JP7597014B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition containing an epoxy resin. It also relates to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

A known manufacturing technique for printed wiring boards is the build-up method, in which insulating layers and conductor layers are alternately stacked. In build-up manufacturing methods, the insulating layers are generally formed by curing a resin composition containing an epoxy resin and an inorganic filler. In recent years, with the finer and denser wiring of printed wiring boards and the higher signal frequencies, there is a demand for further reduction in the dielectric tangent of the insulating layer. In addition, since printed wiring boards are generally exposed to high temperature and humidity environments, they are also required to have peel strength resistance to high temperature and humidity environments.

Various cyclic carbonate compounds have been known to date (Patent Documents 1 to 5).

Patent No. 6141261 JP 2018-118946 A Japanese Patent Application Publication No. 5-209041 Patent No. 4273530 Patent No. 6635668

The objective of the present invention is to provide a resin composition that can produce a cured product that retains high peel strength and has a low dielectric tangent even when exposed to a high-temperature, high-humidity environment.

In order to achieve the object of the present invention, the inventors conducted extensive research and unexpectedly discovered that by using a cyclic carbonate compound (A) in a resin composition containing an epoxy resin (B) and an inorganic filler (C), it is possible to obtain a cured product that retains high peel strength even when exposed to a high-temperature, high-humidity environment and has a low dielectric tangent, thereby completing the present invention.

That is, the present invention includes the following.
[1] A resin composition comprising (A) a cyclic carbonate compound, (B) an epoxy resin, and (C) an inorganic filler.
[2] The resin composition according to the above [1], further comprising (D) an active ester compound.
[3] The resin composition according to the above [2], wherein the content of the (A) component is 1% by mass to 10% by mass, where the total amount of the (A) component, the (B) component, and the (D) component is taken as 100% by mass.
[4] The resin composition according to the above [2] or [3], wherein the content of the (D) component is 12 mass% or more, when the non-volatile components in the resin composition are 100 mass%.
[5] The resin composition according to any one of the above [1] to [4], wherein the component (A) contains a compound selected from a 5-membered cyclic carbonate compound and a 6-membered cyclic carbonate compound.
[6] The component (A) is represented by formula (1):

[Wherein,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent (1) a hydrogen atom, (2) an alkyl group which may be substituted with a group selected from RO-, RCO-, RCOO- and ROCO-, (3) an alkenyl group which may be substituted with a group selected from RO-, RCO-, RCOO- and ROCO-, (4) an aralkyl group which may be substituted with a group selected from R-, RO-, RCO-, RCOO- and ROCO-, or (5) a group represented by formula (2-1):

or (6) a group represented by formula (2-2):

represents a group represented by
R ^1' , R ^2' , R ^3' , R ^4' , R ^5' and R ^6' each independently represent (1) a hydrogen atom, (2) an alkyl group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, (3) an alkenyl group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, or (4) an aralkyl group which may be substituted with a group selected from R-, RO-, RCO-, RCOO-, and ROCO-;
A ¹ and A ² each independently represent -O-, -CO-, -COO-, or -OCO-;
X and Y each independently represent (1) an alkylene group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, or (2) an alkenylene group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-;
R each independently represents an alkyl group, an alkenyl group, an aralkyl group, or an aryl group, each of which may be substituted with a group selected from a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an aralkyl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an aralkyl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, and an aralkyl-carbonyl-oxy group;
Z's each independently represent a divalent hydrocarbon group which may have a substituent;
n represents 0, 1, 2, or 3;
* indicates the binding site.]
The resin composition according to any one of the above [1] to [5], comprising a compound represented by the following formula:
[7] The resin composition according to any one of [1] to [6] above, wherein the content of the component (B) is 1% by mass to 20% by mass, based on 100% by mass of the non-volatile components in the resin composition.
[8] The resin composition according to any one of [1] to [7] above, wherein the content of the component (C) is 60% by mass or more, based on 100% by mass of non-volatile components in the resin composition.
[9] The resin composition according to any one of the above [1] to [8], further comprising a curing agent selected from the group consisting of phenol-based curing agents and carbodiimide-based curing agents.
[10] The resin composition according to any one of [1] to [9] above, wherein the dielectric loss tangent (Df) of a cured product of the resin composition is 0.0030 or less when measured at 5.8 GHz and 23° C.
[11] The resin composition according to any one of [1] to [10] above, wherein the elongation at break of a cured product of the resin composition is 0.2% or more when measured at 23°C in accordance with JIS K7127.
[12] The resin composition according to any one of the above [1] to [11], which is for forming an insulating layer for forming a conductor layer.
[13] The resin composition according to any one of [1] to [11] above, which is for forming an insulating layer of a printed wiring board.
[14] A cured product of the resin composition according to any one of [1] to [13] above.
[15] A sheet-like laminate material containing the resin composition according to any one of [1] to [13] above.
[16] A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of [1] to [13] above, provided on the support.
[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.

The resin composition of the present invention can provide a cured product that retains high peel strength even when exposed to a high-temperature, high-humidity environment and has a low dielectric tangent.

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 may be modified as desired without departing from the scope of the claims of the present invention and their equivalents.

<Resin Composition>
The resin composition of the present invention comprises (A) a cyclic carbonate compound, (B) an epoxy resin, and (C) an inorganic filler, and can provide a cured product that can maintain high peel strength even when exposed to a high-temperature and high-humidity environment and has a low dielectric tangent.

The resin composition of the present invention may further contain optional components in addition to (A) the cyclic carbonate compound, (B) the epoxy resin, and (C) the inorganic filler. Examples of the optional components include (D) an active ester compound, (D') other curing agents, (E) a compound containing a radical polymerizable group, (F) a thermoplastic resin, (G) a curing accelerator, (H) other additives, and (I) an organic solvent.

Below, we will explain each component contained in the resin composition in detail.

<(A) Cyclic Carbonate Compound>
The resin composition of the present invention contains (A) a cyclic carbonate compound. The (A) cyclic carbonate compound is a compound containing a cyclic structure containing a carbonate skeleton (-O-C(=O)-O-). The (A) cyclic carbonate compound has one or more cyclic structures containing a carbonate skeleton in one molecule, and in one embodiment, preferably has one or two cyclic structures. In one embodiment, the (A) cyclic carbonate compound preferably contains a compound selected from a 5-membered cyclic carbonate compound having an ethylene carbonate skeleton and a 6-membered cyclic carbonate compound having a trimethylene carbonate skeleton, more preferably contains a compound selected from a 5-membered cyclic carbonate compound having one or two ethylene carbonate skeletons in one molecule and a 6-membered cyclic carbonate compound having one or two trimethylene carbonate skeletons in one molecule, and even more preferably contains a 6-membered cyclic carbonate compound having one or two trimethylene carbonate skeletons in one molecule.

In a particularly preferred embodiment, the cyclic carbonate compound (A) has the formula (1):

This includes compounds represented by the formula:

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent (1) a hydrogen atom, (2) an alkyl group which may be substituted with a group selected from RO-, RCO-, RCOO- and ROCO-, (3) an alkenyl group which may be substituted with a group selected from RO-, RCO-, RCOO- and ROCO-, (4) an aralkyl group which may be substituted with a group selected from R-, RO-, RCO-, RCOO- and ROCO-, or (5) a group represented by formula (2-1):

or (6) a group represented by formula (2-2):

The symbol * indicates the bonding site.

The term "alkyl group" refers to a linear, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl group is preferably an alkyl group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a sec-pentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a tert-octyl group, a cyclopentyl group, and a cyclohexyl group.

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

The term "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.

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

In one embodiment, R ¹ , R ² , R ⁵ , and R ⁶ are each independently preferably (1) a hydrogen atom, or (2) an alkyl group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-; more preferably (1) a hydrogen atom, or (2) an alkyl group which may be substituted with RO-; particularly preferably (1) a hydrogen atom, or (2) an alkyl group.

In one embodiment, R ³ and R ⁴ are each independently preferably (1) a hydrogen atom, (2) an alkyl group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, (3) a group represented by formula (2-1), or (4) a group represented by formula (2-2); more preferably (1) a hydrogen atom, (2) an alkyl group which may be substituted with RO-, (3) a group represented by formula (2-1), or (4) a group represented by formula (2-2); and even more preferably (1) a hydrogen atom, (2) an alkyl group, or (3) a group represented by formula (2-2).

R ^1' , R ^2' , R ^3' , R ^4' , R ^5' and R ^6' each independently represent (1) a hydrogen atom, (2) an alkyl group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, (3) an alkenyl group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, or (4) an aralkyl group which may be substituted with a group selected from R-, RO-, RCO-, RCOO-, and ROCO-.

In one embodiment, R ^1' , R ^2' , R ^3' , R ^4' , R ^5' and R ^6' are each independently preferably (1) a hydrogen atom or (2) an alkyl group optionally substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-; more preferably (1) a hydrogen atom or (2) an alkyl group optionally substituted with RO-; particularly preferably (1) a hydrogen atom or (2) an alkyl group.

A ¹ and A ² each independently represent -O-, -CO-, -COO-, or -OCO-. In one embodiment, A ¹ and A ² are preferably -O-.

