Resin composition

Abstract

To provide a resin composition capable of reducing occurrence of crack after desmear treatment and also capable of obtaining a cured matter whose dissipation factor (Df) is reduced.SOLUTION: A resin composition contains (A) a compound having a terminal carbon-carbon double bond and a cyclopentadiene ring, (B) an epoxy resin and (C) an active ester compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition containing an epoxy resin, and further to a cured product, a sheet-like laminate material, a resin sheet, a 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 the build-up method, the insulating layers are generally formed by curing a resin composition.

[0003] Since printed wiring boards are generally exposed to a wide range of temperature environments, from low-temperature environments such as room temperature to high-temperature environments such as reflow, if the dimensional stability is poor, the resin material of the insulating layer will repeatedly expand and contract, and the resulting distortion will cause cracks. In addition, in recent years, there has been a demand for further improvement in the dielectric properties of the insulating layer, such as the dielectric loss tangent.

[0004] To date, compounds having a terminal carbon-carbon double bond and a cyclopentadiene ring have been known (Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent No. 9,902,695 Summary of the Invention [Problem to be solved by the invention]

[0006] When an active ester compound is used as a curing agent for an epoxy resin composition for forming an insulating layer instead of a general phenol-based curing agent, the dielectric tangent can be further reduced, but cracks tend to easily occur after a desmear treatment.

[0007] An object of the present invention is to provide a resin composition which can suppress the occurrence of cracks after a desmear treatment and give a cured product having a low dielectric loss tangent (Df). [Means for solving the problem]

[0008] Means for Solving the Problems of the Invention The present inventors conducted intensive studies in order to achieve the objects of the present invention, and unexpectedly found that by using a resin composition containing (A) a compound having a terminal carbon-carbon double bond and a cyclopentadiene ring, (B) an epoxy resin, and (C) an active ester compound, it is possible to suppress the occurrence of cracks after a desmear treatment and to obtain a cured product having a low dielectric loss tangent (Df), thereby completing the present invention.

[0009] That is, the present invention includes the following. [1] A resin composition comprising: (A) a compound having a terminal carbon-carbon double bond and a cyclopentadiene ring, (B) an epoxy resin, and (C) an active ester compound. [2] The component (A) is represented by the formula (A1):

[0010] [ka]

[0011] [In the formula, R each independently represents a substituent, and at least one R is a group having a terminal carbon-carbon double bond; Each X independently represents an organic group. Each a independently represents 0, 1, 2, 3, or 4, and the sum of the n+1 a's is 1 or more; n represents an integer of 0 or 1 or more. The resin composition according to the above [1], comprising a compound represented by the following formula: [3] The component (A) is represented by the formula (A2):

[0012] [ka]

[0013] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrogen atom or an alkyl group, R 4 each independently represents a substituent, X 1 each independently represents a hydrocarbon group, Each Y independently represents a single bond, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; Z represents a single bond or an arylene group which may be substituted with an alkyl group; b's each independently represent 0, 1, 2, or 3; n represents 0 or an integer of 1 or more; Each m independently represents 0, 1, 2, or 3. The resin composition according to the above [1] or [2], comprising a compound represented by the following formula: [4] The resin composition according to the above [2] or [3], wherein n is 0. [5] The resin composition according to any one of the above [1] to [4], wherein the content of the component (A) is 20 mass % or less, based on 100 mass % of the non-volatile components in the resin composition. [6] The resin composition according to any one of the above [1] to [5], wherein the content of the component (A) is 0.5 mass% or more, based on 100 mass% of the non-volatile components in the resin composition. [7] The resin composition according to any one of the above [1] to [6], wherein a mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 0.05 to 3. [8] The resin composition according to any one of the above [1] to [7], wherein a mass ratio of the component (A) to the component (C) (component (A) / component (C)) is 0.05 to 3. [9] The resin composition according to any one of the above [1] to [8], further comprising (D) an inorganic filler.

[10] The resin composition according to the above [9], wherein the component (D) is silica.

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

[10] above, wherein the content of the (D) component is 40 mass% or more, based on 100 mass% of the non-volatile components in the resin composition.

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

[11] , wherein a dielectric loss tangent (Df) of a cured product of the resin composition is 0.0032 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 a 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.

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

[13] above.

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

[13] .

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

[13] above.

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

[13] above.

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

[17] above. Effect of the Invention

[0014] According to the resin composition of the present invention, it is possible to suppress the occurrence of cracks after a desmear treatment and to obtain a cured product having a low dielectric loss tangent (Df). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present invention will be described in detail below with reference to preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be modified and implemented as desired without departing from the scope of the claims of the present invention and their equivalents.

[0016] <Resin composition> The resin composition of the present invention contains (A) a compound having a terminal carbon-carbon double bond and a cyclopentadiene ring, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, it is possible to suppress the occurrence of cracks after a desmear treatment and to obtain a cured product having a low dielectric loss tangent (Df).

[0017] The resin composition of the present invention may further contain optional components in addition to (A) the compound having a terminal carbon-carbon double bond and a cyclopentadiene ring, (B) the epoxy resin, and (C) the active ester compound, such as (D) an inorganic filler, (E) a radical polymerizable compound, (F) a curing accelerator, (G) other additives, and (H) an organic solvent.

[0018] Each component contained in the resin composition will be described in detail below.

[0019] <(A) Compound Having a Terminal Carbon-Carbon Double Bond and a Cyclopentadiene Ring> The resin composition of the present invention contains (A) a compound having a terminal carbon-carbon double bond (CH2=C<) and a cyclopentadiene ring (hereinafter sometimes referred to as "cyclopentadiene compound") as a non-volatile component. The (A) cyclopentadiene compound is, in other words, a compound having a cyclopentadiene ring to which a group having a terminal carbon-carbon double bond is bonded. The (A) cyclopentadiene compound has one or more (in one embodiment, preferably one) groups having a terminal carbon-carbon double bond in one molecule. The (A) cyclopentadiene compound has one or more (in one embodiment, preferably one or two, more preferably one) cyclopentadiene ring in one molecule.

[0020] (A) The cyclopentadiene compound, in one embodiment, preferably has the formula (A1):

[0021] [ka]

[0022] [In the formula, R each independently represents a substituent, and at least one R is a group having a terminal carbon-carbon double bond; Each X independently represents an organic group. Each a independently represents 0, 1, 2, 3, or 4, and the sum of the n+1 a's is 1 or more; n represents an integer of 0 or 1 or more. The compound includes a compound represented by the formula:

[0023] Each R independently represents a substituent, and at least one R is a group having a terminal carbon-carbon double bond.

