JP2023077967A - resin composition - Google Patents

Abstract

To provide a resin composition capable of giving a cured product that can keep high peel strength even under high-temperature and high-humidity conditions, with its dielectric loss tangent being kept low.SOLUTION: A resin composition comprises (A) a cyclic carbonate compound, (B) an epoxy resin, and (C) an inorganic filler.SELECTED DRAWING: None

Description

The present invention relates to resin compositions containing epoxy resins. Furthermore, it relates to a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

2. Description of the Related Art As a technique for manufacturing printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing a resin composition containing an epoxy resin or an inorganic filler. In recent years, as the wiring of printed wiring boards has become finer and denser, and the frequency of signals has increased, further reduction of the dielectric loss tangent of the insulating layer has been demanded. In addition, since printed wiring boards are generally exposed to high temperature and high humidity environments, peel strength resistance to high temperature and high humidity environments is also required.

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

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

An object of the present invention is to provide a resin composition that can maintain high peel strength even when exposed to a high-temperature, high-humidity environment and that can provide a cured product with a low dielectric loss tangent.

In order to achieve the object of the present invention, the present inventors have made intensive studies, and found that by using (A) a cyclic carbonate compound in a resin composition containing (B) an epoxy resin and (C) an inorganic filler, Surprisingly, the present inventors have found that a cured product can be obtained that can maintain high peel strength even when exposed to a high-temperature, high-humidity environment and whose dielectric loss tangent is kept low, leading to the completion of the present invention.

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

[In the formula,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a group selected from (1) a hydrogen atom, (2) RO—, RCO—, RCOO— and ROCO— an optionally substituted alkyl group, (3) an alkenyl group optionally substituted by a group selected from RO—, RCO—, RCOO—, and ROCO—, (4) R—, RO—, RCO—, RCOO-, and an aralkyl group optionally substituted with a group selected from ROCO-, (5) formula (2-1):

or (6) formula (2-2):

showing a group represented by;
R ^1′ , R ^2′ , R ^3′ , R ^4′ , R ^5′ and R ^6′ are each independently (1) a hydrogen atom, (2) RO—, RCO—, RCOO— and ROCO an alkyl group optionally substituted by a group selected from -, (3) RO-, RCO-, RCOO-, and an alkenyl group optionally substituted by a group selected from ROCO-, or (4) R- , RO-, RCO-, RCOO-, and an aralkyl group optionally substituted with a group selected from ROCO-;
A ¹ and A ² each independently represent -O-, -CO-, -COO- or -OCO-;
X and Y are each independently (1) an alkylene group optionally substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, or (2) RO-, RCO-, RCOO -, and represents an alkenylene group optionally substituted with a group selected from ROCO-;
Each R is independently 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. , alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, aralkyl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy group, aryl-carbonyl-oxy group, and an alkyl group, an alkenyl group, an aralkyl group, or an aryl group, each optionally substituted with a group selected from an aralkyl-carbonyl-oxy group;
Z each independently represents 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 [1] to [5] above, comprising a compound represented by
[7] Any one of [1] to [6] above, wherein the content of component (B) is 1% by mass to 20% by mass when the non-volatile component in the resin composition is 100% by mass. of the resin composition.
[8] The resin composition according to any one of [1] to [7] above, wherein the content of component (C) is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass. thing.
[9] The resin composition according to any one of [1] to [8] above, further comprising a curing agent selected from the group consisting of phenol-based curing agents and carbodiimide-based curing agents.
[10] The resin according to any one of [1] to [9] above, wherein the cured product of the resin composition has a dielectric loss tangent (Df) of 0.0030 or less when measured at 5.8 GHz and 23°C. Composition.
[11] Any one of the above [1] to [10], wherein the cured product of the resin composition has an elongation at break of 0.2% or more when measured at 23° C. according to JIS K7127. of the resin composition.
[12] The resin composition according to any one of [1] to [11] above, which is used 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 described in 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] provided on the support.
[17] A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of [1] to [13] above.
[18] A semiconductor device including the printed wiring board according to [17] above.

INDUSTRIAL APPLICABILITY According to the resin composition of the present invention, it is possible to obtain a cured product that can maintain high peel strength even when exposed to a high-temperature and high-humidity environment and that has a low dielectric loss tangent.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

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

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

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

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

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

Including the compound represented by.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a group selected from (1) a hydrogen atom, (2) RO—, RCO—, RCOO— and ROCO— an optionally substituted alkyl group, (3) an alkenyl group optionally substituted by a group selected from RO—, RCO—, RCOO—, and ROCO—, (4) R—, RO—, RCO—, RCOO-, and an aralkyl group optionally substituted with a group selected from ROCO-, (5) formula (2-1):

or (6) formula (2-2):

represents a group represented by * indicates the binding site.

Alkyl (group) means a linear, branched and/or cyclic monovalent saturated aliphatic hydrocarbon group. 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 an alkyl (group) having 1 to 6 carbon atoms, unless otherwise specified. ) is more preferred. Examples of alkyl (group) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, sec-pentyl group and neopentyl group. , tert-pentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, tert-octyl group, cyclopentyl group, cyclohexyl group and the like.

Alkenyl (group) means a linear, branched and/or cyclic monovalent aliphatically unsaturated hydrocarbon group having at least one carbon-carbon double bond. Alkenyl (group), unless otherwise specified, is preferably an alkenyl (group) having 2 to 14 carbon atoms, more preferably an alkenyl (group) having 2 to 10 carbon atoms, and an alkenyl (group) having 2 to 6 carbon atoms. More preferred. Examples of alkenyl (group) include vinyl group, propenyl group (allyl group, 1-propenyl group, isopropenyl group), butenyl group (1-butenyl group, crotyl group, methallyl group, isocrotyl group, etc.), pentenyl group ( 1-pentenyl group, etc.), hexenyl group (1-hexenyl group, etc.), heptenyl group (1-heptenyl group, etc.), octenyl group (1-octenyl group, etc.), cyclopentenyl group (2-cyclopentenyl group, etc.), cyclo hexenyl group (3-cyclohexenyl group, etc.) and the like.

Aryl (group) means a monovalent aromatic hydrocarbon group having one hydrogen atom removed from an aromatic carbocyclic ring. The aryl (group) is preferably an aryl (group) having 6 to 14 carbon atoms, particularly preferably an aryl (group) having 6 to 10 carbon atoms, unless otherwise specified. Aryl (group) includes, for example, phenyl group, 1-naphthyl group, 2-naphthyl group and the like.

Aralkyl (group) means an alkyl group substituted with one or more (preferably one) aryl group. Aralkyl (group) is preferably an aralkyl (group) having 7 to 15 carbon atoms, particularly preferably an aralkyl (group) having 7 to 11 carbon atoms, unless otherwise specified. Aralkyl (group) includes, for example, benzyl group, phenethyl group, hydrocinnamyl group, α-methylbenzyl group, α-cumyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like.

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

R ³ and R ⁴ are, in one embodiment, each independently preferably substituted with a group selected from (1) a hydrogen atom, (2) 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 optionally substituted with RO—, (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, or (3) a group represented by formula (2-2).

R ^1′ , R ^2′ , R ^3′ , R ^4′ , R ^5′ and R ^6′ are each independently (1) a hydrogen atom, (2) RO—, RCO—, RCOO— and ROCO an alkyl group optionally substituted by a group selected from -, (3) RO-, RCO-, RCOO-, and an alkenyl group optionally substituted by a group selected from ROCO-, or (4) R- , RO--, RCO--, RCOO--, and aralkyl group optionally substituted with a group selected from 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) RO— , RCO—, RCOO—, and an alkyl group optionally substituted by a group selected from ROCO—; more preferably (1) a hydrogen atom, or (2) an alkyl optionally substituted by RO— is particularly preferably (1) a hydrogen atom or (2) an alkyl group.

