is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 2% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of the thermoplastic resin (F) in the resin composition is not particularly limited, but is, based on 100% by mass of the nonvolatile components in the resin composition, for example, 0% by mass or more, 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 0.7% by mass or more.

[0158] <(G) Other additives> The resin composition of the present invention may further contain any additives. Examples of such additives include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; thermosetting resins other than epoxy resins such as epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, and silicone resins; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt 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 leveling agents and acrylic polymer leveling agents; thickeners such as bentone and montmorillonite; and defoamers such as silicone defoamers, acrylic defoamers, fluorine-based defoamers, and vinyl resin defoamers. surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers. The (G) other additives may be used singly or in any combination of two or more kinds in any ratio. The content of the (G) other additives can be appropriately determined by a person skilled in the art.

[0159] <(H) Organic Solvent> The resin composition of the present invention may further contain an arbitrary organic solvent. As the (H) organic solvent, any known organic solvent can be used appropriately, and the type thereof is not particularly limited. Examples of the (H) 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; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methoxypropionic acid. Examples of suitable organic solvents include ether ester solvents such as methyl ether, 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, and trimethylbenzene. The organic solvent (H) may be used singly or in combination of two or more in any ratio.

[0160] The content of (H) organic solvent in the varnish-like resin composition before drying is not particularly limited, but is, when all components in the resin composition are taken as 100% by mass, 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. The content of (H) organic solvent in the resin composition after drying to form a resin composition layer in a resin sheet is not particularly limited, but is, when all components in the resin composition are taken as 100% by mass, 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.

[0161] <Method of manufacturing resin composition> The resin composition of the present invention can be produced, for example, by adding (A) epoxy resin, (B) radically polymerizable group-containing compound, (C) curing accelerator, optionally (D) inorganic filler, optionally (E) epoxy resin curing agent, optionally (F) thermoplastic resin, optionally (G) other additives, and optionally (H) organic solvent to any preparation vessel in any order and / or simultaneously in part or in whole, and mixing them. Furthermore, the temperature can be appropriately set during the process of adding and mixing each component, and heating and / or cooling may be performed temporarily or throughout the process. Furthermore, during or after the process of adding and mixing, the resin composition may be stirred or shaken using a stirring or shaking device such as a mixer to uniformly disperse the resin composition. Furthermore, degassing may be performed under low-pressure conditions, such as under vacuum, simultaneously with the stirring or shaking.

[0162] <Characteristics of resin composition> The resin composition of the present invention comprises (A) an epoxy resin, (B) a radically polymerizable group-containing compound, and (C) a curing accelerator, wherein the curing accelerator (C) comprises (C1) a compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms. Such a resin composition can provide a cured product with excellent crack resistance.

[0163] A cured product of the resin composition of the present invention can be characterized by being able to suppress the occurrence of cracks after desmearing (roughening treatment). Thus, in one embodiment, after producing a circuit board and subjecting it to desmearing as in the following Test Example 3, when 100 copper pads of the circuit board are observed, the cracks can be found in preferably less than 15% (15% or less), particularly preferably less than 5% (5% or less).

[0164] In one embodiment, a cured product of the resin composition of the present invention may be characterized by a low coefficient of linear thermal expansion (CTE). Thus, in one embodiment, the coefficient of linear thermal expansion (CTE) of the cured product, measured as in Test Example 1 below, is preferably 40 ppm / K or less, more preferably 35 ppm / K or less, even more preferably 30 ppm / K or less, still more preferably 25 ppm / K or less, and particularly preferably 22 ppm / K or less, in the range of 25°C to 150°C. The lower limit of the coefficient of linear thermal expansion (CTE) is not particularly limited, but may be, for example, 1 ppm / K or more.

[0165] In one embodiment, the cured product of the resin composition of the present invention may be characterized by a higher glass transition temperature (Tg). Thus, in one embodiment, the glass transition temperature (Tg) measured in the following Test Example 1 may be preferably 120°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, still more preferably 145°C or higher, and particularly preferably 150°C or higher.

[0166] In one embodiment, the cured product of the resin composition of the present invention may be characterized by a lower dielectric loss tangent (Df). Thus, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition, as measured at 5.8 GHz and 23°C as in Test Example 2 below, may be preferably 0.010 or less, more preferably 0.009 or less, even more preferably 0.008 or less, even more preferably 0.007 or less, still more preferably 0.006 or less or 0.0055 or less, and particularly preferably 0.005 or less or 0.0045 or less.