X and Y each independently represent (1) an alkylene group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, or (2) an alkenylene group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-.

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.

The term "alkenylene group" refers to a linear, branched, and/or cyclic divalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, the alkenyl group is preferably an alkenylene group having 2 to 14 carbon atoms, more preferably an alkenylene group having 2 to 10 carbon atoms, and even more preferably an alkenylene group having 2 to 6 carbon atoms. Examples of alkenylene (groups) include -CH=CH-, -CH ₂ CH=CH-, -CH=C(CH ₃ )-, -C(CH ₃ )=CH-, -CH ₂ CH ₂ CH=CH-, -CH ₂ CH=CHCH ₂ -, -CH=CHCH ₂ CH ₂ -, -CH ₂ CH=C(CH ₃ )-, -C(CH ₃ )=CHCH ₂ -, -CH ₂ C(CH ₃ )=CH-, -CH=C(CH ₃ )CH ₂ -, -CH(CH ₃ )CH=CH-, -CH=CHCH(CH ₃ )-, and the like.

In one embodiment, X and Y are each independently preferably an alkylene group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-; more preferably an alkylene group which may be substituted with RO-; and even more preferably an alkylene group.

Each R independently represents an alkyl group, alkenyl group, aralkyl group, or aryl group, each of which may be substituted with a group selected from a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an aralkyl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an aralkyl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, and an aralkyl-carbonyl-oxy group.

In one embodiment, each R is preferably an alkyl group, an alkenyl group, an aralkyl group, or an aryl group, and more preferably an alkyl group.

Each Z is independently a divalent hydrocarbon group which may have a substituent.

A divalent hydrocarbon group is a divalent hydrocarbon group that has one or more (e.g., 1 to 100, 2 to 50, 2 to 30) carbon atoms as the skeletal atoms. The divalent hydrocarbon group includes a straight chain structure, a branched chain structure, and/or a cyclic structure. The divalent hydrocarbon group may be a hydrocarbon group that does not include an aromatic ring, or may be a hydrocarbon group that includes an aromatic ring.

Examples of divalent hydrocarbon groups include alkylene groups, alkenylene groups, aromatic carbocyclic groups, non-aromatic carbocyclic groups, alkylene-aromatic carbocyclic-alkylene groups, alkenylene-aromatic carbocyclic-alkenylene groups, alkylene-non-aromatic carbocyclic-alkylene groups, alkenylene-non-aromatic carbocyclic-alkenylene groups, aromatic carbocyclic-aromatic carbocyclic groups, non-aromatic carbocyclic-non-aromatic carbocyclic groups, aromatic carbocyclic-alkylene-aromatic carbocyclic groups, aromatic carbocyclic-alkenylene-aromatic carbocyclic groups, aromatic carbocyclic-aromatic carbocyclic-aromatic carbocyclic groups, aromatic carbocyclic-non-aromatic carbocyclic groups. Examples of such a group include a non-aromatic carbocycle-aromatic carbocycle group, a non-aromatic carbocycle-alkylene-non-aromatic carbocycle group, a non-aromatic carbocycle-alkylene-non-aromatic carbocycle group, a non-aromatic carbocycle-aromatic carbocycle-non-aromatic carbocycle group, and a non-aromatic carbocycle-non-aromatic carbocycle-non-aromatic carbocycle group, in which the non-aromatic carbocycle may be fused with an aromatic carbocycle and may be substituted with a group selected from an alkyl group, an alkenyl group, and an aryl group, and the aromatic carbocycle may be fused with a non-aromatic carbocycle and may be substituted with a group selected from an alkyl group, an alkenyl group, and an aryl group.

An aromatic carbocycle means a carbocycle that follows Huckel's rule, in which the number of electrons contained in the π electron system on the ring is 4p+2 (p is a natural number). An aromatic carbocycle has only carbon atoms as ring constituent atoms. In one embodiment, the aromatic carbocycle is preferably a 6- to 14-membered aromatic carbocycle, and more preferably a 6- to 10-membered aromatic carbocycle. Suitable specific examples of aromatic carbocycles include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc., more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

A non-aromatic carbocycle is a carbocycle that is not aromatic and has aromaticity throughout the ring. A non-aromatic carbocycle has only carbon atoms as ring constituent atoms. A non-aromatic carbocycle may be a saturated carbocycle consisting of only single bonds, or a non-aromatic unsaturated carbocycle having at least one of a double bond and a triple bond. The non-aromatic carbocycle is preferably a non-aromatic carbocycle having 3 to 20 carbon atoms, more preferably a non-aromatic carbocycle having 4 to 15 carbon atoms, and even more preferably a non-aromatic carbocycle having 4 to 10 carbon atoms. Specific examples of suitable non-aromatic carbocycles include monocyclic saturated carbocycles such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, and a cyclononadecane ring. bicyclic saturated carbocyclic rings such as a bicyclo[2.2.1]heptane ring (norbornane ring), a bicyclo[4.4.0]decane ring (decalin ring), a bicyclo[5.3.0]decane ring, a bicyclo[4.3.0]nonane ring (hydrindane ring), a bicyclo[3.2.1]octane ring, a bicyclo[5.4.0]undecane ring, a bicyclo[3.3.0]octane ring, and a bicyclo[3.3.1]nonane ring; tricyclic saturated carbocyclic rings such as a tricyclo[5.2.1.0 ^2,6 ]decane ring (tetrahydrodicyclopentadiene ring), a tricyclo[3.3.1.1 ^3,7 ]decane ring (adamantane ring), and a tricyclo[6.2.1.0 ^{2,7 ]} undecane ring; tetracyclic saturated carbocyclic rings such as a pentacyclo[9.2.1.1 4,7 . 0 ^2,7 ]dodecane ring; and five-ring saturated carbocyclic rings such as a pentacyclo[9.2.1.1 ^4,7 . ^{0 2,1} 0.0 ^3,8 ]pentadecane ring and a pentacyclo[6.5.1.1 ^3,6 . ^{0 2,7} . ^{0 9,13} ]pentadecane ring (tetrahydrotricyclopentadiene ring).

The "substituents" that the divalent hydrocarbon group in Z may have are not particularly limited, but include, for example, halogen atoms, alkyl-oxy groups, alkenyl-oxy groups, aryl-oxy groups, aralkyl-oxy groups, alkyl-carbonyl groups, alkenyl-carbonyl groups, aryl-carbonyl groups, aralkyl-carbonyl groups, alkyl-oxy-carbonyl groups, alkenyl-oxy-carbonyl groups, aryl-oxy-carbonyl groups, aralkyl-oxy-carbonyl groups, alkyl-carbonyl-oxy groups, alkenyl-carbonyl-oxy groups, aryl-carbonyl-oxy groups, aralkyl-carbonyl-oxy groups, alkyl-carbonyl-oxy groups, alkenyl-carbonyl-oxy groups, aryl-carbonyl-oxy groups, aralkyl-carbonyl-oxy groups, and groups of the formula (Z-1):

A group represented by formula (Z-2):

The * indicates the bonding site.

A halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom.

R ^1'' , R ^2'' , R ^3'' , R ^4'' , R ^5'' and R ^6'' each independently represent (1) a hydrogen atom, (2) an alkyl group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, (3) an alkenyl group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, or (4) an aralkyl group which may be substituted with a group selected from R-, RO-, RCO-, RCOO-, and ROCO-, and in one embodiment, the suitable ranges are the same as those of R ^1' , R ^2' , R ^3' , R ^4' , R ^5' , and R ^6' .

Each ^A3 independently represents -O-, -CO-, -COO-, or -OCO-, and in one embodiment, the suitable range is the same as that of ^A1 and ^A2 .

Y' each independently represents (1) an alkylene group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, or (2) an alkenylene group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, and in one embodiment, the preferred ranges are the same as those of X and Y.

In one embodiment, each Z is preferably independently selected from the formula (Z1):

is a group represented by the formula (Z2):

is a group represented by the formulas (Z3-1) to (Z3-36):

A group represented by any one of the formulas (Z3-25) is particularly preferred. * indicates a bonding site.

Ring Z ^a and ring Z ^b each independently represent an aromatic carbocyclic ring which may have a substituent. In one embodiment, ring Z ^a and ring Z ^b each independently represent a benzene ring which may have a substituent, more preferably a benzene ring which may be substituted with an alkyl group, and particularly preferably an (unsubstituted) benzene ring.

^Xz represents a single bond or ^{-CRz1Rz2- ,} and in one embodiment, is preferably ^{-CRz1Rz2- .}

n ^z represents 0, 1, 2, or 3, and in one embodiment, is preferably 0, 1, or 2, and more preferably 0 or 1. The n ^z units may be the same or different from one another.

R ^z1 and R ^z2 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, or R ^z1 and R ^z2 bond together to represent ^a non-aromatic carbocyclic ring which may have a substituent and which may be fused with an aromatic carbocyclic ring. In one embodiment, R ^z1 and R ^z2 are bonded together to represent a non-aromatic carbocyclic ring which may have a substituent and which may be fused with an aromatic carbocyclic ring, preferably ^a monocyclic saturated carbocyclic ring which may have a substituent and which may be fused with a benzene ring, more preferably a cyclopentane ring which may be fused with a benzene ring.