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

X and Y are each independently (1) an alkylene group optionally substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, or (2) RO-, RCO-, RCOO -, and represents an alkenylene group optionally substituted with a group selected from ROCO-.

Alkylene (group) refers to a linear, branched and/or cyclic divalent aliphatic saturated hydrocarbon group. Alkylene (group), unless otherwise specified, is preferably an alkylene (group) having 1 to 14 carbon atoms, more preferably an alkylene (group) having 1 to 10 carbon atoms, still more preferably a carbon atom It is an alkylene (group) of numbers 1 to 6. Examples of alkylene (group) include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched chain alkylene groups such as an ethylidene group, a propylidene group, an isopropylidene group, an ethylmethylmethylene group, and a diethylmethylene group;

Alkenylene (group) means a straight-chain, branched-chain and/or cyclic divalent unsaturated aliphatic hydrocarbon group having at least one carbon-carbon double bond. Alkenyl (group), unless otherwise specified, is preferably an alkenylene (group) having 2 to 14 carbon atoms, more preferably an alkenylene (group) having 2 to 10 carbon atoms, and an alkenylene (group) having 2 to 6 carbon atoms. More preferred. Examples of alkenylene (group) 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.

X and Y are, in one embodiment, each independently preferably an alkylene group optionally substituted by a group selected from RO-, RCO-, RCOO- and ROCO-; It is an alkylene group optionally substituted with RO-; more preferably an alkylene group.

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

Each R, in one embodiment, is independently preferably an alkyl group, an alkenyl group, an aralkyl group, or an aryl group, more preferably an alkyl group.

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

A divalent hydrocarbon group is a divalent hydrocarbon group having only one or more (eg, 1 to 100, 2 to 50, 2 to 30) carbon atoms as skeleton atoms. A 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 containing no aromatic ring or a hydrocarbon group containing 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 group, alkenylene-non-aromatic carbocyclic-alkenylene group, aromatic carbocyclic-aromatic carbocyclic group, non-aromatic carbocyclic-non-aromatic carbocyclic group, aromatic carbocyclic -alkylene-aromatic carbocyclic group, aromatic carbocyclic ring-alkenylene-aromatic carbocyclic group, aromatic carbocyclic ring-aromatic carbocyclic ring-aromatic carbocyclic group, aromatic carbocyclic ring-non-aromatic carbocyclic ring-aromatic carbocyclic group, non-aromatic carbocyclic-alkylene-non-aromatic carbocyclic group, non-aromatic carbocyclic-alkylene-non-aromatic carbocyclic group, non-aromatic carbocyclic-aromatic carbocyclic-non-aromatic carbon cyclic group, non-aromatic carbocyclic-non-aromatic carbocyclic-non-aromatic carbocyclic group, etc., wherein the non-aromatic carbocyclic ring may be condensed with an aromatic carbocyclic ring; , an alkenyl group and an aryl group, the aromatic carbocyclic ring may be condensed with a non-aromatic carbocyclic ring, and a group selected from an alkyl group, an alkenyl group and an aryl group. may be substituted.

An aromatic carbocyclic ring means a carbocyclic ring having 4p+2 (p is a natural number) electrons contained in the π-electron system on the ring and conforming to Hückel's rule. Aromatic carbocycles have only carbon atoms as ring atoms. In one embodiment, the aromatic carbocyclic ring is preferably a 6- to 14-membered aromatic carbocyclic ring, more preferably a 6- to 10-membered aromatic carbocyclic ring. Preferred specific examples of the aromatic carbocyclic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and the like, more preferably benzene ring or naphthalene ring, and particularly preferably benzene ring.

A non-aromatic carbocyclic ring is a carbocyclic ring that is not an aromatic carbocyclic ring having aromaticity throughout the ring. Non-aromatic carbocycles have only carbon atoms as ring atoms. The non-aromatic carbocyclic ring can be a saturated carbocyclic ring consisting only of a single bond, or a non-aromatic unsaturated carbocyclic ring having at least one of a double bond and a triple bond. The non-aromatic carbocyclic ring is preferably a non-aromatic carbocyclic ring having 3 to 20 carbon atoms, more preferably a non-aromatic carbocyclic ring having 4 to 15 carbon atoms, and a non-aromatic carbocyclic ring having 4 to 10 carbon atoms. is more preferred. Preferred specific examples of non-aromatic carbocyclic rings include cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, and cyclotridecane. monocyclic saturated carbocyclic rings such as ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring; bicyclo[2.2.1]heptane ring (norbornane ring), bicyclo[4.4.0]decane ring (decane ring), bicyclo[5.3.0]decane ring, bicyclo[4.3.0]nonane ring (hydrindane ring), bicyclo[3.2.1]octane bicyclic saturated carbocyclic ring such as ring, bicyclo[5.4.0]undecane ring, bicyclo[3.3.0]octane ring, bicyclo[3.3.1]nonane ring; tricyclo[5.2. 1.0 ^2,6 ]decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 ^3,7 ]decane ring (adamantane ring), tricyclo[6.2.1.0 ^2,7 ] tricyclic saturated carbocyclic ring such as undecane ring; tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]tetracyclic saturated carbocyclic ring such as dodecane ring; pentacyclo[9.2.1.1 ^4,7 . 0 ^2,1 0.0 ^3,8 ]pentadecane ring, pentacyclo[6.5.1.1 ^3,6 . 0 ^{2, 7} . 0 ^9,13 ]pentadecane ring (tetrahydrotricyclopentadiene ring) and other pentacyclic saturated carbocyclic rings.

The "substituent" that the divalent hydrocarbon group in Z may have is not particularly limited, but for example, a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group , aralkyl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, aralkyl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, aralkyl-oxy -carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy group, aryl-carbonyl-oxy group, aralkyl-carbonyl-oxy group, formula (Z-1):

A group represented by the formula (Z-2):

Groups represented by and the like. * indicates the binding 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) RO—, RCO— , RCOO-, and an alkyl group optionally substituted by a group selected from ROCO-, (3) an alkenyl group optionally substituted by a group selected from RO-, RCO-, RCOO-, and ROCO-, or (4) an aralkyl group optionally substituted with a group selected from R-, RO-, RCO-, RCOO-, and ROCO-, and in one embodiment, the preferred range is R ^1' , R ^2′ , R ^3′ , R ^4′ , R ^5′ and R ^6′ .

A ³ each independently represents -O-, -CO-, -COO-, or -OCO-, and in one embodiment, the preferred range is the same as A ¹ and A ² .

Y' is each independently an alkylene group optionally substituted with a group selected from (1) RO-, RCO-, RCOO-, and ROCO-, or (2) RO-, RCO-, RCOO- , and ROCO—, and in one embodiment, the preferred ranges are the same as those for X and Y.

Z are, in one embodiment, each independently preferably of formula (Z1):

is a group represented by; more preferably formula (Z2):

is a group represented by; more preferably formulas (Z3-1) to (Z3-36):

is a group represented by any one of; particularly preferably a group represented by formula (Z3-25). * indicates the binding site.

Ring Z ^a and ring Z ^b each independently represent an optionally substituted aromatic carbocyclic ring. In one embodiment, ring Z ^a and ring Z ^b are each independently preferably a benzene ring optionally having a substituent, more preferably a benzene optionally substituted with an alkyl group It is a ring, particularly preferably a (unsubstituted) benzene ring.