[0167] In one embodiment, a cured product of the resin composition of the present invention may be characterized by a lower 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 2 below is not particularly limited, but may be preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.7 or less, even more preferably 3.5 or less, and particularly preferably 3.3 or less.

[0168] <Applications of resin composition> The resin composition of the present invention can be suitably used as a resin composition for insulating applications, particularly as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer. It can also be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board) in the printed wiring board described below. The resin composition of the present invention can also 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, semiconductor encapsulants, hole-filling resins, and component-embedding resins.

[0169] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring formation layer (resin composition for forming a rewiring formation layer) as an insulating layer for forming a rewiring layer, and as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the encapsulating layer. (1) a step of laminating a temporary fixing film on 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 step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0170] Furthermore, the resin composition of the present invention provides an insulating layer with good component embedding properties, and therefore can be suitably used when the printed wiring board is a circuit board with built-in components.

[0171] <Sheet-type laminated material> The resin composition of the present invention can be used by applying it in the form of a varnish, but industrially it is generally preferred to use it in the form of a sheet-like laminate material containing the resin composition.

[0172] As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

[0173] 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.

[0174] The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of thinning the printed wiring board and providing a cured product of the resin composition with excellent insulating properties even when the cured product is thin. 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.

[0175] 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.

[0176] 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, with inexpensive polyethylene terephthalate being particularly preferred.

[0177] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be 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.).

[0178] The surface of the support that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0179] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may also be used as the support with a release layer, including, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0180] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0181] In one embodiment, the resin sheet may further include an optional layer as needed. Examples of such optional layers include a protective film conforming to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0182] The resin sheet can be produced, for example, by preparing a liquid (varnish) resin composition as is or by dissolving the resin composition in an organic solvent, applying the liquid (varnish) resin composition onto a support using a die coater or the like, and then drying the applied composition to form a resin composition layer.

[0183] 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.

[0184] Drying may be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out so that the content of organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by 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% by mass to 60% by mass of organic solvent is used, a resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0185] 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.

[0186] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

[0187] The sheet-like fiber substrate used for the prepreg is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. 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.

[0188] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0189] The thickness of the prepreg may be in the same range as that of the resin composition layer in the resin sheet described above.

[0190] 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).

[0191] <Printed wiring board> The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

[0192] 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 so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., thermally curing) the resin composition layer to form an insulating layer.

[0193] The "inner layer substrate" used in step (I) is a member that will become the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and this 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 referred to as an "inner layer circuit board." Furthermore, the "inner layer substrate" of the present invention also includes intermediate products on which an insulating layer and / or a conductor layer is to be further formed during the production of a printed wiring board. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0194] The inner layer substrate and the resin sheet can be laminated, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as a "thermocompression bonding member") include a heated metal plate (such as a SUS end plate) or a metal roll (SUS roll). Note that rather than pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press it via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently conform to the surface irregularities of the inner layer substrate.

[0195] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination may be carried out under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0196] The lamination can be performed using 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 vacuum pressure laminator.

[0197] After lamination, the laminated resin sheets 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 lamination. The smoothing treatment may be performed using a commercially available laminator. Note that lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0198] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0199] In step (II), the resin composition layer is cured (for example, by heat curing) 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 typically employed for forming insulating layers for printed wiring boards may be used.

[0200] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but in one embodiment, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0201] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0202] When manufacturing a printed wiring board, the following steps may be further performed: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. These steps (III) to (V) may be performed according to various methods known to those skilled in the art and used in manufacturing printed wiring boards. When the support is removed after step (II), the removal of the support may be performed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

[0203] In another embodiment, the printed wiring board of the present invention can be produced using the above-mentioned prepreg. The production method is basically the same as when a resin sheet is used.

[0204] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be determined appropriately depending on the design of the printed wiring board.

[0205] Step (IV) is a step of roughening the insulating layer. Typically, smear removal is also performed in this step (IV). The roughening treatment procedure and conditions are not particularly limited, and known procedures and conditions commonly used in forming insulating layers for printed wiring boards 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.

[0206] The swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions and surfactant solutions, and is preferably an alkaline solution, with sodium hydroxide solution and potassium hydroxide solution being more preferred. Commercially available swelling liquids include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment using a swelling liquid is not particularly limited, but can be carried out by, for example, immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes. To keep the swelling of the resin in 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.

[0207] The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using an oxidizing agent such as alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan.

[0208] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan.

[0209] Treatment with a 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 standpoint 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.