Each ^Rz independently represents a substituent. In one embodiment, each ^Rz independently represents preferably an alkyl group.

The "substituents" which the aromatic carbocycle in ring Z ^a and ring Z ^b may have, the "substituents" which the alkyl group, alkenyl group, aryl group, aralkyl group, and non-aromatic carbocycle which may be condensed with the aromatic carbocycle in R ^z1 and R ^z2 may have, and the "substituents" in R ^z are not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an aralkyl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an aralkyl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, an aralkyl-carbonyl-oxy group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, an aralkyl-carbonyl-oxy group, and the like.

Each z is independently 0, 1, 2, or 3. In one embodiment, each z is independently preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 0.

n represents 0, 1, 2, or 3. In one embodiment, each n is independently preferably 0 or 1. The n units may be the same or different for each unit.

The molecular weight of the (A) cyclic carbonate compound is preferably 10,000 or less, more preferably 5,000 or less, even more preferably 2,000 or less, and particularly preferably 1,000 or less. The lower limit can be, for example, 88 (the molecular weight of ethylene carbonate) or more, 102 (the molecular weight of trimethylene carbonate) or more, etc.

Specific examples of (A) cyclic carbonate compounds include those represented by formulas (A1) to (A17):

Examples of compounds represented by the formula:

The content of the (A) cyclic carbonate compound in the resin composition is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 2.5% 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) cyclic carbonate compound in the resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 0.8% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass.

The content of the (A) cyclic carbonate compound relative to the total amount of the (A) cyclic carbonate compound and the (B) epoxy resin (when the (D) active ester compound is used, the total amount of the (A) cyclic carbonate compound, the (B) epoxy resin, and the (D) active ester compound) is not particularly limited, but is preferably 0.01% by mass to 50% by mass, more preferably 0.1% by mass to 20% by mass, even more preferably 0.5% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass, when the total amount of the (A) cyclic carbonate compound and the (B) epoxy resin (the total amount of the (A) cyclic carbonate compound, the (B) epoxy resin, and the (D) active ester compound) is taken as 100% by mass.

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

(B) Examples of epoxy resins include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ether Examples of the epoxy resin include ester type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, etc. (B) The epoxy resin may be used alone or in combination of two or more kinds.

The resin composition preferably contains, as the epoxy resin (B), 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 epoxy resin (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

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

Preferably, the liquid epoxy resin has two or more epoxy groups in one molecule.

As liquid epoxy resins, glycirol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane dimethanol type epoxy resins, cyclic aliphatic glycidyl ethers, and epoxy resins having a butadiene structure are preferred, and glycirol type epoxy resins, cyclic aliphatic glycidyl ethers, bisphenol A type epoxy resins, and bisphenol F type epoxy resins are more preferred.

Specific examples of liquid epoxy resins include Nagase ChemteX's "EX-992L," Mitsubishi Chemical's "YX7400," DIC's "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy resins); Mitsubishi Chemical's "828US," "828EL," "jER828EL," "825," and "Epicoat 828EL" (bisphenol A-type epoxy resins); Mitsubishi Chemical's "jER807" and "1750" (bisphenol A-type epoxy resins). phenol F type epoxy resin); Mitsubishi Chemical Corporation's "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical Corporation's "630", "630LSD", and "604" (glycidylamine type epoxy resin); ADEKA Corporation's "ED-523T" (glycilol type epoxy resin); ADEKA Corporation's "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin); ADEKA Corporation's "EP-4088S" (dicyclopentasiloxane type epoxy resin); bisphenol A type epoxy resin); "ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin); "EX-991L" manufactured by Nagase ChemteX Corporation (alkyleneoxy skeleton and butadiene skeleton-containing epoxy resin); "Celloxide 2021P" manufactured by Daicel Corporation (alicyclic epoxy resin having an ester skeleton) Examples include Daicel's "PB-3600", Nippon Soda's "JP-100" and "JP-200" (epoxy resins with butadiene structure); Nippon Steel Chemical & Material's "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin); Osaka Gas Chemical's "EG-280" (fluorene structure-containing epoxy resin); and Nagase ChemteX's "EX-201" (cyclic aliphatic glycidyl ether).

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.

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

Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin); DIC's "N-690" (cresol novolac type epoxy resin); DIC's "N-695" (cresol novolac type epoxy resin); DIC's "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy resin); and DIC's "EXA-7311". , "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon 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", and "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 types.

When a combination of a solid epoxy resin and a liquid epoxy resin is used as the epoxy resin (B), the mass ratio thereof (solid epoxy resin:liquid epoxy resin) is preferably 100:1 to 1:100, more preferably 50:1 to 1:50, and particularly preferably 10:1 to 1:10.

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 groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the (B) epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

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 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 epoxy resin (B) in the resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass.

The mass ratio of the epoxy resin (B) to the cyclic carbonate compound (A) in the resin composition (component (B)/component (A)) is not particularly limited, but is preferably 0.1 or more, more preferably 0.5 or more, and particularly preferably 1 or more. The upper limit of the mass ratio of the epoxy resin (B) to the cyclic carbonate compound (A) in the resin composition (component (B)/component (A)) is not particularly limited, but is preferably 100 or less, more preferably 50 or less, and particularly preferably 10 or less.

<(C) Inorganic filler>
The resin composition of the present invention contains an inorganic filler (C). The inorganic filler (C) is contained in the resin composition in the form of particles.

(C) An inorganic compound is used as the material for the inorganic filler. (C) Examples of the material for the inorganic filler include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica or aluminosilicate 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. (C) The inorganic filler may be used alone or in any combination of two or more kinds in any ratio.

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

(C) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 4 μm or less, even more preferably 3 μm or less, and particularly preferably 2.7 μm or less. (C) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. (C) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction/scattering particle size distribution measuring device, and the median diameter is used 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 a flow cell method to measure the volumetric particle size distribution of the inorganic filler, and the average particle size was calculated as the median diameter from the obtained particle size distribution. An example of a laser diffraction type particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

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

(C) The inorganic filler may be a non-hollow inorganic filler with a porosity of 0 volume% (preferably non-hollow silica, non-hollow aluminosilicate), or a hollow inorganic filler with a porosity of more than 0 volume% (preferably hollow silica, hollow aluminosilicate), or may contain both. (C) The inorganic filler preferably contains only a hollow inorganic filler (preferably hollow silica, hollow aluminosilicate), or contains both a non-hollow inorganic filler (preferably non-hollow silica, non-hollow aluminosilicate) and a hollow inorganic filler (preferably hollow silica, hollow aluminosilicate). The porosity of the hollow inorganic filler is preferably 90 volume% or less, more preferably 85 volume% or less. The lower limit of the porosity of the (C) inorganic filler may be, for example, more than 0 volume%, 1 volume% or more, 5 volume% or more, 10 volume% or more, 20 volume% or more, etc. The porosity P (vol %) of an inorganic filler is defined as the volume-based ratio of the total volume of one or more voids present inside the particle to the total volume of the particle based on the outer surface of the particle (total volume of voids/volume of particle), and is calculated, for example, according to the following formula (I) using the measured value D _M (g/cm ³ ) of the actual density of the inorganic filler and the theoretical value D _T (g/cm ³ ) of the material density of the material forming the inorganic filler.

The actual density of the inorganic filler can be measured, for example, using a true density measuring device. An example of a true density measuring device is the ULTRAPYCNOMETER 1000 manufactured by QUANTACROME. For example, nitrogen is used as the measurement gas.

(C) From the viewpoint of improving moisture resistance and dispersibility, it is preferable that the inorganic filler is treated with a surface treatment agent. Examples of the surface treatment agent include a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane, an organosilazane compound, and a titanate coupling agent. In addition, the surface treatment agent may be used alone or in any combination of two or more types.

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

From the viewpoint of improving the dispersibility of the inorganic filler, it is preferable that the degree of surface treatment with the surface treatment agent falls within a specified range. Specifically, it is preferable that 100% by mass of the inorganic filler is 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.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and even more preferably 0.2 mg/m ² or more. 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 sheet form, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and even more preferably 0.5 mg/m ² or less.

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

The content of the inorganic filler (C) in the resin composition is not particularly limited, but is preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, and particularly preferably 78% 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 inorganic filler (C) in the resin composition is not particularly limited, but is preferably 5% by mass or more, or 10% by mass or more, more preferably 20% by mass or more, or 30% by mass or more, even more preferably 40% by mass or more, or 50% by mass or more, even more preferably 55% by mass or more, or 60% by mass or more, and particularly preferably 65% by mass or more, or 70% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass.

The mass ratio of the inorganic filler (C) to the cyclic carbonate compound (A) in the resin composition (component (C)/component (A)) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and particularly preferably 10 or more. The upper limit of the mass ratio of the inorganic filler (C) to the cyclic carbonate compound (A) in the resin composition (component (C)/component (A)) is not particularly limited, but is preferably 1,000 or less, more preferably 500 or less, and particularly preferably 100 or less.