X ^z represents a single bond or -CR ^z1 R ^z2 -, and in one embodiment is preferably -CR ^z1 R ^z2 -.

n ^z represents 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1 in one embodiment. The ^nz units may be the same or different for each unit.

R ^z1 and R ^z2 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group , or represents an optionally substituted aralkyl group, or R ^z1 and R ^z2 are bonded together, optionally substituted and fused with an aromatic carbocyclic ring represents a non-aromatic carbocyclic ring. R ^z1 and R ^z2 are, in one embodiment, R ^z1 and R ^z2 joined together, preferably an optionally substituted non-substituted aromatic carbocyclic ring. It is an aromatic carbocyclic ring, more preferably an optionally substituted monocyclic saturated carbocyclic ring optionally condensed with a benzene ring, particularly preferably condensed with a benzene ring. cyclopentane ring.

Each ^Rz independently represents a substituent. Each R ^z is, in one embodiment, independently preferably an alkyl group.

A "substituent" that the aromatic carbocyclic ring in ring Z ^a and ring Z ^b may have, an alkyl group, an alkenyl group, an aryl group, an aralkyl group and an aromatic carbocyclic ring in R ^z1 and R ^z2 The "substituent" that the optionally non-aromatic carbocyclic ring may have and the "substituent" in R ^z are not particularly limited, but examples include halogen atoms, alkyl groups, alkenyl groups , aryl group, aralkyl group, alkyl-oxy group, alkenyl-oxy group, aryl-oxy group, aralkyl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, aralkyl-carbonyl group, alkyl-oxy -carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, aralkyl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy group, aryl-carbonyl-oxy group, aralkyl-carbonyl- An oxy group and the like can be mentioned.

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

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

(A) The molecular weight of the 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 (molecular weight of ethylene carbonate) or more, 102 (molecular weight of trimethylene carbonate) or more.

(A) Specific examples of the cyclic carbonate compound include formulas (A1) to (A17):

The compound represented by is mentioned.

The content of (A) the cyclic carbonate compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 20% by mass or less, more preferably It is 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 2.5% by mass or less. The lower limit of the content of (A) the cyclic carbonate compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.01% by mass or more. , more preferably 0.05% by mass or more, still 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.

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

<(B) Epoxy resin>
The resin composition of the present invention contains (B) an epoxy resin. (B) Epoxy resin means an epoxy equivalent of 5,000 g/eq. It is a curable resin having the following epoxy groups.

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

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

Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ). As the epoxy resin, the resin composition of the present invention may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. You can stay.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Liquid epoxy resins include glycyrrol 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. Resins, alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol-type epoxy resins, cycloaliphatic glycidyl ethers, and epoxy resins having a butadiene structure are preferred, and glycyrrol-type epoxy resins, cycloaliphatic glycidyl ethers, and bisphenol A-type epoxy resins. Resins and bisphenol F type epoxy resins are more preferred.

Specific examples of the liquid epoxy resin include "EX-992L" manufactured by Nagase ChemteX Corporation, "YX7400" manufactured by Mitsubishi Chemical Corporation, "HP4032", "HP4032D", and "HP4032SS" manufactured by DIC Corporation (naphthalene type epoxy resin ); Mitsubishi Chemical "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical "jER807", "1750" (bisphenol F type epoxy resin); "jER152" (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical; ED-523T” (glycirrol type epoxy resin); ADEKA “EP-3950L”, “EP-3980S” (glycidylamine type epoxy resin); ADEKA “EP-4088S” (dicyclopentadiene type epoxy resin ); "ZX1059" manufactured by Nippon Steel Chemical & Materials 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); Nagase "EX-991L" manufactured by Chemtex (epoxy resin containing alkyleneoxy skeleton and butadiene skeleton); "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel ”, “JP-100” and “JP-200” manufactured by Nippon Soda Co., Ltd. (epoxy resin having a butadiene structure); type epoxy resin); “EG-280” (fluorene structure-containing epoxy resin) manufactured by Osaka Gas Chemicals; “EX-201” (cycloaliphatic glycidyl ether) manufactured by Nagase ChemteX.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolak type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol phthalate A mijin-type epoxy resin is preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP -7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" ", "HP6000" (naphthylene ether type epoxy resin); Nippon Kayaku "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku; epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "YX4000H" manufactured by Mitsubishi Chemical, "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin); "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi "YX7700" (phenol aralkyl type epoxy resin) manufactured by Chemical Company; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" manufactured by Mitsubishi Chemical Corporation (bisphenol AF type epoxy resin); Mitsubishi Chemical Company "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical Corporation "jER1010" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation "jER1031S" (tetraphenylethane type epoxy resin); Nippon Kayaku "WHR991S" (phenol phthalimidine type epoxy resin) manufactured by Co., Ltd., and the like. These may be used individually by 1 type, and may be used in combination of 2 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 is 50:1 to 1:50, particularly preferably 10:1 to 1:10.

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

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

The content of the (B) epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 30% by mass or less, more preferably 25% by mass. % by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of the (B) epoxy resin in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.01% by mass or more, More preferably 0.1% by mass or more, still more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more.

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

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

(C) An inorganic compound is used as the material of the inorganic filler. (C) Examples of inorganic filler materials include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate , titanium oxide, zirconium oxide, barium titanate, barium 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. As silica, spherical silica is preferable. (C) Inorganic fillers may be used singly or in combination of two or more at any ratio.

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

The average particle size of the inorganic filler (C) 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 2.0 μm or less. 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, still 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 Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. A measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

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

(C) The inorganic filler is a non-hollow inorganic filler with a porosity of 0 vol% (preferably non-hollow silica, non-hollow aluminosilicate), or a hollow inorganic filler with a porosity of more than 0 vol% ( Hollow silica, hollow aluminosilicate) may be preferred, or both may be included. (C) The inorganic filler contains only hollow inorganic fillers (preferably hollow silica or hollow aluminosilicate) or non-hollow inorganic fillers (preferably non-hollow silica or non-hollow hollow aluminosilicate) and hollow inorganic fillers (preferably hollow silica, hollow aluminosilicate). The porosity of the hollow inorganic filler is preferably 90% by volume or less, more preferably 85% by volume or less. (C) The lower limit of the porosity of the inorganic filler may be, for example, more than 0% by volume, 1% by volume or more, 5% by volume or more, 10% by volume or more, or 20% by volume or more. The porosity P (% by volume) of the inorganic filler is the volume-based ratio of the total volume of one or more pores present inside the particle to the volume of the entire particle based on the outer surface of the particle (the number of pores total volume/particle volume), e.g., the measured actual density D _M (g/cm 3 ) of the inorganic filler and the theoretical material density D _T (g/cm ³ ) of the material forming the inorganic filler. /cm ³ ), it is calculated by the following formula (I).

The actual density of the inorganic filler can be measured using, for example, a true density measuring device. Examples of the true density measuring device include ULTRAPYCNOMETER 1000 manufactured by QUANTACHROME. Nitrogen, for example, is used as the measuring gas.

(C) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate compounds. A coupling agent etc. are mentioned. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in combination.

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

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

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. 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 more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and 0.5 mg/m ^{2 or less} . More preferred are:

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

The content of (C) the inorganic filler in the resin composition is not particularly limited. It may be 85% by mass or less, more preferably 80% by mass or less, and particularly preferably 78% by mass or less. The lower limit of the content of the inorganic filler (C) in the resin composition is not particularly limited. , or 10% by mass or more, more preferably 20% by mass or more, or 30% by mass or more, 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, Particularly preferably, it is 65% by mass or more, or 70% by mass or more.