[0210] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after the roughening treatment is not particularly limited, but is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, etc. Furthermore, the root mean square roughness (Rq) of the insulating layer surface after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0211] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., 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.

[0212] The conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a 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.

[0213] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0214] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, it is preferable to form the conductor layer by a semi-additive method. An example of forming the conductor layer by a semi-additive method will be described below.

[0215] 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, exposing a portion of the plating seed layer corresponding to the 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, thereby forming a conductor layer having the desired wiring pattern.

[0216] In another embodiment, the conductor layer may be formed using a metal foil. When a metal foil is used to form the conductor layer, step (V) is preferably performed between steps (I) and (II). For example, after step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The resin composition layer and the metal foil may be laminated by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed using the metal foil on the insulating layer by a conventionally known technique such as a subtractive method or a modified semi-additive method.

[0217] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0218] <Semiconductor device> The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0219] Examples of semiconductor devices include various semiconductor devices used in electrical appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0220] The present invention will be described in more detail 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).

[0221] Example 1 Thirty parts of a bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: approximately 180 g / eq.) and 30 parts of a biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: approximately 269 g / eq.) were heated and dissolved in 55 parts of solvent naphtha with stirring, and then cooled to room temperature. The mixed solution was added with 280 parts of spherical 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.), 14 parts of a triazine skeleton-containing phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl group equivalent weight approximately 151, 2-methoxypropanol solution with a solid content of 50%), 55 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent weight approximately 223, toluene solution with a non-volatile content of 65% by mass), and 10 parts of a phenoxy resin. A varnish-like resin composition was prepared by mixing 10 parts of a resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK with 30% by mass of non-volatile components and cyclohexanone), 3 parts of a vinyl compound ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., dioxane glycol diacrylate), and 6 parts of a curing accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, a 2-methoxypropanol solution with a solids content of 5% by mass) and dispersing the mixture uniformly using a high-speed rotating mixer.

[0222] (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 ultrasonically for 10 minutes. Using a laser diffraction particle size distribution analyzer (HORIBA, Ltd., "LA-960"), blue and red light sources were used, and the particle size distribution of the inorganic filler was measured on a volume basis using a flow cell system. From the particle size distribution obtained, the average particle size of the inorganic filler was calculated as the median diameter.

[0223] <Example 2> A varnish-like resin composition was prepared in the same manner as in Example 1, except that the amount of curing accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, 2-methoxypropanol solution with a solid content of 5% by mass) was changed from 6 parts to 4 parts, and 2 parts of curing accelerator (DMAP, 4-dimethylaminopyridine, MEK solution with a solid content of 5% by mass) was further mixed in.

[0224] Example 3 A varnish-like resin composition was prepared in the same manner as in Example 2, 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.).

[0225] Example 4 A varnish-like resin composition was prepared in the same manner as in Example 2, 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.).

[0226] <Example 5> A varnish-like resin composition was prepared in the same manner as in Example 2, except that 55 parts of the active ester compound (DIC Corporation's "HPC-8000-65T," active group equivalent weight: approximately 223, non-volatile components: 65% by mass in toluene solution) were not used, the amount of triazine skeleton-containing phenolic curing agent (DIC Corporation's "LA-3018-50P," hydroxyl group equivalent weight: approximately 151, solids content: 50% in 2-methoxypropanol solution) was changed from 14 parts to 40 parts, and the amount of spherical silica (Admatechs Corporation's "SO-C2," average particle size: 0.5 μm) surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM573") was changed from 280 parts to 220 parts.

[0227] Example 6 A varnish-like resin composition was prepared in the same manner as in Example 2, except that 3 parts of an allyl group-containing benzoxazine compound ("ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd.) was used instead of 3 parts of an acrylate compound ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., dioxane glycol diacrylate).

[0228] Example 7 A varnish-like resin composition was prepared in the same manner as in Example 2, except that 4.6 parts of an oligophenylene ether-styrene resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Inc., a toluene solution with a nonvolatile content of 65%) was used instead of 3 parts of an acrylate compound ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., dioxane glycol diacrylate).

[0230] (Method for measuring the average porosity of inorganic fillers) The 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 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 ) and the average porosity of the inorganic filler was measured 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.

[0231] <Comparative Example 1> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 6 parts of a curing accelerator ("1B2PZ" manufactured by Shikoku Chemicals Corporation, 1-benzyl-2-phenylimidazole, MEK solution with a solids content of 5% by mass) was used instead of 6 parts of curing accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, 2-methoxypropanol solution with a solids content of 5% by mass).