<(D) Active Ester Compound>
The resin composition of the present invention preferably contains an active ester compound (D). The active ester compound (D) may be used alone or in combination of two or more kinds in any ratio. The active ester compound (D) may function as an epoxy resin curing agent that reacts with the epoxy resin (B) to cure the epoxy resin.

(D) As the 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, and phenol novolak. Here, "dicyclopentadiene-type diphenol compounds" refer to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, the active ester compound (D) 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 among these, at least one selected from a dicyclopentadiene-type active ester compound and a naphthalene-type active ester compound is more preferable. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable.

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

The active ester group equivalent of the (D) active ester compound (reactive group equivalent as a curing agent) is preferably 50 g/eq. to 500 g/eq., more preferably 50 g/eq. to 400 g/eq., and even more preferably 100 g/eq. to 300 g/eq. The active ester group equivalent is the mass of the active ester compound per equivalent of active ester group.

The content of the (D) active ester compound in the resin composition is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 12% by mass or more, and particularly preferably 13% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass. The upper limit of the content of the (D) active ester compound 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 25% by mass or less, and particularly preferably 20% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

The mass ratio of the (D) active ester compound to the (A) cyclic carbonate compound in the resin composition (component (D)/component (A)) is not particularly limited, but is preferably 0.5 or more, more preferably 1 or more, and particularly preferably 5 or more. The upper limit of the mass ratio of the (D) active ester compound to the (A) cyclic carbonate compound in the resin composition (component (D)/component (A)) is not particularly limited, but is preferably 100 or less, more preferably 30 or less, and particularly preferably 15 or less.

<(D') Other Curing Agents>
The resin composition of the present invention may further contain a (D') curing agent other than the component (D) as an optional component. The (D') other curing agent may be used alone or in any combination of two or more. The (D') other curing agent may function as an epoxy resin curing agent that reacts with the (B) epoxy resin to cure it, similar to the (D) active ester curing agent.

(D') Other curing agents are not particularly limited, but examples thereof include phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and thiol-based curing agents. Among these, curing agents selected from the group consisting of phenol-based curing agents and carbodiimide-based curing agents are preferred, and it is more preferred that the resin composition of the present invention contains both a phenol-based curing agent and a carbodiimide-based curing agent.

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

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

Commercially available carbodiimide curing agents include, for example, "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-07," and "Carbodilite V-09" manufactured by Nisshinbo Chemical Co., Ltd.; and "Stavaxol P," "Stavaxol P400," and "Hi-Kasil 510" manufactured by Rhein Chemie.

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

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

Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins have been partially converted to triazine. Specific examples of cyanate ester-based hardeners include Lonza Japan's "PT30" and "PT60" (both of which are phenol novolac-type multifunctional cyanate ester resins), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been converted to triazine and formed into a trimer).

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

(D') The reactive group equivalent of the other curing agent is preferably 50 g/eq. to 3000 g/eq., more preferably 100 g/eq. to 1000 g/eq., even more preferably 100 g/eq. to 500 g/eq., and particularly preferably 100 g/eq. to 300 g/eq. The reactive group equivalent is the mass of the curing agent per equivalent of reactive group. The reactive group means a group that reacts with the epoxy resin, and varies depending on the type of curing agent, such as a phenolic curing agent being a phenolic hydroxyl group and a carbodiimide curing agent being a carbodiimide group.

The content of the (D') other curing agent 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 3.5% 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 (D') other curing agent in the resin composition is not particularly limited, but may be, for example, 0% by mass or more, 0.1% by mass or more, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 2.5% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass.

The content of the (D) active ester compound in the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, assuming that the total of the (D) active ester compound and (D') other curing agents in the resin composition is 100% by mass.

The ratio of the total molar equivalent number of epoxy groups in the (B) epoxy resin to the total molar equivalent number of curing agent reactive groups in the (D) active ester compound and (D') other curing agents in the resin composition (curing agent reactive groups/epoxy groups) is preferably in the range of 0.2 to 2, more preferably in the range of 0.5 to 1.8, and even more preferably in the range of 1 to 1.5. "The total molar equivalent number of epoxy groups in the (B) epoxy resin" indicates the sum of the values obtained by dividing the mass of the (B) epoxy resin present in the resin composition by the epoxy equivalent. In addition, "The total molar equivalent number of curing agent reactive groups in the (D) active ester compound and (D') other curing agents" indicates the sum of the value obtained by dividing the mass of the (D) active ester compound present in the resin composition by the active ester group equivalent, and the value obtained by dividing the mass of the (D') other curing agents by the reactive group equivalent.

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

The radically polymerizable group is a group having a radically polymerizable ethylenically unsaturated bond, and is not particularly limited. Examples thereof include, but are not limited to,
(1) Formula (R):

[In the formula, each R ^a independently represents a hydrogen atom or a methyl group; each X ^a independently represents a carbonyl group, a methylene group, or a phenylene group; and * represents a bonding site.]
A group represented by
(2) Maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) and the like.

In the first embodiment, the radical polymerizable group-containing compound (E) preferably contains a thermoplastic resin (e.g., a number average molecular weight of 800 or more) having two or more groups represented by the above formula (R). The thermoplastic resin is not particularly limited, but examples thereof include phenoxy resin, polyvinyl acetal resin, polystyrene resin, polyethylene resin, polypropylene resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, and polyester resin. In this embodiment, the radical polymerizable group-containing compound (E) contains a modified resin of these resins having two or more groups represented by the above formula (R).

In the first embodiment, the (E) radical polymerizable group-containing compound more preferably contains a resin selected from a modified polyphenylene ether resin having two or more groups represented by the above formula (R) and a modified polystyrene resin having two or more groups represented by the above formula (R), and even more preferably contains a modified polyphenylene ether resin having two or more groups represented by the above formula (R), and particularly preferably contains a compound represented by the formula (2):

[In the formula, R ^b each independently represents a hydrogen atom or a methyl group; X ^b each independently represents a carbonyl group, a methylene group, a phenylene group, or a phenylene-methylene group (the bonding direction is not particularly limited, but it is preferable that the phenylene side is bonded to the C in "R ^b -C"); R ¹¹ and R ¹² each independently represent an alkyl group; R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ , and R ²⁴ each independently represent a hydrogen atom or an alkyl group; A represents a single bond, -C(R ^c ) ₂ -, -O-, -CO-, -S-, -SO-, or -SO ₂ -; R ^c each independently represents a hydrogen atom or an alkyl 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.

Each R ^b independently represents a hydrogen atom or a methyl group. Each X ^b independently represents a carbonyl group, a methylene group, a phenylene group, or a phenylene-methylene group (the bonding direction is not particularly limited, but it is preferable that the phenylene side is bonded to C in "R ^b -C"), and is preferably a carbonyl group or a phenylene-methylene group.

R ¹¹ and R ¹² each independently represent an alkyl group, preferably a methyl group. R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom. R ²¹ and R ²² each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, more preferably a methyl group. R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

A represents a single bond, -C(R ^c ) ₂ -, -O-, -CO-, -S-, -SO-, or -SO ₂ -, and is preferably a single bond, -C(R ^c ) ₂ -, or -O-. Each ^{R c} independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group. p represents 0 or 1, and is preferably 1. Each q and r independently represents an integer of 1 or more, and is preferably an integer of 1 to 200, and more preferably an integer of 1 to 100.

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

The number average molecular weight of the radically polymerizable group-containing compound (E) in the first embodiment is preferably 800 to 10,000, more preferably 900 to 5,000. The number average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

Commercially available products of the radically polymerizable group-containing compound (E) in the first embodiment include, for example, "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Company, Inc.; and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether resins) manufactured by SABIC Innovative Plastics.

In the second embodiment, the radical polymerizable group-containing compound (E) is preferably represented by formula (3'):

[In the formula, ring B represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent; i and j each independently represent an integer of 0 or 1 or more, and the sum of i and j is 6 or more; * represents a bonding site.]
The maleimide compound includes a maleimide compound having a partial structure represented by the following formula: The maleimide compound means a compound containing at least one maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) in one molecule. The number of maleimide groups in one molecule of the maleimide compound in the second embodiment is preferably 2 or more, and particularly preferably 2. The maleimide compound in the second embodiment may be used alone or in combination of two or more at any ratio.

The monocycloalkane ring means a monocyclic aliphatic saturated hydrocarbon ring. The monocycloalkane ring is preferably a monocycloalkane ring having 4 to 14 carbon atoms, more preferably a monocycloalkane ring having 4 to 10 carbon atoms, and particularly preferably a monocycloalkane ring having 5 or 6 carbon atoms. Examples of the monocycloalkane ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. The monocycloalkene ring means a monocyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond. The monocycloalkene ring is preferably a monocycloalkene ring having 4 to 14 carbon atoms, more preferably a monocycloalkene ring having 4 to 10 carbon atoms, and particularly preferably a monocycloalkene ring having 5 or 6 carbon atoms. Examples of monocycloalkene rings include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, and a cyclohexadiene ring.