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

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

(D) Active ester compounds generally have two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. is preferably used. The active ester compound is preferably 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 carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, the (D) active ester compound includes a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolak, and a benzoylated product of phenol novolak. Active ester compounds are preferred, and among them, at least one selected from dicyclopentadiene type active ester compounds and naphthalene type active ester compounds is more preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable.

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

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

The content of (D) the active ester compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably It is 5% by mass or more, more preferably 10% by mass or more, even more preferably 12% by mass or more, and particularly preferably 13% by mass or more. The upper limit of the content of (D) the active ester compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, or more. It is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

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

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

(D') Other curing agents include, but are not limited to, phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, Examples include cyanate ester-based curing agents and thiol-based curing agents. Among them, a curing agent selected from the group consisting of a phenolic curing agent and a carbodiimide curing agent is preferable, and the resin composition of the present invention more preferably contains both a phenolic curing agent and a carbodiimide curing agent.

As the phenolic curing agent, a phenolic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to adherends, a nitrogen-containing phenolic curing agent is preferred, and a triazine skeleton-containing phenolic curing agent is more preferred. Among them, a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of the phenol-based curing agent include, for example, Meiwa Chemical Co., Ltd. "MEH-7700", "MEH-7810", "MEH-7851", Nippon Kayaku Co., Ltd. "NHN", "CBN", " GPH", Nippon Steel Chemical & Material Co., Ltd. "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN- 375", "SN-395", DIC's "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", " KA-1160” and the like.

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

Examples of commercially available carbodiimide curing agents include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07" and "Carbodilite V-09" manufactured by Nisshinbo Chemical Co., Ltd. "Stabaxol P", "Stabaxol P400", and "Hykasil 510" manufactured by Rhein Chemie.

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, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1 , 3-dione, ethylene glycol bis(anhydrotrimellitate), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid. Commercially available acid anhydride-based curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA" and "OSA" manufactured by Shin Nippon Rika Co., Ltd., and " YH-306", "YH-307", Hitachi Chemical "HN-2200", "HN-5500", Clay Valley "EF-30", "EF-40" "EF-60", "EF -80” and the like.

Amine-based curing agents include curing agents having one or more, preferably two or more amino groups in one molecule. Examples include aliphatic amines, polyether amines, alicyclic amines, Aromatic amines and the like can be mentioned, and among them, aromatic amines are preferable from the viewpoint of achieving the desired effects of the present invention. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. , m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′ -diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)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, for example, Seika "SEIKACURE-S", Nippon Kayaku "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA". , “Kayahard AB”, “Kayahard AS”, “Epicure W” manufactured by Mitsubishi Chemical Corporation, and the like.

Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; Examples include "Fa".

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4, 4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, Polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. or a prepolymer that is entirely triazined to form a trimer), and the like.

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

(D') The reactive group equivalent of other curing agents is preferably 50 g/eq. ~3000g/eq. , more preferably 100 g/eq. ~1000g/eq. , more preferably 100 g/eq. ~500 g/eq. , particularly preferably 100 g/eq. ~300 g/eq. is. Reactive group equivalent weight is the mass of curing agent per equivalent of reactive group. A reactive group means a group that reacts with an epoxy resin, and is a phenolic hydroxyl group in the case of a phenol-based curing agent, and a carbodiimide group in the case of a carbodiimide-based curing agent, and varies depending on the type of curing agent.

The content of (D') other curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more It is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3.5% by mass or less. The lower limit of the content of (D') other curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, 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, and the like.

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

The ratio of the total number of molar equivalents of epoxy groups in (B) the epoxy resin in the resin composition to the total number of molar equivalents of curing agent reactive groups in (D) the active ester compound and (D') other curing agents in the resin composition (curing Agent-reactive group/epoxy group) 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. "Total number of molar equivalents of epoxy groups in (B) epoxy resin" indicates the sum of values obtained by dividing the mass of (B) epoxy resin present in the resin composition by the epoxy equivalent. In addition, "(D) the active ester compound and (D') the total number of molar equivalents of the curing agent reactive groups in the other curing agent" means that the mass of the (D) active ester compound present in the resin composition is the active ester group It shows the sum of the value obtained by dividing by the equivalent weight and the value obtained by dividing the mass of (D') other curing agents by the reactive group equivalent weight.

<(E) radically polymerizable group-containing compound>
The resin composition of the present invention may contain (E) a radically polymerizable group-containing compound. (B) A radically polymerizable group-containing compound is a compound containing one or more (preferably two or more) radically polymerizable groups in one molecule. (E) Radically polymerizable group-containing compounds may be used singly or in combination of two or more.

A radically polymerizable group is a group having a radically polymerizable ethylenically unsaturated bond, and is not particularly limited.
(1) Formula (R):

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

(E) In the first embodiment, the radically polymerizable group-containing compound preferably contains a thermoplastic resin (for example, a number average molecular weight of 800 or more) having two or more groups represented by the above formula (R). Examples of thermoplastic resins include, but are not limited to, phenoxy resins, polyvinyl acetal resins, polystyrene resins, polyethylene resins, polypropylene resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, and polysulfone resins. , polyether sulfone resins, polyphenylene ether resins, polyether ether ketone resins, polyester resins, and the like, and (E) the radically polymerizable group-containing compound is represented by the above formula (R) of these resins in the embodiment. including modified resins having two or more groups that are

(E) The compound containing a radically polymerizable group, in the first embodiment, more preferably has two or more groups represented by the above formula (R), and a modified polyphenylene ether resin having two or more groups represented by the above formula (R). containing a resin selected from modified polystyrene resins having two or more groups represented by the above formula (R), more preferably containing a modified polyphenylene ether resin having two or more groups represented by the formula ( 2):

[wherein 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 particularly Although not limited, the phenylene side is preferably bonded to 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 represents a hydrogen atom or an alkyl group; A is 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; q and r each independently indicates an integer greater than or equal to 1. ]
Including the resin represented by. The q unit and the r unit may be the same or different for each unit.

Each R ^b independently represents a hydrogen atom or a methyl group. Each X ^b is independently a carbonyl group, a methylene group, a phenylene group, or a phenylene-methylene group (although the bonding direction is not particularly limited, the phenylene side is preferably bonded to C in “R ^b —C” ), 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 -, preferably a single bond, -C(R ^c ) ₂ - or -O-. Each R ^c independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. p represents 0 or 1, preferably 1; q and r each independently represent an integer of 1 or more, preferably an integer of 1-200, more preferably an integer of 1-100.

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

The number average molecular weight of (E) the radically polymerizable group-containing compound 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).

Examples of commercially available products of (E) the radically polymerizable group-containing compound in the first embodiment include "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 resin) manufactured by SABIC Innovative Plastics.

(E) In the second embodiment, the radically polymerizable group-containing compound preferably has the formula (3′):

[Wherein, ring B represents an optionally substituted monocycloalkane ring or an optionally substituted monocycloalkene ring; or an integer of 1 or more, and the sum of i and j is 6 or more; * indicates a binding site. ]
Including a maleimide compound having a partial structure represented by A 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, particularly preferably 2. The maleimide compound in the second embodiment may be used singly or in combination of two or more at any ratio.

A monocycloalkane ring means a monocyclic saturated aliphatic 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 monocycloalkane rings include cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring and the like. A monocycloalkene ring means a monocyclic aliphatically 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 cyclobutene ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring, cyclopentadiene ring, cyclohexadiene ring and the like.