[0024] In this specification, the term "group having a terminal carbon-carbon double bond" is not particularly limited, but in one embodiment, for example, is a monovalent group consisting of two or more (e.g., 2 to 100, preferably 2 to 50, particularly preferably 2 to 20) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms having one or more terminal carbon-carbon double bonds, and may have a straight-chain structure, a branched-chain structure, and / or a cyclic structure. The group may be either a group not containing an aromatic ring or a group containing an aromatic ring, but in one embodiment, it is preferable that the group is a group containing an aromatic ring.

[0025] The aromatic ring means a ring that follows the Huckel rule, in which the number of electrons contained in the π electron system on the ring is 4p+2 (p is a natural number). The aromatic ring may be an aromatic carbocycle having only carbon atoms as ring-constituting atoms, or an aromatic heterocycle having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms in addition to carbon atoms as ring-constituting atoms, but in one embodiment, it is preferably an aromatic carbocycle. 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. Suitable specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, and more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

[0026] The "group having a terminal carbon-carbon double bond" is preferably represented by the formula (a1):

[0027] [ka]

[0028] [In the formula, R 1 , R 2 and R 3 each independently represents a hydrogen atom or an alkyl group, Each Y independently represents a single bond, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; Z represents a single bond or an arylene group which may be substituted with an alkyl group; m represents 0, 1, 2, or 3; * indicates binding site.] and particularly preferably a group represented by formula (a2):

[0029] [ka]

[0030] [In the formula, R 5 each independently represents an alkyl group, c represents 0, 1, or 2; * indicates the binding site; Other symbols are as above.] It is a group represented by the following formula:

[0031] R 1 and R 2 each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0032] 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, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 2,4-dimethylcyclohexyl group, a 2,2,4-trimethylcyclohexyl group, a cyclopentylmethyl group, and a cyclohexylmethyl group.

[0033] R 3 represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0034] Each Y is independently a single bond, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-. In one embodiment, Y is preferably a single bond or -O-, and particularly preferably a single bond.

[0035] Z represents a single bond or an arylene group which may be substituted with an alkyl group, and in one embodiment, is preferably an arylene group which may be substituted with an alkyl group, more preferably a phenylene group which may be substituted with an alkyl group (1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group), and particularly preferably an (unsubstituted) phenylene group.

[0036] The arylene group refers to a divalent aromatic hydrocarbon group obtained by removing two hydrogen atoms from an aromatic carbon ring. Unless otherwise specified, the arylene group is preferably an arylene group having 6 to 14 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include a phenylene group (1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group), a naphthylene group (1,2-naphthylene group, 1,3-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 1,8-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group), and the like.

[0037] m represents 0, 1, 2, or 3, and in one embodiment, is preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 1. R 5 each independently represents an alkyl group, and in one embodiment, is preferably a methyl group. c represents 0, 1, or 2, and in one embodiment, is preferably 0 or 1, and particularly preferably 0.

[0038] In the present specification, the term "substituent" is not particularly limited, but in one embodiment, for example, it is a monovalent group consisting of one or more (for example, 1 to 100, preferably 1 to 50, particularly preferably 1 to 20) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, which may have a straight-chain structure, a branched-chain 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 the substituent include a "group having a terminal carbon-carbon double bond" (preferably a group represented by formula (a1), more preferably a group represented by formula (a2)), as well as monovalent substituents such as an alkyl group, an aryl group, an aryl-alkyl group (an alkyl group substituted with an aryl group), an alkyl-aryl group (an aryl group substituted with an alkyl group), an alkyl-oxy group, an aryl-oxy group, an alkyl-carbonyl group, an aryl-carbonyl group, an alkyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, and an aryl-carbonyl-oxy group.

[0039] The aryl group refers to a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbon ring. Unless otherwise specified, the aryl group is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0040] Each X independently represents an organic group, and in one embodiment, preferably represents a hydrocarbon group, more preferably represents an alkylene group.

[0041] In this specification, the term "organic group" is not particularly limited, but in one embodiment, it is a divalent group consisting of one or more (e.g., 1 to 100, preferably 1 to 50, particularly preferably 1 to 20) skeletal atoms selected from, for example, carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, and may have a straight-chain structure, a branched-chain 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.

[0042] In the present specification, the term "hydrocarbon group" refers to a divalent group having one or more (for example, 1 to 100, preferably 1 to 50, particularly preferably 1 to 20) carbon atoms as the skeleton atom of an organic group, which may have a straight chain structure, a branched chain 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 the "hydrocarbon group" include an alkylene group, an arylene group, an alkylene-arylene group, an arylene-arylene group, an arylene-alkylene-arylene group, an alkylene-arylene-alkylene group, and an alkylene-arylene-arylene-alkylene group.

[0043] The alkylene group refers to a linear, branched, and / or cyclic divalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkylene group is preferably an alkylene group having 1 to 14 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; and branched alkylene groups such as ethylidene, propylidene, isopropylidene, ethylmethylmethylene, and diethylmethylene.

[0044] Each a independently represents 0, 1, 2, 3, or 4, and the sum of n+1 a's is 1 or more. In one embodiment, each a independently represents preferably 1, 2, 3, or 4, more preferably 1, 2, or 3, and even more preferably 1 or 2. n represents 0 or an integer of 1 or more, and in one embodiment, preferably 0, or 1 to 100, more preferably 0, 1 to 10, even more preferably 0, 1, or 2, and particularly preferably 0.

[0045] (A) In one embodiment, the cyclopentadiene compound is more preferably represented by formula (A2):

[0046] [ka]

[0047] [In the formula, R 4 each independently represents a substituent, X 1 each independently represents a hydrocarbon group, b's each independently represent 0, 1, 2, or 3; Other symbols are as above.] The compound includes a compound represented by the formula:

[0048] R 4 Each of X independently represents a substituent, and in one embodiment, X is preferably a group represented by formula (a1), an alkyl group, or an aryl group, and more preferably a group represented by formula (a1). 1 Each independently represents a hydrocarbon group, and in one embodiment, is preferably an alkylene group. Each b independently represents 0, 1, 2, or 3, and in one embodiment, is preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 0.