The "substituents" of the monocycloalkane ring and the monocycloalkene ring include the same as the "substituents" that may be possessed by the aromatic carbon ring in ring Z' described above.

Ring B is a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent. Ring B is preferably a monocycloalkane ring which may have a substituent selected from an alkyl group and an alkenyl group; or a monocycloalkene ring which may have a group selected from an alkyl group and an alkenyl group. Ring B is more preferably a monocycloalkane ring which may have a substituent selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms; or a monocycloalkene ring which may have a group selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms.

i and j each independently represent an integer of 0 or 1 or more, and the sum of i and j is 6 or more (preferably 8 or more, more preferably 10 or more). i and j each preferably independently represent an integer of 0 to 20, and the sum of i and j is 6 or more (preferably 8 or more, more preferably 10 or more). i and j more preferably each independently represent an integer of 1 to 20, and the sum of i and j is 6 or more (preferably 8 or more, more preferably 10 or more). i and j are even more preferably each independently represent an integer of 5 to 10. i and j are particularly preferably 8.

In the second embodiment, the radical polymerizable group-containing compound (E) is particularly preferably represented by formula (3):

[In the formula, R ¹⁰ each independently represents a substituent; ring C each independently represents an aromatic ring which may have a substituent; D ¹ and D ² each independently represent a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO-, or -OCO-; R ^x each independently represents a hydrogen atom or an alkyl group; a each independently represents 0 or 1; b each independently represents 0 or an integer of 1 or more; c each independently represents 0, 1, or 2; m each independently represents 0 or an integer of 1 or more; and other symbols are the same as above.]
The b units, c units and m units may be the same or different from each other.

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 carbocyclic ring having only carbon atoms as ring constituent atoms, or an aromatic heterocyclic ring having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms in addition to carbon atoms as ring constituent atoms, but in one embodiment, it is preferably an aromatic carbocyclic ring. In one embodiment, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 6- to 14-membered aromatic ring, and even more preferably a 6- to 10-membered aromatic ring. Specific examples of suitable aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like, more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

The "substituent" in R ¹⁰ and the "substituent" on the aromatic ring include the same as the "substituent" which the aromatic carbocyclic ring in the above-mentioned ring Z' may have.

Ring C is independently an aromatic ring which may have a substituent, preferably a benzene ring which may be substituted with a group selected from an alkyl group. ^{D 1} and D ² are independently a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO-, or -OCO-, preferably a single bond, -C(R ^x ) ₂ -, or -O-. R ^x is independently a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. a is independently 0 or 1, preferably 0. b is independently an integer of 0 or 1 or more, preferably 0, 1, 2, or 3, more preferably 0, 1, or 2. c is independently 0, 1, or 2, preferably 0. m is an integer of 0 or 1 or more, preferably 0.

Formula (D) contained in formula (3):

[In the formula, * indicates a binding site; other symbols are as above.]
The partial structure represented by the formula (D-1) to (D-3):

[In the formula, * is the same as above.]
Examples of the partial structure include those represented by the following formula:

In the second embodiment, the radical polymerizable group equivalent of the (E) radical polymerizable group-containing compound is preferably 200 g/eq. to 2500 g/eq., more preferably 250 g/eq. to 2000 g/eq., and even more preferably 300 g/eq. to 1500 g/eq. The radical polymerizable group equivalent of the (E) radical polymerizable group-containing compound represents the mass of the resin per equivalent of the radical polymerizable group.

The weight average molecular weight of the radically polymerizable group-containing compound (E) in the second embodiment is preferably 400 to 10,000, more preferably 500 to 7,000, and particularly preferably 600 to 5,000.

Commercially available products of the radically polymerizable group-containing compound (E) in the second embodiment include, for example, "BMI-689," "BMI-1500," "BMI-1700," and "BMI-3000J" manufactured by Designer Molecules, Inc., and "SLK-6895-T90" manufactured by Shin-Etsu Chemical Co., Ltd.

In the third embodiment, the radical polymerizable group-containing compound (E) is preferably represented by formula (4):

[In the formula, R ²⁰ each independently represents a hydrogen atom or an alkyl group; ring E, ring F, and ring G each independently represent an aromatic ring which may have a substituent; Z ¹ each independently represents a single bond, -C(R ^z ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO-; R ^z each independently represents a hydrogen atom or an alkyl group; s represents an integer of 1 or more; each t independently represents 0 or 1; and each u independently represents 0, 1, 2, or 3.]
The maleimide compound according to the third embodiment includes a maleimide compound represented by the formula: wherein the s unit and the u unit may be the same or different for each unit. The maleimide compound according to the third embodiment may be used alone or in combination of two or more types at any ratio.

^R20 each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. Ring E, ring F, and ring G each independently represent an aromatic ring which may have a substituent, 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.

Each ^Z1 independently represents a single bond, -C( ^Rz ) _2- , -O-, -CO-, -S-, -SO-, _-SO2- , -CONH-, or -NHCO-, preferably a single bond, -C( ^Rz ) _2- , or -O-, more preferably a single bond or -C( ^Rz ) _2- , and particularly preferably a single bond. Each ^Rz independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

s represents an integer of 1 or more, preferably an integer from 1 to 10. Each t is independently 0 or 1, preferably 1. Each u is independently 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 1.

In the third embodiment, the radical polymerizable group equivalent of the radical polymerizable group-containing compound (E) is preferably 150 g/eq. to 1000 g/eq., more preferably 200 g/eq. to 500 g/eq.

In the third embodiment, the weight average molecular weight of the radically polymerizable group-containing compound (E) is preferably 100 to 10,000, more preferably 150 to 5,000, and particularly preferably 200 to 3,000.

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

(E) The radically polymerizable group-containing compound may contain any one of the preferred thermoplastic resins in the first embodiment, the preferred maleimide compounds in the second embodiment, and the preferred maleimide compounds in the third embodiment alone, or may contain a combination of two or more of these in any ratio.

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

The content of the (E) radical polymerizable group-containing compound in the resin composition is not particularly limited, but is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% 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 (E) radical polymerizable group-containing compound in the resin composition is not particularly limited, but may be, for example, 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, etc., when the non-volatile components in the resin composition are taken as 100% by mass.

<(F) Thermoplastic resin>
The resin composition of the present invention may further contain a thermoplastic resin (F) as an optional component. The thermoplastic resin (F) is a component other than the epoxy resin (B) described above.

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

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

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

Specific examples of phenoxy resins include Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton); Mitsubishi Chemical's "YX8100" (phenoxy resin containing a bisphenol S skeleton); Mitsubishi Chemical's "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton), Nippon Steel Chemical & Material's "FX280" and "FX293"; Mitsubishi Chemical's "YX7200B35", "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482".

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, with polyvinyl butyral resins being preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd.; and S-LEC BH series, BX series (e.g. BX-5Z), KS series (e.g. KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

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

Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxyl group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, polyphenylene ether-polybutadiene resins, etc.

Specific examples of polyamide-imide resins include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

An example of a polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

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

A specific example of a polyphenylene ether resin is NORYL SA90 manufactured by SABIC. A specific example of a polyetherimide resin is ULTEM manufactured by GE.

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

Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexane dimethyl terephthalate resin, etc.

From the viewpoint of further improving film formability, the weight average molecular weight (Mw) of the (F) thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, particularly preferably 20,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, particularly preferably 50,000 or less.

The content of the (F) thermoplastic resin relative to the total non-volatile components in the resin composition is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, when the total non-volatile components in the resin composition is 100% by mass. The lower limit of the content of the (F) thermoplastic resin relative to the total non-volatile components is not particularly limited, but is, for example, 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, when the total non-volatile components in the resin composition is 100% by mass.

<(G) Curing Accelerator>
The resin composition of the present invention may further contain a curing accelerator (G) as an optional component. The curing accelerator (G) functions as a curing catalyst that accelerates the curing of the epoxy resin (B).

(G) Curing accelerators include, for example, 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. (G) Curing accelerators preferably contain a curing accelerator selected from imidazole-based curing accelerators and amine-based curing accelerators, and more preferably contain an imidazole-based curing accelerator. (G) Curing accelerators may be used alone or in combination of two or more.

Examples of phosphorus-based curing accelerators include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, and tetraphenylphosphine. aromatic phosphonium salts such as sulfonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition products such as triphenylphosphine-p-benzoquinone addition products; tributylphosphine, tri-t Aliphatic phosphines such as 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, ) phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether and other aromatic phosphines.

Examples of urea-based hardening accelerators 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 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].

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

Examples of imidazole-based curing accelerators 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-furan. phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-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, Examples include 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.

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

Metal-based curing accelerators include, for example, 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. Organometallic salts include, for example, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

Commercially available amine-based curing accelerators may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

The content of the (G) curing accelerator in the resin composition is not particularly limited, but is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% 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 (G) 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, etc., when the non-volatile components in the resin composition are taken as 100% by mass.

