JP2021172756A - Resin composition - Google Patents

Abstract

To provide a resin composition that gives a cured product having reduced unevenness after lamination.SOLUTION: A resin composition contains (A) a compound having a repeating unit represented by formula (1), (B) an epoxy resin, and (C) an active ester compound. (In formula (1), ring A is an optionally substituted nitrogen-containing aromatic ring; ring B and ring C independently represent an optionally substituted aromatic ring; X is a single bond or divalent non-aromatic hydrocarbon group).SELECTED DRAWING: None

Description

The present invention relates to a resin composition containing an epoxy resin. Further, the present invention relates to a cured product obtained by using the resin composition, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device.

As a manufacturing technique for printed wiring boards, a manufacturing method by 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 the resin composition. It is known that in the step of laminating the resin composition on the sheet support base material, unevenness may occur after the laminating treatment.

So far, resin compositions using a polymer of bisphenol ether containing a nitrogen-containing heterocycle have been known (Patent Documents 1 and 2).

International Publication No. 2019/05/4335 International Publication No. 2020/021827

An object of the present invention is to provide a resin composition capable of obtaining a cured product in which unevenness after lamination is suppressed.

As a result of diligent studies to achieve the object of the present invention, the resin composition containing (B) epoxy resin and (C) active ester compound is represented by the formula (A) (1). By using a compound containing a repeating unit, it has been found that a cured product in which unevenness after lamination can be suppressed can be obtained, and the present invention has been completed.

That is, the present invention includes the following contents.
[1] Equation (A) (1):

[In the formula, ring A represents a nitrogen-containing aromatic ring which may have a substituent; ring B and ring C each independently represent an aromatic ring which may have a substituent; X represents a single bond or divalent non-aromatic hydrocarbon group. ]
A resin composition containing a compound containing a repeating unit represented by (B), an epoxy resin (B), and an active ester compound (C).
[2] The component (A) is the formula (1A) or (1B) :.

[In the formula, X ¹ , X ² , X ³ and X ⁴ each independently indicate N, CH or CR ^a , and at least one of ^{X 1} , X ² , X ³ and X ^{4 is N.} R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an alkenyl group, or R ¹ and R ² are bonded together together and are selected from an alkyl group and an alkenyl group. It forms a cycloalkane ring which may have a group or a cycloalkane ring which may have a group selected from an alkyl group and an alkenyl group; ^Ra , R ^b and R ^c are independent of each other. , B and c each independently represent an integer of 0-3. ]
The resin composition according to the above [1], which is a compound containing a repeating unit represented by.
[3] The content of the component (A) is 0.01% by mass to 3% by mass when the non-volatile component in the resin composition is 100% by mass, according to the above [1] or [2]. Resin composition.
[4] The resin composition according to any one of [1] to [3] above, wherein the component (B) contains an epoxy resin containing (B-1) a fused ring structure.
[5] The resin composition according to the above [4], wherein the component (B-1) is a monomer-type condensed ring structure-containing epoxy resin.
[6] The content of the component (B) is 1% by mass to 30% by mass when the non-volatile component in the resin composition is 100% by mass, according to any one of the above [1] to [5]. Resin composition.
[7] The resin composition according to any one of the above [1] to [6], wherein the mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 10 to 50. thing.
[8] The content of the component (C) is 5% by mass to 30% by mass when the non-volatile component in the resin composition is 100% by mass, according to any one of the above [1] to [7]. Resin composition.
[9] The resin composition according to any one of the above [1] to [8], wherein the mass ratio of the component (C) to the component (A) (component (C) / component (A)) is 30 to 100. thing.
[10] The resin composition according to any one of the above [1] to [9], further comprising (D) an inorganic filler.
[11] The resin composition according to the above [10], wherein the component (D) is silica.
[12] The resin composition according to the above [10] or [11], wherein the content of the component (D) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[13] The resin composition according to the above [12], wherein the content of the component (D) is 70% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[14] The resin composition according to any one of the above [1] to [13], which further contains (E) a radically polymerizable compound.
[15] The resin composition according to any one of [1] to [14] above, further comprising (F-1) a carbodiimide-based curing agent.
[16] A cured product of the resin composition according to any one of the above [1] to [15].
[17] A sheet-like laminated material containing the resin composition according to any one of the above [1] to [15].
[18] A resin sheet having a support and a resin composition layer formed from the resin composition according to any one of the above [1] to [15] provided on the support.
[19] A printed wiring board provided with an insulating layer made of a cured product of the resin composition according to any one of the above [1] to [15].
[20] A semiconductor device including the printed wiring board according to the above [19].