[0049] In one embodiment, the cyclopentadiene compound (A) is more preferably represented by formula (A3):

[0050] [ka]

[0051] [In the formula, each symbol is as defined above.] The compound includes a compound represented by the formula:

[0052] Specific examples of the (A) cyclopentadiene compound include those represented by the formulas (A-1) to (A-12):

[0053] [ka]

[0054] [where n 0 represents an integer of 2 or more (preferably 2 to 100, more preferably 2 to 10), and n 1 and n 2 each independently represents an integer of 1 or more (preferably 1 to 50, more preferably 1 to 5). In one embodiment, among them, the compound represented by formula (A-2) is particularly preferred.

[0055] The molecular weight of the (A) cyclopentadiene compound is preferably 10,000 or less, more preferably 5,000 or less, further preferably 1,000 or less, and particularly preferably 500 or less. The lower limit can be, for example, 100 or more.

[0056] An example of a commercially available product of the (A) cyclopentadiene compound is "SLK-250" manufactured by Shin-Etsu Chemical Co., Ltd.

[0057] The content of the (A) cyclopentadiene 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 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 6% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. The lower limit of the content of the (A) cyclopentadiene compound in the resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, and particularly preferably 3% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass.

[0058] <(B) Epoxy resin> The resin composition of the present invention contains, as a non-volatile component, an epoxy resin (B). The epoxy resin (B) is a curable resin having an epoxy group.

[0059] (B) Epoxy resins include, for example, 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, and the like. Examples of the epoxy resins include 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, phenolphthalimidine type epoxy resins, phenolphthalein type epoxy resins, etc. (B) The epoxy resins may be used alone or in combination of two or more.

[0060] The resin composition preferably contains, as the (B) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile components of the (B) epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0061] 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 a liquid epoxy resin as the epoxy resin, or may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. The resin composition of the present invention preferably contains a solid epoxy resin as the epoxy resin.

[0062] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0063] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferred.

[0064] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "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; "EP-3950L" and "EP-3980S" ( glycidylamine type epoxy resin); ADEKA's "EP-4088S" (dicyclopentadiene type epoxy resin); Nippon Steel Chemical & Material Chemical's "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase Chemtex's "EX-721" (glycidyl ester type epoxy resin); Daicel's "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton); Daicel's "PB-3600", Nippon Soda's "JP-100" and "JP-200" (epoxy resin having a butadiene structure); Nippon Steel Chemical & Material's "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin), etc. These may be used alone or in combination of two or more types.

[0065] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0066] Preferred solid epoxy resins include bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, phenol aralkyl type epoxy resins, tetraphenylethane type epoxy resins, phenolphthalimidine type epoxy resins, and phenolphthalein type epoxy resins.

[0067] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy resins) manufactured by DIC Corporation; and "EXA-7311" manufactured by DIC Corporation. , "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN475V", "ESN4 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", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "Y Examples of epoxy resins include "X7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical; and "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.These may be used alone or in combination of two or more.

[0068] The epoxy equivalent of the (B) 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 group. This epoxy equivalent can be measured according to JIS K7236.

[0069] The weight average molecular weight (Mw) of the epoxy resin (B) is preferably from 100 to 5,000, more preferably from 250 to 3,000, and further preferably from 400 to 1500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0070] The content of the epoxy resin (B) 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 12% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. The lower limit of the content of the epoxy resin (B) in the resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass.

[0071] The mass ratio of the cyclopentadiene compound (A) to the epoxy resin (B) in the resin composition (component (A) / component (B)) is not particularly limited, but is preferably 0.01 or more, more preferably 0.05 or more, and particularly preferably 0.1 or more. The upper limit of the mass ratio of the cyclopentadiene compound (A) to the epoxy resin (B) in the resin composition (component (A) / component (B)) is not particularly limited, but is preferably 5 or less, more preferably 3 or less, and particularly preferably 1 or less.

[0072] <(C) Active ester compound> The resin composition of the present invention contains an active ester compound (C) as a non-volatile component. The active ester compound (C) may be used alone or in combination of two or more at any ratio. The active ester compound (C) may function as an epoxy resin curing agent that reacts with the epoxy resin (B) to cure the resin.

[0073] As the (C) active ester compound, generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used. 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. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, phenol novolac, etc. Here, the term "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0074] Specifically, the (C) active ester compound is preferably a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, or an active ester compound containing a benzoylated product of phenol novolac, and more preferably at least one selected from a dicyclopentadiene type active ester compound and a naphthalene type active ester compound, and even more preferably a dicyclopentadiene type active ester compound. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferred.

[0075] (C) Commercially available active ester compounds include, as active ester compounds containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); as active ester compounds containing a naphthalene structure, "HP-B-8151-62T", "EXB-8100L-65T", "EXB-815060T", "EXB-815 0-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", and "EXB-8" (manufactured by DIC Corporation); an active ester compound containing phosphorus, "EXB9401" (manufactured by DIC Corporation), an active ester compound which is an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester compound which is a benzoylated product of phenol novolac, "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and an active ester compound containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Corporation), etc.

[0076] The active ester group equivalent of the (C) active ester compound is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and further preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester compound per equivalent of the active ester group.

[0077] The content of the (C) active ester compound in the resin composition is not particularly limited, but is preferably 0.1% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. It is more preferably 1 mass% or more, even more preferably 5 mass% or more, even more preferably 10 mass% or more, and particularly preferably 12 mass% or more. The upper limit of the content of the (C) active ester compound in the resin composition is not particularly limited, but is preferably 50 mass% or less, more preferably 40 mass% or less, even more preferably 30 mass% or less, even more preferably 25 mass% or less, and particularly preferably 20 mass% or less, when the non-volatile components in the resin composition are 100 mass%.

[0078] The mass ratio of the cyclopentadiene compound (A) to the active ester compound (C) in the resin composition (component (A) / component (C)) is not particularly limited, but is preferably 0.01 or more, more preferably 0.05 or more, and particularly preferably 0.1 or more. The upper limit of the mass ratio of the cyclopentadiene compound (A) to the active ester compound (C) in the resin composition (component (A) / component (C)) is not particularly limited, but is preferably 5 or less, more preferably 3 or less, and particularly preferably 1 or less.

[0079] <(D) Inorganic filler> The resin composition of the present invention may contain an inorganic filler (D) as an optional non-volatile component. The inorganic filler (D) is contained in the resin composition in the form of particles.