[0232] <Comparative Example 2> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 6 parts of a curing accelerator ("2P4MZ" manufactured by Shikoku Chemicals Corporation, 2-phenyl-4-methylimidazole, 2-methoxypropanol solution with a solids content of 5% by mass) was used instead of 6 parts of curing accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, 2-methoxypropanol solution with a solids content of 5% by mass).

[0233] <Comparative Example 3> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 6 parts of a curing accelerator ("TBP-DA" manufactured by Shikoku Chemicals Corporation, tetrabutylphosphonium decanoate, MEK solution with a solids content of 5% by mass) was used instead of 6 parts of curing accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, 2-methoxypropanol solution with a solids content of 5% by mass).

[0234] <Comparative Example 4> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 6 parts of a curing accelerator ("DMAP," 4-dimethylaminopyridine, MEK solution with a solids content of 5% by mass) was used instead of 6 parts of a curing accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, 2-methoxypropanol solution with a solids content of 5% by mass).

[0235] <Comparative Example 5> A varnish-like resin composition was prepared in the same manner as in Example 1, except that 6 parts of curing accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, 2-methoxypropanol solution with a solids content of 5% by mass) was not used.

[0236] <Comparative Example 6> A varnish-like resin composition was prepared in the same manner as in Example 2, except that 3 parts of a vinyl compound ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., dioxane glycol diacrylate) was not used.

[0237] <Test Example 1: Measurement of glass transition temperature and linear thermal expansion coefficient of cured product> A PET film with an alkyd resin-based release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. The varnish-like resin compositions prepared in the Examples and Comparative Examples were uniformly applied onto the release layer of the support so that the thickness of the resin composition layer after drying would be 40 μm, and the resulting layer was dried at 80 to 120°C (average 100°C) for 5 minutes to produce a resin sheet.

[0238] The resulting resin sheet, with a resin composition layer thickness of 40 μm, was heated at 200°C for 90 minutes to thermally cure the resin composition layer, after which the support was peeled off to obtain a cured product for evaluation. The cured product for evaluation was cut into test pieces measuring 5 mm wide and 15 mm long. The test pieces were subjected to thermomechanical analysis using a thermomechanical analyzer (Rigaku Corporation, "Thermo Plus TMA8310") by the tensile load method. Specifically, the test pieces were loaded into the thermomechanical analyzer and subjected to two consecutive measurements under the following conditions: a load of 1 g and a heating rate of 5°C / min. The glass transition temperature (°C) and the linear thermal expansion coefficient (ppm / K) in the in-plane direction over a temperature range of 25°C to 150°C were calculated from the two measurements.

[0239] <Test Example 2: Measurement of relative dielectric constant and dielectric loss tangent of cured product> The cured product for evaluation obtained in the same manner as in Test Example 1 was cut into test pieces measuring 2 mm in width and 80 mm in length. The dielectric constant and dielectric loss tangent of the test pieces were measured by the cavity resonance perturbation method using an "HP8362B" manufactured by Agilent Technologies at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurements were performed on two test pieces, and the average values were calculated.

[0240] <Test Example 3: Evaluation of crack resistance> (1) Preparation of inner layer board Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") with an inner layer circuit formed on it were etched 1 μm deep with a microetching agent (MEC "CZ8101") to roughen the copper surface.

[0241] (2) Laminating resin sheets Using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator "CVP700"), the resin sheet obtained in the same manner as in Test Example 1 was laminated onto both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. Lamination was performed by reducing the pressure for 30 seconds to 13 hPa or less, followed by pressure bonding at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, a heat press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

[0242] (3) Thermal curing of the resin composition layer The inner layer substrate laminated with the resin sheet was placed in an oven at 130°C and heated for 30 minutes, then transferred to an oven at 170°C and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. The support was then peeled off to obtain a cured substrate having the insulating layer, inner layer substrate, and insulating layer in this order.

[0243] (4) Roughening treatment The cured substrate was subjected to a desmear treatment as a roughening treatment, which was the following wet desmear treatment.