According to the resin composition of the present invention, it is possible to obtain a cured product in which unevenness after lamination is suppressed.

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

<Resin composition>
The resin composition of the present invention contains (A) a compound containing a repeating unit represented by the formula (1), (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, it is possible to obtain a cured product in which unevenness after lamination is suppressed. Further, in a specific embodiment, a cured product having a low dielectric loss tangent (Df) can be obtained. Further, in a specific embodiment, a cured product having good plating adhesion (peel strength of the plated conductor layer) can be obtained.

The resin composition of the present invention further contains an arbitrary component in addition to the compound containing the repeating unit represented by the formula (A) (1), the epoxy resin (B), and the active ester compound (C). May be good. Optional components include, for example, (D) inorganic filler, (E) radically polymerizable compound, (F) curing agent, (G) curing accelerator, (H) other additives, and (I) organic solvent. Can be mentioned. Hereinafter, each component contained in the resin composition will be described in detail.

<Compound containing a repeating unit represented by the formula (1) in (A)>
The resin composition of the present invention has the formula (A) (1):

[In the formula, ring A represents a nitrogen-containing aromatic ring which may have a substituent; ring B and ring C each independently represent an aromatic ring which may have a substituent; X represents a single bond or divalent non-aromatic hydrocarbon group. ]
Includes compounds containing repeating units represented by.

Ring A represents a nitrogen-containing aromatic ring which may have a substituent. The aromatic ring means a ring according to Hückel's law in which the number of electrons contained in the π-electron system on the ring is 4n + 2 (n is a natural number). The nitrogen-containing aromatic ring represented by ring A has one or more (preferably two or more, particularly preferably two) nitrogen atoms in addition to carbon atoms as ring-constituting atoms, and further oxygen. It may have a hetero atom other than a nitrogen atom such as an atom or a sulfur atom. The nitrogen-containing aromatic ring represented by ring A is preferably a 5- to 14-membered nitrogen-containing aromatic ring, more preferably a 5- to 10-membered nitrogen-containing aromatic ring, and even more preferably a 5- or 6-membered nitrogen-containing aromatic ring. A 6-membered nitrogen-containing aromatic ring is particularly preferred. The nitrogen-containing aromatic ring represented by ring A includes not only a monocyclic aromatic ring and a fused ring in which two or more monocyclic aromatic rings are condensed, but also one or more monocyclic aromatic rings. Also included is a fused ring in which one or more monocyclic non-aromatic rings are condensed.

Preferable specific examples of the nitrogen-containing aromatic ring represented by ring A include, for example, a pyrrole ring, an imidazole ring, a pyrazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, and a tetrazole ring. Monocyclic nitrogen-containing aromatic rings such as pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,2,3-triazine ring, 1,2,4-triazine ring, 1,3,5-triazine ring; A fused ring of a benzene ring and a monocyclic nitrogen-containing aromatic ring such as a ring, an isoindole ring, a benzoimidazole ring, an indazole ring, a benzotriazole ring, a quinoxaline ring, a synnoline ring, a quinazoline ring, or a phthalazine ring; Rings, 4-azaindole rings, 5-azaindole rings, 6-azaindole rings, 7-azaindole rings, 7-azaindazole rings, pyrazolo [1,5-a] pyrimidine rings, 1,8-naphthylidine rings, Includes monocyclics such as pyrido [3,2-d] pyrimidine ring, pyrido [4,3-d] pyrimidine ring, pyrido [3,4-b] pyrimidine ring, pyrido [2,3-b] pyrimidine ring, etc. Examples thereof include fused rings of nitrogen aromatic rings, preferably a monocyclic nitrogen-containing aromatic ring, more preferably a 6-membered monocyclic nitrogen-containing aromatic ring, and further preferably a pyrimidine ring. Alternatively, it is a pyrimidine ring, and particularly preferably a pyrimidine ring.

In the present specification, the "substituent" is not particularly limited, but for example, an alkyl group, an alkenyl group, an aryl group, an alkyl-aryl group (an aryl group substituted with one or more alkyl groups). , Aryl-aryl group (aryl group substituted with one or more aryl groups), aryl-alkyl group (alkyl group substituted with one or more aryl groups), alkyl-oxy group, alkenyl-oxy group, aryl -Oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl Examples thereof include a monovalent substituent such as a −oxy group and an aryl-carbonyl-oxy group, and if substitutable, a divalent substituent such as an oxo group (= O) may also be included.