[0080] (D) An inorganic compound is used as the material of the inorganic filler. (D) Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, spherical silica is preferable as the silica. The (D) inorganic filler may be used alone or in combination of two or more kinds in any ratio.

[0081] (D) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Company; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; and "DAW-03" and "FB-105FD" manufactured by Denka Company, Ltd.

[0082] The average particle size of the (D) inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less. The lower limit of the average particle size of the (D) inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. The average particle size of the (D) inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering type particle size distribution measuring device, and the median diameter is taken as the average particle size. The measurement sample can be prepared by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device with blue and red light source wavelengths, and the particle size distribution of the inorganic filler on a volume basis was measured using a flow cell method, and the average particle size was calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction type particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

[0083] The specific surface area of ​​the (D) inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 The upper limit of the specific surface area of ​​the inorganic filler (D) 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 the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method.

[0084] (D) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. The surface treatment agent may be used alone or in any combination of two or more.

[0085] 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).

[0086] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably 0.2% to 3% by mass, and even more preferably 0.3% to 2% by mass.

[0087] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable.2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, it is more preferable that the melt viscosity is 1.0 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0088] (D) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, the "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used.

[0089] The content of the (D) inorganic filler in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100 mass%, it may be preferably 90 mass% or less, more preferably 85 mass% or less, even more preferably 80 mass% or less, and particularly preferably 75 mass% or less. The lower limit of the content of the (D) inorganic filler in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100 mass%, it may be, for example, 0 mass% or more, 1 mass% or more, 10 mass% or more, preferably 20 mass% or more, 30 mass% or more, more preferably 40 mass% or more, 50 mass% or more, even more preferably 50 mass% or more, 55 mass% or more, even more preferably 60 mass% or more, 65 mass% or more, particularly preferably 68 mass% or more, 70 mass% or more.

[0090] The mass ratio of the cyclopentadiene compound (A) to the inorganic filler (D) in the resin composition (component (A) / component (D)) is not particularly limited, but is preferably 0.005 or more, more preferably 0.01 or more, and particularly preferably 0.05 or more. The upper limit of the mass ratio of the cyclopentadiene compound (A) to the inorganic filler (D) in the resin composition (component (A) / component (D)) is not particularly limited, but is preferably 1 or less, more preferably 0.5 or less, and particularly preferably 0.1 or less.

[0091] <(E) Radical Polymerizable Compound> The resin composition of the present invention may contain (E) a radical polymerizable compound as an optional non-volatile component. The (E) radical polymerizable compound described here is a component that does not fall under (A) a cyclopentadiene compound. The (E) radical polymerizable compound may be used alone or in any combination of two or more kinds.

[0092] In one embodiment, the radical polymerizable compound (E) is a radical polymerizable compound having an ethylenically unsaturated bond. The radical polymerizable compound (E) is not particularly limited, but may have a radical polymerizable group such as an unsaturated hydrocarbon group such as an allyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a 2-vinylphenyl group, a 3-vinylphenyl group, or a 4-vinylphenyl group; an α,β-unsaturated carbonyl group such as an acryloyl group, a methacryloyl group, or a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group). The radical polymerizable compound (E) preferably has two or more radical polymerizable groups.

[0093] In the first embodiment, the radical polymerizable compound (E) preferably contains a thermoplastic resin having a vinylphenyl group and / or a (meth)acryloyl group. The (meth)acryloyl group means an acryloyl group or a methacryloyl group. The vinylphenyl group includes a 2-vinylphenyl group, a 3-vinylphenyl group, a 4-vinylphenyl group, or a group in which the aromatic carbon atom of each of these groups is further substituted with one or more alkyl groups. It is preferable that each molecule contains two or more vinylphenyl groups and / or (meth)acryloyl groups. Examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polystyrene resin, a polyethylene resin, a polypropylene resin, a polybutadiene resin, a polyimide resin, a polyamideimide resin, a polyetherimide resin, a polysulfone resin, a polyethersulfone resin, a polyphenylene ether resin, a polyetheretherketone resin, and a polyester resin. In the embodiment, the radical polymerizable compound (E) contains a modified resin having a vinylphenyl group and / or a (meth)acryloyl group of these resins.

[0094] In the first embodiment, the (E) radically polymerizable compound more preferably contains a resin selected from a modified polyphenylene ether resin having a vinylphenyl group and / or a (meth)acryloyl group (hereinafter referred to as a "modified polyphenylene ether resin"), and a modified polystyrene resin having a vinylphenyl group and / or a (meth)acryloyl group (hereinafter referred to as a "modified polystyrene resin").

[0095] A suitable example of the modified polyphenylene ether resin is a compound represented by the formula (E-1):

[0096] [ka]

[0097] [In the formula, R 11 and R 12 each independently represents an alkyl group; R 13 , R 14 , R 21 , R22 , R 23 and R 24 each independently represents a hydrogen atom or an alkyl group; R 31 and R 32 each independently represents a vinylphenyl group or a (meth)acryloyl group; Y 1 is a single bond, -C(R y )2-, -O-, -CO-, -S-, -SO-, or -SO2-; R y each independently represents a hydrogen atom or an alkyl group; Y 2 represents a single bond or an alkylene group; p represents 0 or 1; and q and r each independently represent an integer of 1 or more. The q units and the r units may be the same or different for each unit.

[0098] R 11 and R 12 R each independently represents an alkyl group, and in one embodiment, is preferably a methyl group. 13 and R 14 R each independently represents a hydrogen atom or an alkyl group, and in one embodiment, R is preferably a hydrogen atom. 21 and R 22 R each independently represents a hydrogen atom or an alkyl group, and in one embodiment, R is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. 23 and R 24 each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group.

[0099] R 31 and R 32 each independently represents a vinylphenyl group or a (meth)acryloyl group; Y 2 represents a single bond or an alkylene group. In one embodiment, preferably, R 31 and R 32 is a vinyl phenyl group, and Y 2is an alkylene group (particularly preferably a methylene group), or R 31 and R 32 is a (meth)acryloyl group, and Y 2 is a single bond.