[0244] (wet desmear treatment) The cured substrate was immersed in a swelling solution (Atotech Japan's "Swelling Dip Securigant P," an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, then in an oxidizing solution (Atotech Japan's "Concentrate Compact CP," an aqueous solution of approximately 6% potassium permanganate and 4% sodium hydroxide) at 80°C for 20 minutes, then in a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P," an aqueous sulfuric acid solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

[0245] According to JIS K 5600-5-6, the roughened test substrates were subjected to a wet desmearing process to create a grid of notches, and the presence or absence of cracks in the cured coating was evaluated by observing them with an optical microscope. Specifically, grid-like notches were created at 1 mm intervals in the cured coating of the test substrate, forming 10 vertical and 10 horizontal notches, for a total of 100 coating pieces. Here, the coating piece refers to each portion of the cured coating separated by the notches. These 100 coating pieces were observed with an optical microscope, and the number of coating pieces with cracks was counted. Based on the ratio of the number of coating pieces with cracks to the total number of coating pieces (100), crack resistance was evaluated according to the following evaluation criteria.

[0246] Evaluation criteria "○": Almost no cracks in the cured coating (less than 5%) "△": Slight cracks in the cured coating (5% to less than 15%) "X": Numerous cracks in the cured coating (15% or more)

[0247] The content of non-volatile components contained in the resin compositions of the Examples and Comparative Examples, as well as the measurement results and evaluation results of the Test Examples, are summarized in Table 1 below.

[0248] [Table 1]

[0249] The results shown in Table 1 above show that a cured product with excellent crack resistance can be obtained by using a resin composition comprising (A) an epoxy resin, (B) a radically polymerizable group-containing compound, and (C) a curing accelerator, wherein component (C) comprises (C1) a compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms.

Claims

1. A resin composition for an insulating layer, comprising (A) an epoxy resin, (B) a radical polymerizable group-containing compound (excluding "a compound having a maleimide group"), (C) a curing accelerator, and (E) an epoxy resin curing agent, The component (C) includes (C1) a compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having from 7 to 30 carbon atoms, The component (C1) is a compound represented by the formula (C): 【Chemical 1】 [In the formula, R 1 represents an alkyl group having 7 or more carbon atoms or an alkenyl group having 7 or more carbon atoms; R 2 represents a group represented by the following formula (R2): R 3 and R 4 each independently represent a hydrogen atom or a substituent, or R 3 and R 4 bond together to form an aromatic ring which may have a substituent or a non-aromatic ring which may have a substituent; A double line, a dashed line and a solid line, represents a single bond or a double bond.] The compound includes a compound represented by A resin composition for an insulating layer, wherein the component (E) contains an active ester-based curing agent or a phenol-based curing agent. 【Chemistry 2】 [In the formula, X represents an alkylene group having 1 to 6 carbon atoms: Y represents a single bond, —O—, —CO—, —S—, —SO—, —SO 2 —, —NH—, —COO—, —OCO—, —CONH—, or —NHCO—; * indicates a binding site.]

2. 2. The resin composition according to claim 1, wherein the content of the component (C1) is 0.001% by mass to 1% by mass, where the total amount of nonvolatile components in the resin composition is 100% by mass.

3. 3. The resin composition according to claim 1, wherein the content of the component (A) is 10% by mass to 30% by mass, where the total amount of nonvolatile components in the resin composition is 100% by mass.

4. The resin composition according to any one of claims 1 to 3, wherein component (B) has a radical polymerizable group selected from the group consisting of an acryloyl group, a methacryloyl group, an allyl group, a methallyl group, a vinyl group, and an isopropenyl group.

5. The resin composition according to any one of claims 1 to 4, wherein the content of the component (B) is 0.001 mass% or more and 20 mass% or less, when the total amount of non-volatile components in the resin composition is 100 mass%.

6. The resin composition according to any one of claims 1 to 5, wherein the component (E) comprises an active ester-based curing agent.

7. The resin composition according to any one of claims 1 to 6, wherein the component (E) comprises a phenol-based curing agent.

8. The resin composition according to any one of claims 1 to 7, wherein the cured product of the resin composition has a dielectric constant (Dk) of 3.5 or less when measured at 5.8 GHz and 23°C.

9. The resin composition according to any one of claims 1 to 8, wherein the dielectric loss tangent (Df) of a cured product of the resin composition is 0.005 or less when measured at 5.8 GHz and 23 ° C.

10. The resin composition according to any one of claims 1 to 9, wherein the coefficient of linear thermal expansion (CTE) of a cured product of the resin composition is 1 ppm / K or more and 25 ppm / K or less in the range of 25 ° C to 150 ° C.

11. The resin composition according to any one of claims 1 to 10, wherein the glass transition temperature (Tg) of a cured product of the resin composition is 150°C or higher and 162°C or lower.

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

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

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

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

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

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