<(H) Other Additives>
The resin composition of the present invention may further contain any additive. Examples of such additives include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; thermosetting resins other than epoxy resins such as epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, and silicone resins; organic fillers such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, and rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as bentone and montmorillonite; silicone defoamers, acrylic defoamers, fluorine-based defoamers, and the like. defoaming agents such as terbium-based defoaming agents and vinyl resin-based defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent brightening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphine oxide compounds, etc.) Examples of the flame retardants include flame retardants such as mercury oxide, red phosphorus, nitrogen-based flame retardants (e.g. melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g. antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; 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. (H) Other additives may be used alone or in combination of two or more at any ratio. The content of (H) other additives can be appropriately determined by a person skilled in the art.

<(I) Organic Solvent>
The resin composition of the present invention may further contain an arbitrary organic solvent. As the (I) organic solvent, known ones may be appropriately used, and the type is not particularly limited. As the (I) 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 the organic solvent include ether ester solvents such as methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, and the like; ester alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butylcarbitol), and the like; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like; sulfoxide solvents such as dimethyl sulfoxide, and the like; nitrile solvents such as acetonitrile, propionitrile, and the like; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane, and the like; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene, and the like. (I) The organic solvent may be used alone or in any combination of two or more kinds at any ratio.

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

<Method of producing resin composition>
The resin composition of the present invention can be produced, for example, by adding (A) a cyclic carbonate compound, (B) an epoxy resin, (C) an inorganic filler, if necessary (D) an active ester compound, if necessary (D') other curing agents, if necessary (E) a radical polymerizable group-containing compound, if necessary (F) a thermoplastic resin, if necessary (G) a curing accelerator, if necessary (H) other additives, if necessary, and if necessary (I) an organic solvent in any order and/or all at once and mixing them in any preparation vessel. In addition, the temperature can be appropriately set in the process of adding and mixing each component, and heating and/or cooling may be performed temporarily or throughout. In addition, during or after the process of adding and mixing, the resin composition may be stirred or shaken using a stirring device or shaking device such as a mixer to disperse uniformly. In addition, degassing may be performed under low pressure conditions such as under vacuum at the same time as stirring or shaking.

<Characteristics of Resin Composition>
The resin composition of the present invention comprises (A) a cyclic carbonate compound, (B) an epoxy resin, and (C) an inorganic filler, and can provide a cured product that can maintain high peel strength even when exposed to a high-temperature and high-humidity environment and has a low dielectric tangent.

The cured product of the resin composition of the present invention may have the characteristic of being able to retain high peel strength even when exposed to a high temperature and high humidity environment. Thus, in one embodiment, for example, as in the following Test Examples 4 and 5, a copper-plated conductor layer is formed on the cured product, and the copper-plated conductor layer is peeled off in the vertical direction. The peel strength at 25°C calculated from the load may be preferably 0.2 kgf/cm or more, more preferably 0.25 kgf/cm or more, even more preferably 0.3 kgf/cm or more, even more preferably 0.35 kgf/cm or more, and particularly preferably 0.4 kgf/cm or more before the accelerated environmental test (HAST) is performed, whereas after the accelerated environmental test (HAST) is performed for 100 hours under high temperature and high humidity conditions of 130°C and 85% RH, it may be preferably 0.1 kgf/cm or more, more preferably 0.15 kgf/cm or more, even more preferably 0.2 kgf/cm or more, even more preferably 0.25 kgf/cm or more, and particularly preferably 0.3 kgf/cm or more. The upper limit is not particularly limited, but may be, for example, 10 kgf/cm or less before and after the accelerated environmental test (HAST). The decrease rate (%) of the peel strength value before and after the accelerated environmental test (HAST) can be suppressed to preferably 45% or less, more preferably 40% or less, even more preferably 35% or less, even more preferably 30% or less, and particularly preferably 25% or less, or 20% or less. The decrease rate (%) of the peel strength value is calculated as the decrease ratio (%) of the peel strength (kgf/cm) value after the accelerated environmental test (HAST) to the peel strength (kgf/cm) value before the accelerated environmental test (HAST).

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 when measured at 5.8 GHz and 23°C as in Test Example 1 below is not particularly limited, but may be preferably 0.0100 or less, more preferably 0.0080 or less, even more preferably 0.0060 or less, even more preferably 0.0050 or less, or 0.0040 or less, and particularly preferably 0.0035 or less, or 0.0030 or less.

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 when measured at 5.8 GHz and 23°C as in Test Example 1 below is not particularly limited, but may be preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.5 or less, and particularly preferably 3.0 or less.

In one embodiment, the cured product of the resin composition of the present invention may be characterized by excellent mechanical strength. Thus, in one embodiment, the elongation at break of the cured product measured at 23°C in accordance with Japanese Industrial Standard JIS K7127 as in Test Example 2 below is not particularly limited, but may be preferably 0.05% or more, more preferably 0.1% or more, even more preferably 0.15% or more, even more preferably 0.2% or more, and particularly preferably 0.22% or more. The upper limit of the elongation at break is not particularly limited, but may usually be 10% or less, 5% or less, etc.

In one embodiment, the cured product of the resin composition of the present invention may be characterized in that the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is low. Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment measured as in Test Example 3 below is not particularly limited, but may be preferably 500 nm or less, more preferably 400 nm or less, even more preferably 300 nm or less, even more preferably 200 nm or less, and particularly preferably 100 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, etc.

<Applications of resin composition>
The resin composition of the present invention can be suitably used as a resin composition for insulating applications, particularly as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductor layer) 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.

Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring formation layer serving as an insulating layer for forming a rewiring layer (resin composition for forming a rewiring formation 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 on a substrate;
(2) A step of temporarily fixing a semiconductor chip on a temporary fixing film;
(3) forming an encapsulation layer on the semiconductor chip;
(4) peeling the substrate and the temporary fixing film from the semiconductor chip;
(5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) forming a rewiring layer as a conductor layer on the rewiring formation layer.

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

<Sheet-like laminate 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.

The following resin sheets and prepregs are preferred as sheet-like laminate materials.

In one embodiment, the resin sheet comprises 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.

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 insulating properties 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.

Examples of the support include films made of plastic materials, metal foils, and release paper, with films made of plastic materials and metal foils being preferred.

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

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. 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.

The support may be subjected to a matte treatment, corona treatment, or antistatic treatment on the surface that is to be bonded to the resin composition layer.

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. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support with a release layer may be a commercially available product, such as "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, "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.

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 using a support with a release layer, it is preferable that the thickness of the entire support with the release layer is in the above range.

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 similar to the support provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dirt and the like and scratches on the surface of the resin composition layer.

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

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.

Drying may be performed by known methods such as heating or blowing hot air. There are no particular limitations on the drying conditions, but drying is performed so that the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition, for example, when using a resin composition containing 30% by mass to 60% by mass of organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

The resin sheet can be stored in a roll. If the resin sheet has a protective film, it can be used by peeling off the protective film.

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

The sheet-like fiber substrate used for the prepreg is not particularly limited, and may be any commonly used substrate for prepregs, such as glass cloth, aramid nonwoven fabric, or liquid crystal polymer nonwoven fabric. From the viewpoint of making the printed wiring board thinner, 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. There is no particular lower limit to the thickness of the sheet-like fiber substrate. It is usually 10 μm or more.

Prepregs can be manufactured by known methods such as the hot melt method and the solvent method.

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

The sheet-like laminate material of the present invention can be suitably used to form an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be even more suitably used to form an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).

<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.

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

The "inner layer substrate" used in step (I) is a member that will be the substrate of the printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and 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, intermediate products on which an insulating layer and/or a conductor layer is to be formed during the manufacture of a printed wiring board are 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.

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

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 heat-pressure bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heat-pressure bonding 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 heat-pressure bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination may be performed under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., and a batch type vacuum pressure laminator.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example by pressing a heat-pressure bonding member from the support side. The pressing conditions for the smoothing treatment may be the same as the heat-pressure bonding conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. Note that lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

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

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

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

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, and 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.

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

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.

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, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined depending on the design of the printed wiring board.

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 for 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.

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.

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 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.

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 is an example.

Treatment with a neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the standpoint of workability, etc., it is preferable to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

In one embodiment, 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. There is no particular limit to the lower limit, and it can be, for example, 1 nm or more, 2 nm or more, etc. The root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

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, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

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 types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of ease of production, it is preferable to form the conductor layer by a semi-additive method. Below, an example of forming the conductor layer by a semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and the mask pattern is then removed. Thereafter, unnecessary plating seed layer is removed by etching or the like, and a conductor layer having the desired wiring pattern can be formed.

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 perform 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 performed by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, 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.

Metal foils can be manufactured by known methods such as electrolysis and rolling. Commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

<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.

Semiconductor devices include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft).

The present invention will be specifically explained 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. If no temperature is specified, the temperature condition is room temperature (23°C), and if no pressure is specified, the pressure condition is atmospheric pressure (1 atm).