[0100] Y 1 is a single bond, -C(R y )2-, -O-, -CO-, -S-, -SO-, or -SO2-, and in one embodiment, preferably a single bond, -C(R y )2- or -O-. y each independently represents a hydrogen atom or an alkyl group, and in one embodiment, preferably a hydrogen atom or a methyl group. p represents 0 or 1, and in one embodiment, preferably 1. q and r each independently represent an integer of 1 or more, and in one embodiment, preferably an integer of 1 to 200, and more preferably an integer of 1 to 100.

[0101] Commercially available modified polyphenylene ether resins include, for example, "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Company, Inc.; and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether resins) manufactured by SABIC Innovative Plastics.

[0102] A suitable example of the modified polystyrene resin is a polystyrene resin represented by the formula (E-2a):

[0103] [ka]

[0104] [In the formula, R 41 , R 42 and R 43 each independently represents a hydrogen atom or an alkyl group; R 44 each independently represents an alkyl group; and s represents an integer of 0 to 3. and a repeating unit represented by formula (E-2b):

[0105] [ka]

[0106] [In the formula, R 51 , R 52 and R 53 each independently represents a hydrogen atom or an alkyl group; R 54 each independently represents an alkyl group; and t represents an integer of 0 to 3. The repeating unit of formula (E-2a) and the repeating unit of formula (E-2b) contained in one molecule of the modified polystyrene resin may be the same or different units.

[0107] R 41 , R 42 , R 43 , R 51 , R 52 and R 53 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 hydrogen atom. 44 and R 54 each independently represents an alkyl group, and in one embodiment, is preferably an ethyl group or a methyl group. s represents an integer of 0 to 3, and in one embodiment, is preferably 0 or 1, and more preferably 0. t represents an integer of 0 to 3, and in one embodiment, is preferably 0 or 1.

[0108] The molar content of the repeating unit of formula (E-2a) is preferably 8 mol % to 54 mol % when the total of the repeating units of formula (E-2a) and formula (E-2b) is taken as 100 mol %.

[0109] Commercially available modified polystyrene resins include, for example, "ODV-XET(X03)", "ODV-XET(X04)", and "ODV-XET(X05)" (styrene-divinylbenzene copolymers) manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0110] In the second embodiment, the radical polymerizable compound (E) is preferably represented by the formula (E-3):

[0111] [ka]

[0112] [In the formula, R 6 each independently represents a hydrogen atom or an alkyl group; ring A, ring B and ring C each independently represent an aromatic ring which may have a substituent; Z 1 are each independently a single bond, -C(R z )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-; R z each independently represents a hydrogen atom or an alkyl group; each x independently represents an integer of 1 or more; each y independently represents 0 or 1; and each z independently represents 0, 1, 2, or 3. The maleimide compound according to the second embodiment includes a maleimide compound represented by the following formula: The x units and the z units may be the same or different for each unit. The maleimide compound according to the second embodiment may be used alone or in combination of two or more types at any ratio.

[0113] R 6 are each independently a hydrogen atom or an alkyl group, and in one embodiment, are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. Ring A, ring B, and ring C are each independently an aromatic ring which may have a substituent, and in one embodiment, are preferably a benzene ring which may have a substituent, more preferably a benzene ring which may be substituted with a group selected from an alkyl group and an aryl group, and particularly preferably an (unsubstituted) benzene ring.

[0114] Z 1 are each independently a single bond, -C(R z )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-; in one embodiment, preferably a single bond, -C(R z )2- or -O-, more preferably a single bond or -C(R z )2-, and particularly preferably a single bond. z each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group.

[0115] Each x represents an integer of 1 or more, and preferably an integer of 1 to 10. Each y independently represents 0 or 1, and preferably 1. Each z independently represents 0, 1, 2 or 3, and preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 1.

[0116] Commercially available products of the radically polymerizable compound (E) in the second embodiment include, for example, "MIR-3000-70MT" and "MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd.

[0117] In the third embodiment, the radical polymerizable compound (E) is preferably represented by the formula (E-4):

[0118] [ka]

[0119] [In the formula, R 7 each independently represents an alkyl group; ring D and ring E each independently represent an aromatic ring which may have a substituent; and u represents an integer of 1 or greater. The maleimide compounds according to the third embodiment include those represented by the following formula: The u units may be the same or different for each unit. The maleimide compounds according to the third embodiment may be used singly or in any combination of two or more kinds at any ratio.

[0120] R 7 each independently represents an alkyl group, and in one embodiment, preferably a methyl group. Each ring D independently represents an aromatic ring which may have a substituent, and in one embodiment, preferably a benzene ring which may have a substituent, more preferably a benzene ring which may be substituted with a group selected from alkyl groups, and even more preferably a benzene ring substituted with a group selected from alkyl groups. Each ring E independently represents an aromatic ring which may have a substituent, and in one embodiment, preferably a benzene ring which may have a substituent, more preferably a benzene ring which may be substituted with a group selected from alkyl groups, and even more preferably a (unsubstituted) benzene ring. u represents an integer of 1 or more, and preferably an integer of 1 to 20.

[0121] The radical polymerizable compound (E) in the third embodiment can be produced, for example, by using the method described in the Japan Institute of Invention and Innovation's Technical Journal No. 2020-500211 or a method equivalent thereto.

[0122] The (E) radical polymerizable compound may contain any one of the suitable thermoplastic resins contained in the first embodiment, the suitable maleimide compounds contained in the second embodiment, and the suitable maleimide compounds contained in the third embodiment alone, or may contain a combination of two or more of these in any ratio.

[0123] The radical polymerizable group equivalent of the (E) radical polymerizable compound is preferably 250 g / eq. to 2500 g / eq., more preferably 300 g / eq. to 1500 g / eq. The (E) radical polymerizable compound's radical polymerizable group equivalent represents the mass of the resin per equivalent of the radical polymerizable group.

[0124] The weight average molecular weight (Mw) of the radically polymerizable compound (E) is preferably from 500 to 40,000, more preferably from 500 to 10,000, and particularly preferably from 500 to 7000. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0125] The content of the radical polymerizable compound (E) 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 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. The lower limit of the content of the radical polymerizable compound (E) in the resin composition is not particularly limited, but is, for example, 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass.

[0126] <(F) Curing accelerator> The resin composition of the present invention may contain a curing accelerator (F) as an optional non-volatile component. The curing accelerator (F) functions as a curing catalyst that accelerates the curing of the epoxy resin (B).

[0127] Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Among them, imidazole-based curing accelerators are preferred from the viewpoint of improving crosslinking properties. (F) Curing accelerators may be used alone or in combination of two or more.