Alkyl (group) refers to a linear, branched and / or cyclic monovalent aliphatic saturated hydrocarbon group. The alkyl (group) preferably has 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 or 4 to 10 carbon atoms. Examples of the alkyl (group) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. Examples thereof include a group, a decyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group and the like. Alkenyl (group) refers to a linear, branched and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl (group) preferably has 2 to 14 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 6 or 4 to 10 carbon atoms. Examples of the alkenyl (group) include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a cyclohexenyl group and the like. Aryl (group) refers to a monovalent aromatic hydrocarbon group. The aryl (group) is preferably an aryl (group) having 6 to 14 carbon atoms. Examples of the aryl (group) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.

Ring B and Ring C each independently represent an aromatic ring which may have a substituent. The aromatic ring represented by ring B or ring C has a carbon ring having a carbon atom as a ring-constituting atom, or a heteroatom such as an oxygen atom, a nitrogen atom, and a sulfur atom in addition to a carbon atom as a ring-constituting atom. It can be a heterocycle, but in one embodiment it is preferably a carbon ring. The aromatic ring represented by ring B or ring C is preferably a 5- to 14-membered aromatic ring, more preferably a 5- to 10-membered aromatic ring, further preferably a 5- or 6-membered aromatic ring, and a 6-membered aromatic ring. Is particularly preferable. The aromatic ring represented by ring B or ring C includes not only a monocyclic aromatic ring and a fused ring in which two or more monocyclic aromatic rings are condensed, but also one or more monocyclic aromatic rings. A fused ring in which one or more monocyclic non-aromatic rings are condensed on the ring is also included.

Preferable specific examples of the aromatic ring represented by ring B or ring C include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isooxazole ring, a thiazole ring, an imidazole ring, and a pyridine ring. Monocyclic aromatic rings such as pyridazine ring, pyrimidine ring, pyrazine ring; naphthalene ring, anthracene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzoimidazole ring, indazole ring, benzoxazole. A fused ring in which two or more monocyclic aromatic rings such as a ring, a benzoisooxazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, an aclysine ring, a quinazoline ring, a synnoline ring, and a phthalazine ring are condensed; Examples thereof include a fused ring in which one or more monocyclic non-aromatic rings are condensed with one or more monocyclic aromatic rings such as a ring, a fluorene ring, and a tetralin ring, and a monocyclic aromatic ring is preferable. It is more preferably a 6-membered monocyclic aromatic ring, and particularly preferably a benzene ring.

X is a single bond or divalent non-aromatic hydrocarbon group. The divalent non-aromatic hydrocarbon group represented by X is a saturated or unsaturated linear, branched chain and / or cyclic divalent non-aromatic hydrocarbon group. The divalent non-aromatic hydrocarbon group represented by X has, for example, a divalent non-valent group having 1 to 100 carbon atoms, preferably 1 to 50, more preferably 1 to 30, and further preferably 1 to 20 carbon atoms. It is an aromatic hydrocarbon group.

X is preferably a divalent non-aromatic hydrocarbon group, and more preferably the formula (X1) :.

[In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an alkenyl group, or R ¹ and R ² are bonded together together and selected from an alkyl group and an alkenyl group. It forms a cycloalkane ring which may have a group, or a cycloalkene ring which may have a group selected from an alkyl group and an alkenyl group; * indicates a binding site. ]
It is a divalent group represented by, and more preferably, the formulas (X2-1) to (X2-3) :.

[In the formula, R ³ , R ⁴ , and R ⁵ each independently represent an alkyl group; x represents an integer of 0-5 (preferably 1-5, more preferably 2-4); * Indicates the binding site. ]
It is a divalent group represented by any of the above, and particularly preferably, it is a divalent group represented by the formula (X2-1).

The cycloalkane ring refers to a cyclic aliphatic saturated hydrocarbon ring. The cycloalkane ring is preferably a cycloalkane ring having 3 to 8 carbon atoms, and more preferably a cycloalkane ring having 5 or 6 carbon atoms. Examples of the cycloalkane ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring and the like. The cycloalkene ring refers to a cyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond. The cycloalkene ring is preferably a cycloalkene ring having 4 to 8 carbon atoms, and more preferably a cycloalkene ring having 5 or 6 carbon atoms. Examples of the cycloalkene ring include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, a cyclohexadiene ring and the like.

The compound containing the repeating unit represented by the formula (A) (1) is preferably the formula (1A) or (1B) :.