Example 1
15 parts of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) was heated and dissolved in 20 parts of solvent naphtha while stirring. This was cooled to room temperature to prepare an epoxy resin solution composition. To this epoxy resin solution composition, 2 parts of a cyclic carbonate compound 1 ("4,4,6-trimethyl-1,3-dioxane-2-one" manufactured by JNC Corporation, a compound represented by formula (A4)), 45 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, active ester group equivalent of about 223 g/eq., toluene solution with a non-volatile content of 65%), and spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 ^m2) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) were added. /g) 130 parts, triazine skeleton-containing phenolic curing agent (DIC Corporation "LA-3018-50P", active group equivalent of about 151 g / eq., 2-methoxypropanol solution with non-volatile content of 50%) 3 parts, carbodiimide curing agent (Nisshinbo Chemical Co., Ltd. "V-03", active group equivalent of about 216 g / eq., toluene solution with non-volatile content of 50%) 8 parts, imidazole curing accelerator (Shikoku Chemical Industry Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole) 0.2 parts, phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", 1:1 solution of MEK and cyclohexanone with non-volatile content of 30% by mass) 2.5 parts were mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin composition.

Example 2
A resin composition was prepared in the same manner as in Example 1, except that 15 parts of a naphthalene type epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of about 145 g/eq.) was used instead of 15 parts of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd.) and the amount of cyclic carbonate compound 1 ("4,4,6-trimethyl-1,3-dioxane-2-one" manufactured by JNC Corporation) was changed from 2 parts to 4 parts.

Example 3
Instead of 2 parts of the cyclic carbonate compound 1 ("4,4,6-trimethyl-1,3-dioxane-2-one" manufactured by JNC Corporation), 1 part of the cyclic carbonate compound 2 ("DEPPO" manufactured by JNC Corporation, a compound represented by formula (A11)) and 1 part of the cyclic carbonate compound 3 ("DXC" manufactured by JNC Corporation, a compound represented by formula (A10)) were used, and an active ester compound ("HPC-8000" manufactured by DIC Corporation) was used. A resin composition was prepared in the same manner as in Example 1, except that 45 parts of an active ester compound (DIC Corporation's "HPC-8150-62T", active ester group equivalent weight of about 220 g/eq., toluene solution with non-volatile content of 62 mass%) was used instead of 45 parts of the active ester compound (DIC Corporation's "HPC-8150-62T", active ester group equivalent weight of about 220 g/eq., non-volatile content of 62 mass%) and the amount of spherical silica (Admatechs Corporation's "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m ² /g) surface-treated with a silane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM-573") was changed from 130 parts to 155 parts.

Example 4
Instead of 15 parts of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd.), 12 parts of naphthol-type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: about 330 g/eq.) and 3 parts of bisphenol-type epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent: about 169 g/eq.) were used to prepare a cyclic carbonate compound 1 ("4,4,6-trimethylsilyl 1,3-diphenyl-2,4 ... Instead of 2 parts of cyclic carbonate compound 3 ("DXC" manufactured by JNC Corporation), 2 parts of methyl-1,3-dioxane-2-one were used, and instead of 45 parts of active ester compound ("HPC-8000-65T" manufactured by DIC Corporation), 45 parts of active ester compound ("HPC-8150-62T" manufactured by DIC Corporation, active ester group equivalent of about 220 g/eq., non-volatile component ratio of 62% by mass in toluene solution) were used. A resin composition was prepared in the same manner as in Example 1.

Example 5
A resin composition was prepared in the same manner as in Example 4, except that 2 parts of cyclic carbonate compound 4 (a compound represented by formula (A16) synthesized by a method similar to that described in Example 13 of Japanese Patent No. 6,141,261) was used instead of 2 parts of cyclic carbonate compound 3 ("DXC" manufactured by JNC Corporation).

Example 6
A resin composition was prepared in the same manner as in Example 4, except that 2 parts of cyclic carbonate compound 5 (a compound represented by formula (A17) synthesized by a method similar to that described in the Examples of JP2018-118946A) was used instead of 2 parts of cyclic carbonate compound 3 ("DXC" manufactured by JNC Corporation).

Example 7
A resin composition was prepared in the same manner as in Example 1, except that 45 parts of an active ester compound (DIC Corporation's "HPC-8150-62T", active ester group equivalent of about 220 g/eq., toluene solution with non-volatile content of 62% by mass) was used instead of 45 parts of the active ester compound (DIC Corporation's "HPC-8000-65T"), and 4 parts of a biphenylaralkyl novolac type maleimide (Nippon Kayaku Co., Ltd.'s "MIR-3000-70MT", MEK/toluene mixed solution with non-volatile content of 70%) was used.

Example 8
A resin composition was prepared in the same manner as in Example 7, except that 15 parts of a naphthalene type epoxy resin (DIC Corporation's "HP-4032-SS", 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of about 145 g/eq.) was used instead of 15 parts of a biphenyl type epoxy resin (Nippon Kayaku Co., Ltd.'s "NC3000L"), and 3 parts of a maleimide-terminated polyimide compound (DMI Corporation's "BMI-1500") was used instead of 4 parts of a biphenyl aralkyl novolac type maleimide (Nippon Kayaku Co., Ltd.'s "MIR-3000-70MT", MEK/toluene mixed solution with a non-volatile content of 70%).

<Example 9>
Instead of 15 parts of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd.), 12 parts of naphthol-type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 330 g / eq.) and 3 parts of bisphenol-type epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of about 169 g / eq.) were used, and instead of 4 parts of biphenylaralkylnovolac-type maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.), 3 parts of methacrylic-modified polyphenylene ether ("SA9000-111" manufactured by SABIC Innovative Plastics Co., Ltd.) were used. A resin composition was prepared in the same manner as in Example 7.

Example 10
A resin composition was prepared in the same manner as in Example 7, except that the amount of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd.) used was changed from 15 parts to 10 parts, and further, 5 parts of a naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of about 145 g/eq.) was used, and 4 parts of a vinylbenzyl-modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with a non-volatile content of 65%) was used in place of 4 parts of a biphenylaralkylnovolac-type maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.).

Example 11
A resin composition was prepared in the same manner as in Example 1, except that the amount of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd.) used was changed from 15 parts to 10 parts, 5 parts of naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of about 145 g/eq.) was used, the amount of spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m ² /g) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 130 parts to 100 parts, and 7 parts of hollow aluminosilicate particles ("MG-005" manufactured by Taiheiyo Cement Corporation, average particle size 1.6 μm, porosity 80% by volume) were used.

<Comparative Example 1>
A resin composition was prepared in the same manner as in Example 1, except that 2 parts of the cyclic carbonate compound 1 ("4,4,6-trimethyl-1,3-dioxane-2-one" manufactured by JNC Corporation) was not used.

<Comparative Example 2>
A resin composition was prepared in the same manner as in Example 8, except that 2 parts of the cyclic carbonate compound 1 ("4,4,6-trimethyl-1,3-dioxane-2-one" manufactured by JNC Corporation) and 3 parts of the maleimide-terminated polyimide compound ("BMI-1500" manufactured by DMI Corporation) were not used, and the amount of spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m ² /g) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 130 parts to 150 parts.

<Comparative Example 3>
Instead of 15 parts of naphthalene-type epoxy resin (DIC Corporation's "HP-4032-SS", 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent of about 145 g/eq.), 12 parts of naphthol-type epoxy resin (Nippon Steel Sumikin Chemical Co., Ltd.'s "ESN475V", epoxy equivalent of about 330 g/eq.) and 12 parts of bisphenol-type epoxy resin (Nippon Steel Sumikin Chemical Co., Ltd.'s "ZX1059", 1:1 mixture of bisphenol A type and bisphenol F type) were used. 1 mixture, epoxy equivalent of about 169 g/eq.) was used, 45 parts of an active ester compound (DIC Corporation's "HPC-8150-62T", active ester group equivalent of about 220 g/eq., toluene solution with non-volatile content of 62% by mass) was reduced from 45 parts to 20 parts, and further 150 parts of spherical silica (Admatechs Corporation's "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m ² /g) surface-treated with a silane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM-573") was reduced to 90 parts. A resin composition was prepared in the same manner as in Comparative Example 2, except for the above points.

<Comparative Example 4>
A resin composition was prepared in the same manner as in Comparative Example 2, except that the amount of spherical silica (Admatechs' SO-C2, average particle size 0.5 μm, specific surface area 5.8 ^m2 /g) surface-treated with a silane coupling agent (Shin-Etsu Chemical's KBM-573) was changed from 150 parts to 125 parts, and 2 parts of a polyester compound (Showa Denko Materials' Teslac 5001-40T, number average molecular weight 27,000, toluene solution with non-volatile content of 40% by mass) was used.

<Production Example 1: Production of resin sheet>
A polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. The resin compositions obtained 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 obtain a resin sheet including a support and a resin composition layer.

<Test Example 1: Measurement of relative dielectric constant (Dk) and dielectric loss tangent (Df)>
The protective film was peeled off from the resin sheet produced in Production Example 1, and the resin composition layer was thermally cured by heating at 200°C for 90 minutes, and then the support was peeled off to obtain a cured film formed of the cured product of the resin composition. No cured film was obtained for Comparative Example 4. The cured film was cut into a width of 2 mm and a length of 80 mm to obtain a cured product A for evaluation.