[0128] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium acetate, tetrabutyl phosphonium decanoate, tetrabutyl phosphonium laurate, bis(tetrabutyl phosphonium)pyromellitate, tetrabutyl phosphonium hydrogenhexahydrophthalate, tetrabutyl phosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butyldimethylphosphonium tetraphenylborate; methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, propyl triphenyl phosphonium bromide, butyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium chloride, tetraphenyl phosphonium bromide, p-tolyl triphenyl phosphonium tetra-p-tolylborate, tetraphenyl phosphonium bromide, and the like. aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine Examples of aromatic phosphines include tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0129] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. aromatic dimethylureas such as butylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0130] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0131] Examples of the imidazole-based curing accelerator 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. Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct imidazole compounds such as 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, as well as adducts of imidazole compounds and epoxy resins.

[0132] As the imidazole-based curing accelerator, commercially available products may be used, for example, "1B2PZ", "2MZA-PW", and "2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0133] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0134] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0135] As the amine-based curing accelerator, a commercially available product may be used, for example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0136] The content of the (F) curing accelerator in the resin composition is not particularly limited, but is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 2% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. The lower limit of the content of the (F) curing accelerator in the resin composition is not particularly limited, but may be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, etc., when the non-volatile components in the resin composition are taken as 100% by mass.

[0137] <(G) Other Additives> The resin composition of the present invention may further contain any additive as a non-volatile component. 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; phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol curing agents. epoxy resin curing agents other than active ester compounds; curing accelerators such as phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; organic fillers such as rubber particles; organic copper compounds, organic zinc compounds, and organic cobalt compounds organic metal compounds such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and other colorants; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, and other leveling agents; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; benzotriazole-based ultraviolet absorbers, etc. ultraviolet absorbers; adhesion improvers such as urea silane; adhesion promoters such as triazole-based adhesion promoters, tetrazole-based adhesion promoters, and triazine-based adhesion promoters; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide);Examples of the additives include dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers. (G) Other additives may be used alone or in combination of two or more kinds at any ratio. The content of (G) other additives can be appropriately determined by those skilled in the art.

[0138] <(H) Organic Solvent> The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the non-volatile components described above. As the (H) organic solvent, a known one can be appropriately used, and the type is not particularly limited. As the (H) organic solvent, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole, etc.; alcohol-based solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methoxypropionic acid, etc. Examples of suitable organic solvents include ether ester 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 (butylcarbitol); 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. (H) The organic solvent may be used alone or in combination of two or more in any ratio.

[0139] In one embodiment, the content of the (H) organic solvent is not particularly limited, but when all components in the resin composition are taken as 100 mass%, it can be, for example, 60 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, etc.

[0140] <Method of producing resin composition> The resin composition of the present invention can be produced, for example, by adding (A) a cyclopentadiene compound, (B) an epoxy resin, (C) an active ester compound, if necessary (D) an inorganic filler, if necessary (E) a radical polymerizable compound, if necessary (F) a curing accelerator, if necessary (G) other additives, if necessary, and if necessary (H) an organic solvent in any preparation vessel in any order and / or all at once and mixing them. In addition, 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. In addition, during or after the process of adding and mixing, the resin composition may be stirred or shaken using a stirring device or shaking device such as a mixer to disperse it uniformly. In addition, degassing may be performed under low pressure conditions such as under vacuum at the same time as stirring or shaking.

[0141] <Characteristics of resin composition> The resin composition of the present invention contains (A) a cyclopentadiene compound, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, it is possible to suppress the occurrence of cracks after a desmear treatment and to obtain a cured product having a low dielectric loss tangent (Df).

[0142] The cured product of the resin composition of the present invention can suppress the occurrence of cracks after desmearing. Thus, in one embodiment, after producing a circuit board and subjecting it to desmearing as in the following Test Example 2, when 100 copper pads of the circuit board are observed, the number of cracks may be preferably 10 or less.

[0143] The cured product of the resin composition of the present invention may be characterized by a low dielectric loss tangent (Df). Thus, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition measured at 5.8 GHz and 23° C. as in the following Test Example 1 may be preferably 0.0200 or less, 0.0100 or less, more preferably 0.0090 or less, 0.0080 or less, 0.0070 or less, even more preferably 0.0060 or less, 0.0050 or less, 0.0040 or less, and particularly preferably 0.0035 or less, 0.0032 or less, 0.0030 or less.

[0144] In one embodiment, the cured product of the resin composition of the present invention may be characterized by a low dielectric constant (Dk). Thus, in one embodiment, the dielectric constant (Dk) of the cured product of the resin composition, as measured at 5.8 GHz and 23° C. as in the following Test Example 1, may be preferably 6.0 or less, more preferably 5.0 or less, even more preferably 4.0 or less, even more preferably 3.5 or less, and particularly preferably 3.3 or less.

[0145] <Applications of resin composition> The resin composition of the present invention can be suitably used as a resin composition for insulating purposes, 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) for forming a conductor layer (including a rewiring layer) formed on an insulating layer. In addition, in a printed wiring board described later, it can 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). The resin composition of the present invention can also be used in a wide range of applications requiring a resin composition, such as a resin sheet, a sheet-like laminate material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin.

[0146] In addition, 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 sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer. (1) A step of laminating a temporary fixing film onto a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A process of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0147] 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.

[0148] <Sheet-type laminated material> The resin composition of the present invention can be used by coating in the form of a varnish, but from an industrial perspective, it is generally preferred to use the resin composition in the form of a sheet-like laminate material containing the resin composition.

[0149] As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

[0150] 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.

[0151] The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of making the printed wiring board thinner and being able to provide a cured product with excellent insulation even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, 10 μm or more, etc.

[0152] 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.

[0153] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0154] When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0155] The surface of the support to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0156] In addition, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the support with a release layer may be, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support with a release layer may be a commercially available product, 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 "Unipeel" manufactured by Unitika Limited, which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

[0157] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the total thickness of the support with a release layer is in the above range.

[0158] In one embodiment, the resin sheet may further include an optional layer as necessary. For example, such an optional layer may be a protective film equivalent to the support provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dirt and the like to the surface of the resin composition layer and scratches can be suppressed.