The “substituent” for the monocycloalkane ring and monocycloalkene ring includes the same “substituent” as the “substituent” that the aromatic carbocyclic ring in the ring Z′ described above may have.

Ring B represents an optionally substituted monocycloalkane ring or an optionally substituted monocycloalkene ring. Ring B is preferably a monocycloalkane ring optionally substituted with a group selected from an alkyl group and an alkenyl group; or a monocycloalkene ring optionally substituted with a group selected from an alkyl group and an alkenyl group. be. Ring B is more preferably a monocycloalkane ring optionally substituted with a group selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms; or a monocycloalkane ring having 1 to 14 carbon atoms. is a monocycloalkene ring optionally substituted with a group selected from an alkyl group 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 are preferably each independently 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 are more preferably each independently 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 more preferably each independently an integer of 5-10. i and j are particularly preferably 8.

(E) In the second embodiment, the radically polymerizable group-containing compound 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 a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO-, or - OCO— represents; 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 1 or more represents an integer; c each independently represents 0, 1 or 2; m represents 0 or an integer of 1 or more; other symbols are the same as above. ]
Including the maleimide compound represented by. The b unit, c unit and m unit may be the same or different for each unit.

An aromatic ring means a ring conforming to Hückel's rule in which the number of electrons contained in the π-electron system on the ring is 4p+2 (p is a natural number). The aromatic ring is an aromatic carbocyclic ring having only carbon atoms as ring-constituting atoms, or an aromatic heterocyclic ring having a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom in addition to a carbon atom as a ring-constituting atom. However, in one embodiment, aromatic carbocycles are preferred. 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. Preferable specific examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and the like, more preferably benzene ring or naphthalene ring, particularly preferably benzene ring.

Examples of the “substituent” for R ¹⁰ and the “substituent” for the aromatic ring include those similar to the “substituent” that the aromatic carbocyclic ring for ring Z′ described above may have.

Ring C each independently represents an optionally substituted aromatic ring, preferably a benzene ring optionally substituted by a group selected from an alkyl group. D ¹ and D ² are each independently a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, - represents NHCO-, -COO- or -OCO-, preferably a single bond, -C(R ^x ) ₂ - or -O-. Each R ^x independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. a each independently represents 0 or 1, preferably 0; Each b independently represents an integer of 0 or 1 or more, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2. Each c independently represents 0, 1 or 2, preferably 0. m represents 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 the same as above. ]
Although the partial structure represented by is not particularly limited, for example, formulas (D-1) to (D-3):

[In the formula, * is the same as above. ]
A partial structure represented by is mentioned.

The radically polymerizable group equivalent of (E) the radically polymerizable group-containing compound in the second embodiment is preferably 200 g/eq. ~2500 g/eq. , more preferably 250 g/eq. ~2000g/eq. , more preferably 300 g/eq. ~1500 g/eq. is. (E) The radically polymerizable group equivalent of the radically polymerizable group-containing compound represents the mass of the resin per one equivalent of the radically polymerizable group.

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

Examples of commercially available products of (E) the radically polymerizable group-containing compound in the second embodiment include “BMI-689”, “BMI-1500”, “BMI-1700” and “BMI” manufactured by Designer Molecules. -3000J”, “SLK-6895-T90” manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

(E) In the third embodiment, the radically polymerizable group-containing compound preferably has the formula (4):

[wherein 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 optionally having a substituent; each Z ¹ is independently a single bond, -C(R ^z ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO; - represents; R ^z each independently represents a hydrogen atom or an alkyl group; s represents an integer of 1 or more; t represents 0 or 1; independently indicates 0, 1, 2 or 3; ]
Including the maleimide compound represented by. The s unit and u unit may be the same or different for each unit. The maleimide compound in the third embodiment may be used singly or in combination of two or more at any ratio.

Each R ²⁰ independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. Ring E, ring F and ring G each independently represent an optionally substituted aromatic ring, preferably a benzene ring optionally having a substituent, more preferably A benzene ring optionally substituted with a group selected from an alkyl group and an aryl group, particularly preferably a (unsubstituted) benzene ring.

Z ¹ is each independently a single bond, -C(R ^z ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO- is preferably a single bond, —C(R ^z ) ₂ —, or —O—, more preferably a single bond or —C(R ^z ) ₂ —, particularly preferably a single bond is. 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 of 1-10. Each t independently represents 0 or 1, preferably 1. u each independently represents 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, particularly preferably 1;

The radically polymerizable group equivalent of (E) the radically polymerizable group-containing compound in the third embodiment is preferably 150 g/eq. ~1000g/eq. , more preferably 200 g/eq. ~500 g/eq. is.

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

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

(E) the radically polymerizable group-containing compound is any one of the suitable thermoplastic resin in the first embodiment, the suitable maleimide compound in the second embodiment, and the suitable maleimide compound in the third embodiment, or two or more of these may be contained in combination at any ratio.

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

The content of (E) the radically polymerizable group-containing compound in the resin composition is not particularly limited, but is preferably 50% by mass or less when the non-volatile component in the resin composition is 100% by mass. More preferably 30% by mass or less, still more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less. The lower limit of the content of (E) the radically polymerizable group-containing compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, 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, and the like.

<(F) Thermoplastic resin>
The resin composition of the present invention may further contain (F) a thermoplastic resin as an optional component. (F) The thermoplastic resin is a component that does not correspond to (B) the epoxy resin described above.

(F) Thermoplastic resins include, for example, polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, and polycarbonate resins. , polyether ether ketone resin, polyester resin, and the like. (F) The thermoplastic resin, in one embodiment, preferably contains a thermoplastic resin selected from the group consisting of a polyimide resin and a phenoxy resin, and more preferably contains a phenoxy resin. Moreover, one type of thermoplastic resin may be used alone, or two or more types may be used in combination.

Specific examples of the polyimide resin include “SLK-6100” manufactured by Shin-Etsu Chemical Co., Ltd., “Likacoat SN20” and “Ricacoat PN20” manufactured by Shin Nippon Rika Co., Ltd., and the like.

Examples of phenoxy resins include 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, and terpene. Examples include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

Specific examples of the phenoxy resin include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel Chemical & Materials, Ltd.; "FX280" and "FX293" manufactured by Nippon Steel Chemical &Materials; ”, “YL7769BH30”, “YL6794”, “YL7213”, “YL7290” and “YL7482”.

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

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

Polybutadiene resins include, for example, 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, and isocyanate group-containing resins. Examples include polybutadiene resin, urethane group-containing polybutadiene resin, polyphenylene ether-polybutadiene resin, and the like.

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

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "Ultem" manufactured by GE.

Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxy 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 diol) manufactured by Asahi Kasei Chemicals, "C-1090" and "C-2090" manufactured by Kuraray Co., Ltd. , “C-3090” (polycarbonate diol) and the like. Specific examples of the polyetheretherketone resin include "Sumiproy K" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, and the like.

(F) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, and particularly It is preferably 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less.

The content of the (F) thermoplastic resin relative to the total nonvolatile components in the resin composition is not particularly limited, but is preferably 20% by mass or less when the nonvolatile components in the resin composition are 100% by mass. , more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of the thermoplastic resin (F) with respect to all non-volatile components is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0.0% by mass or more. 01% by mass or more, 0.1% by mass or more, and the like.

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

Examples of (G) curing accelerators include phosphorus curing accelerators, urea curing accelerators, guanidine curing accelerators, imidazole curing accelerators, metal curing accelerators, amine curing accelerators, and the like. . (G) Curing accelerator preferably contains a curing accelerator selected from imidazole curing accelerators and amine curing accelerators, and particularly preferably contains imidazole curing accelerators. (G) The curing accelerator may be used singly or in combination of two or more.

Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydro Aliphatic phosphonium salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 -methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, aromatic phosphonium salts such as butyltriphenylphosphonium thiocyanate; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; 2-butenyl)phosphine, aliphatic phosphines such as tricyclohexylphosphine; -tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butyl) phenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris( 3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4- methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis( diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2′-bis(diphenylphosphino)diphenyl ether, and other aromatic phosphines. be done.

Urea-based curing accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as 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, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] etc.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like.

Examples of imidazole 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, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(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 isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins.

As the imidazole-based curing accelerator, a commercially available product may be used. "P200-H50" of.

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, and zinc (II) acetylacetonate. and the like, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

As the amine-based curing accelerator, a commercially available product may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.

The content of the (G) curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or less, more preferably It is 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less. The lower limit of the content of (G) the curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0 It can be 0.001 wt% or more, 0.01 wt% or more, and the like.

<(H) Other Additives>
The resin composition of the present invention may further contain optional additives. Examples of such additives include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, Thermosetting resins other than epoxy resins such as 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 copper compounds and organics Organometallic compounds such as zinc compounds and organocobalt compounds; coloring agents 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 antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents, vinyl resin antifoaming agents, etc. Antifoaming agent; UV absorber such as benzotriazole UV absorber; Adhesion improver such as urea silane; Antioxidants such as hindered phenol antioxidants; Fluorescent whitening agents such as stilbene derivatives; Surfactants such as fluorine surfactants and silicone surfactants; Phosphorus flame retardants (e.g. phosphoric acid Flame retardants such as ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (e.g. melamine sulfate), halogen flame retardants, inorganic flame retardants (e.g. antimony trioxide); phosphate ester dispersants , polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, cationic dispersants; borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers Stabilizers such as stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic anhydride stabilizers are included. (H) Other additives may be used singly or in combination of two or more at any ratio. (H) The content of other additives can be appropriately set by those skilled in the art.

<(I) Organic solvent>
The resin composition of the present invention may further contain any organic solvent. (I) As the organic solvent, a known solvent can be used as appropriate, and the type is not particularly limited. (I) Examples of organic solvents include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester-based solvents such as butyrolactone; Ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol Solvent; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, 2-hydroxyiso ester alcohol solvents such as methyl butyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide , N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide solvents; dimethyl sulfoxide and other sulfoxide solvents; acetonitrile, propionitrile and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane, etc. and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene. (I) The organic solvent may be used singly or in combination of two or more at any ratio.

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

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

<Characteristics of resin composition>
The resin composition of the present invention contains (A) a cyclic carbonate compound, (B) an epoxy resin, and (C) an inorganic filler. According to such a resin composition, it is possible to obtain a cured product that can maintain high peel strength even when exposed to a high-temperature and high-humidity environment and that has a low dielectric loss tangent.

The cured product of the resin composition of the present invention can have a feature that it can maintain high peel strength even when exposed to a high-temperature and high-humidity environment. Therefore, in one embodiment, for example, a copper-plated conductor layer is formed on the cured product as in Test Examples 4 and 5 below, and the load at 25 ° C. calculated from the load when the copper-plated conductor layer is peeled off in the vertical direction The peel strength is preferably 0.2 kgf/cm or more, more preferably 0.25 kgf/cm or more, still more preferably 0.3 kgf/cm or more, and even more preferably 0.35 kgf before conducting an accelerated environmental test (HAST). /cm or more, particularly preferably 0.4 kgf/cm or more, after performing an accelerated environmental test (HAST) for 100 hours under high temperature and high humidity conditions of 130 ° C. and 85% RH, it is preferably 0.1 kgf/cm or more, more preferably 0.15 kgf/cm or more, still more preferably 0.2 kgf/cm or more, still more preferably 0.25 kgf/cm or more, and particularly preferably 0.3 kgf/cm or more. obtain. Although the upper limit is not particularly limited, it can be, for example, 10 kgf/cm or less both before and after the accelerated environmental test (HAST). The peel strength value decrease rate (%) before and after the accelerated environmental test (HAST) is preferably 45% or less, more preferably 40% or less, even more preferably 35% or less, still more preferably 30% or less, especially Preferably, it can be suppressed to 25% or less, or 20% or less. The rate of decrease in peel strength value (%) is the decrease in the value of peel strength (kgf/cm) after the accelerated environmental test (HAST) relative to the value of the peel strength (kgf/cm) before the accelerated environmental test (HAST). Calculated as a percentage (%).

A cured product of the resin composition of the present invention may have a low dielectric loss tangent (Df). Therefore, 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 preferably 0.0100 or less, more preferably 0.0080 or less, still more preferably 0.0060 or less, still more preferably 0.0050 or less, or 0.0040 or less, particularly preferably 0.0035 or less, or 0.0030 or less obtain.

In one embodiment, the cured product of the resin composition of the present invention may have a low dielectric constant (Dk). Therefore, 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 is preferably can be 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. Therefore, in one embodiment, the elongation at break of the cured product measured at 23° C. in accordance with Japanese Industrial Standards JIS K7127 as in Test Example 2 below is not particularly limited, but is preferably 0.5. 05% or more, more preferably 0.1% or more, still more preferably 0.15% or more, even more preferably 0.2% or more, and particularly preferably 0.22% or more. Although the upper limit of the elongation at break is not particularly limited, it can usually be 10% or less, 5% or less, or the like.

In one embodiment, the cured product of the resin composition of the present invention may be characterized by a low arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment. 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 is preferably 500 nm or less, more preferably may be 400 nm or less, 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.

<Application of resin composition>
The resin composition of the present invention can be suitably used as a resin composition for insulation, particularly as a resin composition for forming an insulation layer. Specifically, a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition). Moreover, in the 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 also includes resin sheets, sheet laminate materials such as prepreg, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, and the like. It can be used in a wide range of applications.

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is used as an insulating layer for forming a rewiring layer. (a resin composition for forming a rewiring layer) and a resin composition for sealing a semiconductor chip (a resin composition for semiconductor chip sealing). A rewiring layer may be further formed on the encapsulation layer when the semiconductor chip package is manufactured.
(1) a step of laminating a temporary fixing film on a substrate;
(2) temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(5) Forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been removed; and (6) Forming a rewiring layer as a conductor layer on the rewiring layer. forming process

Moreover, since the resin composition of the present invention provides an insulating layer having good component embedding properties, it can be suitably used when the printed wiring board is a component built-in circuit board.

<Sheet-like laminated material>
Although the resin composition of the present invention can be applied in the form of a varnish, it is industrially preferably used in the form of a sheet-like laminated material containing the resin composition.

As the sheet-like laminate material, resin sheets and prepregs shown below are preferable.

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 It is preferably 40 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 5 μm or more, 10 μm or more, or the like.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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 of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

In one embodiment, the resin sheet may further contain any layer as necessary. Examples of such an optional layer include a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, the surface of the resin composition layer can be prevented from being dusted or scratched.

For the resin sheet, for example, a liquid (varnish) resin composition is used as it is, or a liquid (varnish) resin composition is prepared by dissolving the resin composition in an organic solvent, which is then coated using a die coater or the like. It can be produced by applying it on a support by drying, and then drying it to form a resin composition layer.

Examples of the organic solvent include the same organic solvents as those described as components of the resin composition. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent 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 the organic solvent, drying at 50 ° C. to 150 ° C. for 3 to 10 minutes A resin composition layer can be formed.