The dielectric constant (Dk value) and dielectric loss tangent (Df value) of the obtained cured product A for evaluation were measured by the cavity resonance perturbation method using an Agilent Technologies "HP8362B" at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurements were performed on three test pieces, and the average value was calculated.

<Test Example 2: Measurement of elongation at break>
For the cured product A for evaluation obtained in the same manner as in Test Example 1, a tensile test was carried out in accordance with Japanese Industrial Standard JIS K7127 at 23°C using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Co., Ltd.) to measure the elongation at break (%).

<Test Example 3: Measurement of arithmetic mean roughness (Ra)>
(1) Surface treatment of the interior substrate A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic "R1515A") having copper foil on the surface was prepared as the inner layer substrate. The copper foil on the surface of this inner layer substrate was etched with a microetching agent (Mech "CZ8101") with a copper etching amount of 1 μm to perform a roughening treatment. Then, it was dried at 190° C. for 30 minutes.

(2) Lamination and curing of resin sheet The resin sheet prepared in Production Example 1 was laminated on both sides of the inner layer substrate using a batch type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) so that the resin composition layer was bonded to the inner layer substrate. This lamination was performed by reducing the pressure for 30 seconds to 13 hPa or less, and then pressing at a temperature of 100°C and a pressure of 0.74 MPa for 30 seconds.

The laminated resin sheet was then heat pressed at atmospheric pressure at 100°C and a pressure of 0.5 MPa for 60 seconds to smooth it out. It was then placed in a 130°C oven and heated for 30 minutes, and then transferred to a 170°C oven and heated for 30 minutes.

(3) Formation of via holes Using a _CO2 laser processing machine (LK-2K212/2C) manufactured by Via Mechanics, the insulating layer was processed under the conditions of a frequency of 2000 Hz, a pulse width of 3 μs, an output of 0.95 W, and a shot number of 3, to form via holes with a top diameter (diameter) of 50 μm on the insulating layer surface and a diameter of 40 μm on the insulating layer bottom surface. After that, the PET film was peeled off.

(4) Roughening Treatment The inner layer substrate was immersed in a swelling liquid, Swelling Dip Securigant P, manufactured by Atotech Japan, for 10 minutes at 60° C. Next, it was immersed in a roughening liquid, Concentrate Compact P, manufactured by Atotech Japan (aqueous solution of KMnO ₄ : 60 g/L, NaOH: 40 g/L), for 20 minutes at 80° C. Finally, it was immersed in a neutralizing liquid, Reduction Solution Securigant P, manufactured by Atotech Japan, for 5 minutes at 40° C. The obtained substrate was designated as evaluation substrate A.

(5) Measurement of arithmetic mean roughness (Ra) The Ra value of the obtained evaluation substrate A was obtained using a non-contact surface roughness meter (WYKO NT3300 manufactured by B-CO Instruments) in VSI mode with a 50x lens over a measurement range of 121 μm×92 μm. Each was measured by calculating the average value of 10 randomly selected points.

<Test Example 4: Measurement of peel strength of plated conductor layer before HAST test>
The evaluation substrate A obtained in the same manner as in Test Example 3 (4) was immersed in an electroless plating solution containing _PdCl2 at 40 ° C for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C for 20 minutes. After heating at 150 ° C for 30 minutes to perform an annealing treatment, an etching resist was formed, and after forming a pattern by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 μm. Next, the substrate obtained by performing an annealing treatment at 200 ° C for 60 minutes was used as the evaluation substrate B.

A 10 mm wide, 150 mm long cut was made in the conductor layer of the obtained evaluation board B in a portion not including a via hole, and one end of this cut was peeled off and held with a gripper (TSE Autocom type testing machine AC-50C-SL), and the load (kgf/cm) was measured when 100 mm was peeled off vertically at a speed of 50 mm/min at room temperature (25°C).

<Test Example 5: Measurement of peel strength of plated conductor layer after HAST test>
Evaluation board B, which was prepared in the same manner as in Test Example 4, was subjected to 100 hours of accelerated environmental testing (HAST) under high temperature and high humidity conditions of 130°C and 85%RH using a highly accelerated life tester (Kusumoto Chemical Industries, Ltd., "PM422"). After that, a notch was made in the evaluation board B after HAST in the same manner as above, and one end of the notch was peeled off and gripped with the gripper of the tensile tester in the same manner as in Test Example 4, and the load (kgf/cm) was measured when 35 mm was peeled off in the vertical direction at a speed of 50 mm/min at room temperature (normal temperature). The measurement was performed in accordance with Japanese Industrial Standard JIS C6481.

The amounts of raw materials used in the resin compositions of each Example and Comparative Example, and the measurement results of the test examples are summarized in Table 1 below.

From the results shown in Table 1 above, it can be seen that when a cyclic carbonate compound (A) is used in a resin composition containing an epoxy resin (B) and an inorganic filler (C), a cured product can be obtained that retains high peel strength even after a HAST test and has a low dielectric tangent, compared to when a cyclic carbonate compound (A) is not used. It can also be seen that in Example 11, which contains a hollow inorganic filler as the inorganic filler (C), the relative dielectric constant is further reduced compared to Example 1.

Claims (20)

A resin composition comprising (A) a cyclic carbonate compound, (B) an epoxy resin, and (C) an inorganic filler,
The component (C) contains silica,
The component (A) is represented by formula (1):

[Wherein,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent (1) a hydrogen atom, (2) an alkyl group which may be substituted with a group selected from RO-, RCO-, RCOO- and ROCO-, (3) an alkenyl group which may be substituted with a group selected from RO-, RCO-, RCOO- and ROCO-, (4) an aralkyl group which may be substituted with a group selected from R-, RO-, RCO-, RCOO- and ROCO-, or (5) a group represented by formula (2-1):

or (6) a group represented by formula (2-2):

represents a group represented by
R ^1' , R ^2' , R ^3' , R ^4' , R ^5' and R ^6' each independently represent (1) a hydrogen atom, (2) an alkyl group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, (3) an alkenyl group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, or (4) an aralkyl group which may be substituted with a group selected from R-, RO-, RCO-, RCOO-, and ROCO-;
A ¹ and A ² each independently represent -O-, -CO-, -COO-, or -OCO-;
X and Y each independently represent (1) an alkylene group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, or (2) an alkenylene group which may be substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-;
R each independently represents an alkyl group, an alkenyl group, an aralkyl group, or an aryl group, each of which may be substituted with a group selected from a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an aralkyl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an aralkyl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, and an aralkyl-carbonyl-oxy group;
Z's each independently represent a divalent hydrocarbon group which may have a substituent;
n represents 0, 1, 2, or 3;
* indicates the binding site.]
A resin composition comprising a compound represented by the formula : The resin composition according to claim 1, further comprising (D) an active ester compound. The resin composition according to claim 2, wherein the content of component (A) is 1% by mass to 10% by mass, where the total amount of components (A), (B), and (D) is taken as 100% by mass. The resin composition according to claim 2 or 3, wherein the content of component (D) is 12% by mass or more, assuming that the non-volatile components in the resin composition are 100% by mass. In formula (1), R ¹ , R ² , R ⁵ and R ⁶ are each independently (1) a hydrogen atom or (2) an alkyl group having 1 to 10 carbon atoms;
In formula (2-1) and formula (2-2), R ^1' , R ^2' , R ^5' and R ^6' are each independently (1) a hydrogen atom, or (2) an alkyl group having 1 to 10 carbon atoms. The resin composition according to any one of claims 1 to 5, wherein the compound represented by formula (1) in the component (A) is a compound selected from the compounds represented by formulas (A1) to (A17).

The resin composition according to any one of claims 1 to 6, wherein the content of component (B) is 1% by mass to 20% by mass, assuming that the non-volatile components in the resin composition are 100% by mass. The resin composition according to any one of claims 1 to 7, wherein the average particle size of the (C) component is 0.2 µm or more. The resin composition according to any one of claims 1 to 8, wherein the content of the component (C) is 5% by mass or more, based on 100% by mass of non-volatile components in the resin composition. The resin composition according to any one of claims 1 to 9 , wherein the content of the component (C) is 60 mass% or more, based on 100 mass% of non-volatile components in the resin composition. The resin composition according to any one of claims 1 to 10 , further comprising a curing agent selected from the group consisting of phenol-based curing agents and carbodiimide-based curing agents. The resin composition according to any one of claims 1 to 11 , wherein a dielectric loss tangent (Df) of a cured product of the resin composition is 0.0030 or less when measured at 5.8 GHz and 23°C. The resin composition according to any one of claims 1 to 12 , wherein the elongation at break of a cured product of the resin composition is 0.2% or more when measured at 23°C in accordance with JIS K7127. The resin composition according to any one of claims 1 to 13 , which is for forming an insulating layer for forming a conductor layer. The resin composition according to any one of claims 1 to 13 , which is used for forming an insulating layer of a printed wiring board. A cured product of the resin composition according to any one of claims 1 to 15 . A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 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 15 provided on the support. 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 15 . A semiconductor device comprising the printed wiring board according to claim 19 .