[0159] The resin sheet can be produced, for example, by preparing a liquid resin composition as is or a resin varnish by dissolving the resin composition in an organic solvent, applying this onto a support using a die coater or the like, and then drying to form a resin composition layer.

[0160] The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of two or more kinds.

[0161] Drying may be performed by a known method such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer becomes 10% 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 or resin varnish, for example, when a resin composition or resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0162] 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.

[0163] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

[0164] The sheet-like fiber substrate used for the prepreg is not particularly limited, and can be a substrate commonly used for prepreg, such as glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, etc. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber substrate is not particularly limited. It is usually 10 μm or more.

[0165] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0166] The thickness of the prepreg may be in the same range as that of the resin composition layer in the above-mentioned resin sheet.

[0167] 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).

[0168] <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.

[0169] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate such that a resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., heat curing) the resin composition layer to form an insulating layer.

[0170] The "inner layer substrate" used in step (I) is a member that becomes the substrate of the printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be called an "inner layer circuit substrate". In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be formed during the manufacture of a printed wiring board is also included in the "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0171] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). It is preferable to press the thermocompression member not directly onto the resin sheet, but via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the inner layer substrate.

[0172] The lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination may be performed under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0173] The lamination can be performed by a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch type vacuum pressure laminator.

[0174] After lamination, the laminated resin sheet may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. The lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0175] The support may be removed between step (I) and step (II) or after step (II).

[0176] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions that are usually adopted when forming an insulating layer for a printed wiring board may be used.

[0177] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, etc., but in one embodiment, the curing temperature is preferably 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.

[0178] Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50° C. to 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.

[0179] In manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art for use in manufacturing printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0180] In another embodiment, the printed wiring board of the present invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as when a resin sheet is used.

[0181] Step (III) is a step of drilling holes in the insulating layer, which allows holes such as via holes and through holes to be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined depending on the design of the printed wiring board.

[0182] Step (IV) is a step of roughening the insulating layer. Usually, smears are also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by carrying out 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.

[0183] The swelling liquid used in the roughening treatment is not particularly limited, but includes an alkaline solution, a surfactant solution, etc., and is preferably an alkaline solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, but can be performed by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes, for example. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 to 15 minutes.

[0184] The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan.

[0185] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be mentioned.

[0186] The treatment with the neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method in which the object that has been roughened with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferred.

[0187] 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. 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.

[0188] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0189] The conductor layer may be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

[0190] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.

[0191] 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 by a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of ease of production, it is preferable to form the conductor layer by the semi-additive method. An example of forming the conductor layer by the semi-additive method will be described below.

[0192] First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0193] In another embodiment, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, it is preferable to carry out step (V) 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 lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is carried out to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method, using the metal foil on the insulating layer.

[0194] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0195] <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 by using the printed wiring board of the present invention.

[0196] Examples of the semiconductor device include various semiconductor devices used in electric appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). EXAMPLES

[0197] The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Unless otherwise specified, the temperature and pressure conditions are room temperature (23°C) and atmospheric pressure (1 atm), respectively.

[0198] <Example 1> Naphthol aralkyl-based epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent: 330 g / eq.) 10 parts, active ester-based curing agent ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with 62% non-volatile content by mass, active ester group equivalent: 234 g / eq.) 22.6 parts, cyclopentadiene compound ("SLK-250" manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts, inorganic filler (spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm, specific surface area: 5.8 m) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 2 A resin composition (resin varnish) was prepared by mixing 70 parts of a cellulose acetate copolymer (100 parts by weight / g), 1 part of a curing accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ"), 10 parts of MEK, and 10 parts of toluene and dispersing the mixture uniformly using a high-speed rotating mixer.

[0199] <Example 2> A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that the amount of naphthol aralkyl-skeleton epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 330 g / eq.) used was changed from 10 parts to 9 parts, the amount of active ester-based curing agent ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with 62% non-volatile content by mass, active ester group equivalent 234 g / eq.) used was changed from 22.6 parts to 21 parts, and 4.3 parts of maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., toluene-MEK mixed solution with 70% non-volatile content) was further added.

[0200] <Example 3> An MEK solution (70% by mass of non-volatile components) of maleimide compound A (Mw / Mn=1.81, u'=1.47 (mainly 1, 2 or 3)) represented by the following formula (1) synthesized by the method described in Synthesis Example 1 of the Japan Institute of Invention and Innovation Disclosure Technical Journal Publication No. 2020-500211 was prepared.

[0201] [ka]

[0202] A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that the amount of naphthol aralkyl skeleton epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 330 g / eq.) used was changed from 10 parts to 9 parts, the amount of active ester curing agent ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with 62 mass% non-volatile component, active ester group equivalent 234 g / eq.) used was changed from 22.6 parts to 21 parts, and 4.3 parts of maleimide compound A (MEK solution with 70% solid content) was further added.

[0203] <Example 4> A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that the amount of naphthol aralkyl skeleton epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 330 g / eq.) used was changed from 10 parts to 9 parts, the amount of active ester curing agent ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with 62 mass% non-volatile content, active ester group equivalent 234 g / eq.) used was changed from 22.6 parts to 21 parts, and 4.6 parts of styryl-modified polyphenylene ether resin ("OPE-2St-1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene mixed solution with 65% non-volatile content) was further added.

[0204] <Example 5> A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that the amount of naphthol aralkyl skeleton epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 330 g / eq.) used was changed from 10 parts to 9 parts, the amount of active ester curing agent ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with 62 mass% non-volatile content, active ester group equivalent 234 g / eq.) used was changed from 22.6 parts to 21 parts, and 4.6 parts of an olefin compound ("ODV-XET-X04" manufactured by Nippon Steel Chemical & Material Co., Ltd., toluene mixed solution with 65% non-volatile content) was further added.

[0205] <Example 6> A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that the amount of naphthol aralkyl skeleton epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 330 g / eq.) used was changed from 10 parts to 9 parts, the amount of active ester curing agent ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with 62 mass% non-volatile components, active ester group equivalent 234 g / eq.) used was changed from 22.6 parts to 21 parts, and 3 parts of a terminal methacrylic modified polyphenylene ether resin ("SA9000-111" manufactured by Sabic Corporation) were further added.

[0206] <Comparative Example 1> The silica particles were spherical and surface-treated with an inorganic filler (an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd.'s "KBM573") without using a cyclopentadiene compound (Shin-Etsu Chemical Co., Ltd.'s "SLK-250"). 2 A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that the amount of 53 parts of polyvinyl chloride (1 / g) was changed from 70 parts to 53 parts.