The resin sheet can be wound into a roll and stored. When 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 base material with the resin composition of the present invention.

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

A prepreg can be manufactured by a known method such as a hot melt method or a 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 laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). for interlayer insulating layers of wiring boards).

<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.

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

The "inner layer substrate" used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer board" as used in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination can be carried out under reduced pressure conditions, preferably at a pressure of 26.7 hPa or less.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch-type vacuum pressurized laminator, and the like.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. Pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned 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 (for example, thermally cured) to form an insulating layer made of the cured resin composition. Curing conditions for the resin composition layer are not particularly limited, and conditions that are usually employed when forming an insulating layer of a printed wiring board may be used.

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

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

When manufacturing a printed wiring board, (III) the step of drilling holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of 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 support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V). If necessary, the steps (II) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.

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

Step (III) is a step of making holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, 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 according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Smear is usually 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 commonly used in forming insulating layers of printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.

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

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 with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes. Further, the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.

Moreover, as a neutralization liquid used for the roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned.

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

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. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more. 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, in which 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 selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method. An example of forming a conductor layer by a semi-additive method is shown below.

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 a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

In other embodiments, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably performed between step (I) and step (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. Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Then, step (II) is performed to form an insulating layer. After that, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.

A metal foil can be manufactured by a known method such as an electrolysis method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.

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

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. The 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. The temperature condition unless otherwise specified is room temperature (23° C.), and the pressure condition unless otherwise specified 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 with stirring. This was cooled to room temperature to prepare an epoxy resin dissolved composition. 2 parts of a cyclic carbonate compound 1 ("4,4,6-trimethyl-1,3-dioxan-2-one" manufactured by JNC, a compound represented by the formula (A4)) was added to the epoxy resin dissolved composition, Active ester compound (manufactured by DIC "HPC-8000-65T", active ester group equivalent of about 223 g / eq., toluene solution with a non-volatile content of 65%) 45 parts, silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM- 573”) surface-treated spherical silica (Admatechs “SO-C2”, average particle diameter 0.5 μm, specific surface area 5.8 m ² /g) 130 parts, triazine skeleton-containing phenolic curing agent (DIC "LA-3018-50P" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent weight of about 151 g / eq., 2-methoxypropanol solution with a nonvolatile content of 50%) 3 parts, carbodiimide curing agent (manufactured by Nisshinbo Chemical Co., Ltd. "V-03", active group Equivalent weight of about 216 g / eq., non-volatile content of 50% toluene solution) 8 parts, imidazole curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole) 0.2 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone having a non-volatile content of 30% by mass) was mixed with 2.5 parts and uniformly dispersed with a high-speed rotating mixer to prepare a resin composition.

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

<Example 3>
Instead of 2 parts of cyclic carbonate compound 1 (“4,4,6-trimethyl-1,3-dioxan-2-one” manufactured by JNC), cyclic carbonate compound 2 (“DEPPO” manufactured by JNC, formula (A11) Compound represented by) 1 part, and 1 part of cyclic carbonate compound 3 ("DXC" manufactured by JNC, compound represented by formula (A10)), and an active ester compound (manufactured by DIC "HPC-8000- 65T”) instead of 45 parts of an active ester compound (“HPC-8150-62T” manufactured by DIC, active ester group equivalent of about 220 g / eq., non-volatile content of 62% by mass of a toluene solution) using 45 parts, Furthermore, spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m ² /g ) was changed from 130 parts to 155 parts, a resin composition was prepared in the same manner as in Example 1.

<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 of about 330 g / eq.), and bisphenol type epoxy Using 3 parts of resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., a 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of about 169 g / eq.), cyclic carbonate compound 1 ("4, 4,6-trimethyl-1,3-dioxan-2-one”) instead of 2 parts of cyclic carbonate compound 3 (“DXC” manufactured by JNC), and an active ester compound (manufactured by DIC “ HPC-8000-65T”) instead of 45 parts of the active ester compound (DIC “HPC-8150-62T”, active ester group equivalent of about 220 g / eq., non-volatile component rate of 62 mass% toluene solution). A resin composition was prepared in the same manner as in Example 1, except that the

<Example 5>
Instead of 2 parts of cyclic carbonate compound 3 ("DXC" manufactured by JNC), cyclic carbonate compound 4 (synthesized by the same method as described in Example 13 of Japanese Patent No. 6141261, represented by formula (A16) A resin composition was prepared in the same manner as in Example 4, except that 2 parts of the compound obtained by the above method were used.

<Example 6>
Instead of 2 parts of cyclic carbonate compound 3 ("DXC" manufactured by JNC), cyclic carbonate compound 5 (synthesized by the same method as described in the example of JP 2018-118946, formula (A17) A resin composition was prepared in the same manner as in Example 4, except that 2 parts of the compound represented by the following were used.

<Example 7>
Instead of 45 parts of the active ester compound (manufactured by DIC "HPC-8000-65T"), an active ester compound (manufactured by DIC "HPC-8150-62T", active ester group equivalent weight of about 220 g / eq., nonvolatile content of 62 mass % toluene solution), and further, 4 parts of biphenyl aralkyl novolac type maleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., MEK / toluene mixed solution with a nonvolatile content of 70%) was used. Except for this, in the same manner as in Example 1, a resin composition was prepared.

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

<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 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.) Using 3 parts, biphenyl aralkyl novolac type maleimide (manufactured by Nippon Kayaku Co., Ltd. " A resin composition was prepared in the same manner as in Example 7, except that 3 parts of methacrylic-modified polyphenylene ether ("SA9000-111" manufactured by SABIC Innovative Plastics) was used instead of 4 parts of MIR-3000-70MT. prepared.

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

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

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

<Comparative Example 2>
Without using 2 parts of cyclic carbonate compound 1 (“4,4,6-trimethyl-1,3-dioxan-2-one” manufactured by JNC) and 3 parts of maleimide-terminated polyimide compound (“BMI-1500” manufactured by DMI) Furthermore, spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m ² / A resin composition was prepared in the same manner as in Example 8, except that the amount of g) was changed from 130 parts to 150 parts.

<Comparative Example 3>
Naphthalene type epoxy resin (manufactured by DIC "HP-4032-SS", 1,6-bis (glycidyloxy) naphthalene, epoxy equivalent of about 145 g / eq.) Instead of 15 parts, naphthol type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 330 g / eq. eq.) 3 parts, and 45 parts of an active ester compound (“HPC-8150-62T” manufactured by DIC, an active ester group equivalent of about 220 g/eq., a toluene solution with a nonvolatile content of 62% by mass) was reduced to 20 parts. Furthermore, spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m ² /g) was reduced from 150 parts to 90 parts. A resin composition was prepared in the same manner as in Comparative Example 2 except for the above matters.

<Comparative Example 4>
Spherical silica (“SO-C2” manufactured by Admatechs, 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.) The amount used was changed from 150 parts to 125 parts, and further, a polyester compound (Showa Denko Materials Co., Ltd. "Teslac 5001-40T", number average molecular weight 27000, nonvolatile content 40% by mass Toluene solution) was used. A resin composition was prepared in the same manner as in Comparative Example 2, except that

<Production example 1: Production of resin sheet>
As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared. On the release layer of this support, the resin compositions obtained in Examples and Comparative Examples were uniformly applied 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 dielectric constant (Dk) and dielectric loss tangent (Df)>
After peeling off the protective film from the resin sheet prepared in Production Example 1, heating at 200 ° C. for 90 minutes to thermally cure the resin composition layer, and then peeling off the support, a cured product of the resin composition A formed cured product film was obtained. For Comparative Example 4, no cured film was obtained. The cured product film was cut into a width of 2 mm and a length of 80 mm to obtain a cured product A for evaluation.