[0207] <Comparative Example 2> Instead of using an active ester hardener (DIC Corporation's "HPC-8150-62T", a toluene solution with 62% non-volatile content, active ester group equivalent of 234 g / eq.), 5 parts of a phenol-based hardener (DIC Corporation's "LA7054", a MEK solution with 60% non-volatile content) was added, and an inorganic filler (an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd.'s "KBM573") was used to treat spherical silica (Admatechs Corporation's "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m) surface-treated with an inorganic filler (an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd.'s "KBM573"). 2 A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that the amount of 1,2-dichlorophenyl ether (1 / g) was changed from 70 parts to 40 parts.

[0208] <Test Example 1: Measurement of dielectric properties> A polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. The resin compositions prepared in the Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to prepare a resin sheet including a support and a 40 μm-thick resin composition layer.

[0209] The resin sheet containing the resin composition layer having a thickness of 40 μm was heated at 190° C. for 90 minutes to thermally cure the resin composition layer. The support was then peeled off to obtain a cured product of the resin composition. This cured product was cut into a test piece having a width of 2 mm and a length of 80 mm. The relative dielectric constant (Dk) and dielectric loss tangent (Df) of the test piece were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by a cavity resonance perturbation method using an Agilent Technologies "HP8362B". Measurements were performed on three test pieces.

[0210] <Test Example 2: Evaluation of cracks after desmear> A polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. The resin compositions prepared in the Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying was 25 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 2.5 minutes to prepare a resin sheet including a support and a resin composition layer having a thickness of 25 μm.

[0211] The resin sheet containing the resin composition layer having a thickness of 25 μm was laminated on both sides of a core material (Hitachi Chemical Co., Ltd. "E705GR", thickness 400 μm) in which circular copper pads (copper thickness 35 μm) having a diameter of 350 μm were formed in a grid shape at intervals of 400 μm so that the residual copper ratio was 60%. Using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd. 2-stage build-up laminator "CVP700"), the resin composition layer was bonded to the inner layer substrate. This lamination was performed by decompressing for 30 seconds to an atmospheric pressure of 13 hPa or less, and then pressing for 30 seconds at a temperature of 100 ° C and a pressure of 0.74 MPa. This was placed in an oven at 130 ° C and heated for 30 minutes, and then transferred to an oven at 170 ° C and heated for 30 minutes. The support layer was then peeled off, and the resulting circuit board was immersed in swelling dip Securigant P (Atotech Japan Co., Ltd.) for 10 minutes at 60°C. Next, the circuit board was immersed in Concentrate Compact P (KMnO4: 60g / L, NaOH: 40g / L aqueous solution) (Atotech Japan Co., Ltd.) for 30 minutes at 80°C. Finally, the circuit board was immersed in reduction solution Securigant P (Atotech Japan Co., Ltd.) for 5 minutes at 40°C. After the roughening treatment, 100 copper pads of the circuit board were observed to check for the presence or absence of cracks in the resin composition layer. If there were 10 or fewer cracks, the result was marked as "good", and if there were more than 10 cracks, the result was marked as "bad".

[0212] The non-volatile component contents of the resin compositions of the Examples and Comparative Examples, and the measurement results and evaluation results of the Test Examples are shown in Table 1 below. [Table 1]

[0213] As shown in Table 1, Comparative Example 1, which does not use a cyclopentadiene compound, tends to cause cracks, while Comparative Example 2, which uses a cyclopentadiene compound but does not use an active ester compound, suppresses cracks but has a high dielectric tangent. In contrast, it can be seen that these problems can be overcome when a resin composition containing (A) a cyclopentadiene compound, (B) an epoxy resin, and (C) an active ester compound is used.

Claims

1. A resin composition comprising: (A) a compound having a terminal carbon-carbon double bond and a cyclopentadiene ring; (B) an epoxy resin; and (C) an active ester compound, The component (A) is represented by the formula (A1): 【Chemistry 1】 [In the formula, R each independently represents a substituent, and at least one R is a group having a terminal carbon-carbon double bond; Each X independently represents an organic group. Each a independently represents 0, 1, 2, 3, or 4, and the sum of the n+1 a's is 1 or more; n represents 0 or an integer of 1 or more. A resin composition comprising a compound represented by the formula:

2. The component (A) is represented by the formula (A2): 【Chemistry 2】 [In the formula, R １ , R ２ and R ３ each independently represents a hydrogen atom or an alkyl group, R ４ each independently represents a substituent, X １ each independently represents a hydrocarbon group, Each Y is independently a single bond, -O-, -CO-, -S-, -SO-, or -SO ２ -, -CONH-, -NHCO-, -COO-, or -OCO-; Z represents a single bond or an arylene group which may be substituted with an alkyl group; b's each independently represent 0, 1, 2, or 3; n represents 0 or an integer of 1 or more; Each m independently represents 0, 1, 2, or 3. The resin composition according to claim 1 , comprising a compound represented by the formula:

3. The resin composition according to claim 1 or 2, wherein n is 0.

4. The resin composition according to any one of claims 1 to 3, wherein the content of the component (A) is 20 mass% or less, when the non-volatile components in the resin composition are 100 mass%.

5. The resin composition according to any one of claims 1 to 4, wherein the content of the component (A) is 0.5 mass% or more, based on 100 mass% of non-volatile components in the resin composition.

6. The resin composition according to any one of claims 1 to 5, wherein a mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 0.05 to 3.

7. The resin composition according to any one of claims 1 to 6, wherein a mass ratio of the component (A) to the component (C) (component (A) / component (C)) is 0.05 to 3.

8. The resin composition according to any one of claims 1 to 7, further comprising (D) an inorganic filler.

9. The resin composition according to claim 8, wherein the component (D) is silica.

10. The resin composition according to claim 8 or 9, wherein the content of the component (D) is 40 mass% or more, based on 100 mass% of nonvolatile components in the resin composition.

11. The resin composition according to any one of claims 1 to 10, wherein the dielectric loss tangent (Df) of a cured product of the resin composition is 0.0032 or less when measured at 5.8 GHz and 23 ° C.

12. The resin composition according to any one of claims 1 to 11, 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.

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

14. A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 12.

15. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 12 provided on the support.

16. 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 12.

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

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