For the obtained cured product A for evaluation, using Agilent Technologies "HP8362B", the dielectric constant (Dk value) and dielectric loss tangent (Df value) was measured. Three test pieces were measured, and the average value was calculated.

<Test Example 2: Measurement of elongation at break>
The cured product A for evaluation obtained in the same manner as in Test Example 1 was subjected to a tensile test at 23 ° C. using a Tensilon universal tester (“RTC-1250A” manufactured by Orientec Co., Ltd.) in accordance with Japanese Industrial Standards JIS K7127. was performed and the elongation at break (%) was measured.

<Test Example 3: Measurement of arithmetic mean roughness (Ra)>
(1) Surface treatment of interior substrate As an inner layer substrate, a glass cloth-based epoxy resin double-sided copper-clad laminate having a copper foil on the surface (copper foil thickness 18 μm, substrate thickness 0.8 mm, manufactured by Panasonic “R1515A” ”) was prepared. The copper foil on the surface of the inner layer substrate was roughened by etching with a microetching agent (“CZ8101” manufactured by MEC Co., Ltd.) at a copper etching amount of 1 μm. After that, drying was performed at 190° C. for 30 minutes.

(2) Lamination and curing of the resin sheet The resin sheet prepared in Production Example 1 is coated with a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) to form a resin composition layer. Both surfaces of the inner layer substrate were laminated so as to be bonded to the inner layer substrate. This lamination was carried out by pressure bonding for 30 seconds at a temperature of 100° C. and a pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds.

Then, the laminated resin sheet was hot-pressed for 60 seconds at 100° C. under atmospheric pressure and a pressure of 0.5 MPa for smoothing. Further, this was put into a 130° C. oven and heated for 30 minutes, then transferred to a 170° C. oven and heated for 30 minutes.

(3) Via hole formation Using a CO ₂ laser processing machine (LK-2K212/2C) manufactured by Via Mechanics Co., Ltd., the insulating layer is processed under the conditions of a frequency of 2000 Hz, a pulse width of 3 μs, an output of 0.95 W, and the number of shots of 3. Then, a via hole having a top diameter (diameter) of 50 μm on the surface of the insulating layer and a diameter of 40 μm on the bottom surface of the insulating layer was formed. 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, at 60° C. for 10 minutes. Next, it was immersed at 80° C. for 20 minutes in a roughening liquid Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) manufactured by Atotech Japan. Finally, it was immersed at 40° C. for 5 minutes in Reduction Solution Securigant P manufactured by Atotech Japan Co., Ltd., which is a neutralizing solution. The obtained substrate was designated as an evaluation substrate A.

(5) Measurement of Arithmetic Average Roughness (Ra) The obtained evaluation substrate A was measured using a non-contact surface roughness meter (WYKO NT3300 manufactured by Bcoinstruments, Inc.) in VSI mode with a 50x lens, measuring a range of 121 μm. The Ra value was obtained from the numerical value obtained as ×92 µm. Each was measured by calculating the average value of 10 randomly selected points.

<Test Example 4: Measurement of peel strength (peel strength) of plated conductor layer before HAST test>
Evaluation board 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. bottom. After annealing by heating at 150° C. for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 μm. Next, an evaluation substrate B was obtained by performing an annealing treatment at 200° C. for 60 minutes.

A 10 mm wide and 150 mm long cut was made in the portion of the conductor layer of the obtained evaluation board B that did not include the via hole, and one end of this cut was peeled off and a gripper (manufactured by TSE Co., Autocom type test Machine AC-50C-SL), and the load (kgf/cm) when peeling off 100 mm in the vertical direction at a speed of 50 mm/min at room temperature (25° C.) was measured.

<Test Example 5: Measurement of peel strength (peel strength) of plated conductor layer after HAST test>
Acceleration for 100 hours under high temperature and high humidity conditions of 130 ° C. and 85% RH using a highly accelerated life test device (“PM422” manufactured by Kusumoto Kasei Co., Ltd.) for evaluation substrate B produced in the same manner as in Test Example 4 An environmental test (HAST) was performed. After that, the evaluation board B after HAST was cut in the same manner as described above, and as in Test Example 4, one end of the cut was peeled off and gripped with the grip of the tensile tester. The load (kgf/cm) was measured when 35 mm was peeled off in the vertical direction at a speed of 1/min. The measurement was performed according to Japanese Industrial Standard JIS C6481.

Table 1 below summarizes the amounts of raw materials used in the resin compositions of Examples and Comparative Examples and the measurement results of Test Examples.

From the results shown in Table 1 above, in the resin composition containing (B) an epoxy resin and (C) an inorganic filler, (A) when a cyclic carbonate compound is used, (A) when a cyclic carbonate compound is not used Compared with , it can be seen that it is possible to obtain a cured product that can maintain high peel strength even after the HAST test and has a low dielectric loss tangent. In addition, in Example 11 containing the hollow inorganic filler as (C) the inorganic filler, it can be seen that the dielectric constant is further reduced as compared with Example 1.

Claims (18)

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

[In the formula,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a group selected from (1) a hydrogen atom, (2) RO—, RCO—, RCOO— and ROCO— an optionally substituted alkyl group, (3) an alkenyl group optionally substituted by a group selected from RO—, RCO—, RCOO—, and ROCO—, (4) R—, RO—, RCO—, RCOO-, and an aralkyl group optionally substituted with a group selected from ROCO-, (5) formula (2-1):

or (6) formula (2-2):

showing a group represented by;
R ^1′ , R ^2′ , R ^3′ , R ^4′ , R ^5′ and R ^6′ are each independently (1) a hydrogen atom, (2) RO—, RCO—, RCOO— and ROCO an alkyl group optionally substituted by a group selected from -, (3) RO-, RCO-, RCOO-, and an alkenyl group optionally substituted by a group selected from ROCO-, or (4) R- , RO-, RCO-, RCOO-, and an aralkyl group optionally substituted with a group selected from ROCO-;
A ¹ and A ² each independently represent -O-, -CO-, -COO- or -OCO-;
X and Y are each independently (1) an alkylene group optionally substituted with a group selected from RO-, RCO-, RCOO-, and ROCO-, or (2) RO-, RCO-, RCOO -, and represents an alkenylene group optionally substituted with a group selected from ROCO-;
Each R is independently 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. , alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, aralkyl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy group, aryl-carbonyl-oxy group, and an alkyl group, an alkenyl group, an aralkyl group, or an aryl group, each optionally substituted with a group selected from an aralkyl-carbonyl-oxy group;
Z each independently represents 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 claims 1 to 5, comprising a compound represented by 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 when the non-volatile component in the resin composition is 100% by mass. . The resin composition according to any one of claims 1 to 7, wherein the content of component (C) is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 8, further comprising a curing agent selected from the group consisting of phenolic curing agents and carbodiimide curing agents. The resin composition according to any one of claims 1 to 9, wherein the cured resin composition has a dielectric loss tangent (Df) of 0.0030 or less when measured at 5.8 GHz and 23°C. The resin composition according to any one of claims 1 to 10, wherein the cured product of the resin composition has an elongation at break of 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 11, which is used for forming an insulating layer for forming a conductor layer. The resin composition according to any one of claims 1 to 11, 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 13. A sheet-like laminate material containing the resin composition according to any one of claims 1 to 13. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 13 provided on the support. A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 13. A semiconductor device comprising the printed wiring board according to claim 17 .