[In the formula, X ¹ , X ² , X ³ and X ⁴ independently represent N, CH or CR ^a (preferably N or CH) and of X ¹ , X ² , X ³ and X ^{4 respectively} . At least one of them (preferably at least two, particularly preferably two) is N; ^Ra , R ^b and R ^c are independent substituents (preferably alkyl groups, alkenyl groups, aryls). Groups, alkyl-aryl groups, aryl-aryl groups, or aryl-alkyl groups, more preferably alkyl groups, alkenyl groups, or aryl groups, particularly preferably aryl groups); b and c are independent of each other. It indicates an integer of 0 to 3 (preferably 0); other symbols are the same as in equation (X1). ]
It is a compound containing a repeating unit represented by, and more preferably, the formulas (1A-1) to (1B-3):

[In the formula, a indicates an integer of 0 to 2 (preferably 0); other symbols are the same as those of the formulas (1A), (1B) and (X2-1) to (X2-3). be. ]
It is a compound containing a repeating unit represented by any of the above, and a compound containing a repeating unit represented by the formula (1A-1) is particularly preferable.

In one embodiment, the compound containing the repeating unit represented by the formula (A) (1) may have a reactive group such as a phenolic hydroxyl group, a thiol group, an amino group, a carboxy group or a sulfo group, and is preferable. , May have a phenolic hydroxyl group. In one embodiment, it is preferable to have two or more reactive groups in one molecule.

In the compound containing the repeating unit represented by the formula (1), the number of repeating units is preferably 5 or more, more preferably 10 or more, still more preferably 30 or more, and particularly preferably 50 or more. The upper limit of the number of repeating units is not particularly limited, but may be, for example, 10,000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, and the like.

The weight average molecular weight (Mw) of the compound containing the repeating unit represented by the formula (A) is not particularly limited, but is preferably 1000 to 200,000, more preferably 5,000 to 150,000, and even more preferably 10,000. ~ 120,000. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The glass transition temperature (Tg) of the compound containing the repeating unit represented by the formula (A) (1) is not particularly limited, but is preferably 100 to 300 ° C, more preferably 150 to 250 ° C. obtain.

The compound containing the repeating unit represented by the formula (1) (A) is synthesized by using, for example, the method described in International Publication No. 2019/054335, International Publication No. 2020/021827, or a method equivalent thereto. can do.

The content of the compound containing the repeating unit represented by the formula (A) (1) 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 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. The lower limit of the content of the compound containing the repeating unit represented by the formula (A) (1) in the resin composition is not particularly limited, but the non-volatile component in the resin composition is set to 100% by mass. In the case, preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, still more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, particularly preferably 0.1% by mass. That is all.

<(B) Epoxy resin>
The resin composition of the present invention contains (B) an epoxy resin. (B) The epoxy resin means a curable resin having an epoxy group. The (B) epoxy resin preferably contains (B-1) a fused ring structure-containing epoxy resin.

<(B-1) Epoxy resin containing condensed ring structure>
(B-1) The condensed ring structure-containing epoxy resin means a resin having one or more condensed rings and one or more (preferably two or more) epoxy groups in one molecule. (B-1) The fused ring structure-containing epoxy resin may be used alone or in combination of two or more at any ratio.

(B-1) The fused ring contained in the condensed ring structure-containing epoxy resin is preferably a condensed aromatic carbocycle. The fused aromatic carbocycle is a bicyclic or more aromatic carbocycle obtained by condensing two or more benzene rings, and the number of carbon atoms is preferably 10 to 18, preferably 10 to 14. More preferably, for example, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like can be mentioned, and a naphthalene ring is particularly preferable.

(B-1) The condensed ring structure-containing epoxy resin may be any of glycidyl ether type, glycidyl amine type, glycidyl ester type, and olefin oxidation (alicyclic) type, and among them, it is glycidyl ether type. Is preferable.

(B-1) The condensed ring structure-containing epoxy resin may be of a monomer type or a repeating structure type. Here, the repeating structure type refers to a polymer structure having an average of 3 or more repeating units containing 1 or 2 or more condensed rings, and the monomer type has no repeating unit or 1 or 2 A molecular structure having two repeating units containing two or more fused rings. The (B-1) condensed ring structure-containing epoxy resin is composed of (B-1-1) a monomer-type condensed ring structure-containing epoxy resin and (B-1-2) a repeating structure-type condensed ring structure-containing epoxy resin. The epoxy resin of choice is preferably a (B-1-1) monomer-type fused ring structure-containing epoxy resin.

Examples of the (B-1-1) monomer-type condensed ring structure-containing epoxy resin include 1,6-bis (glycidyloxy) naphthalene, 1,5-bis (glycidyloxy) naphthalene, and 2,7-bis (). A monomer-type condensed ring structure-containing epoxy resin having one condensed ring in one molecule such as glycidyloxy) naphthalene and 2,6-bis (glycidyloxy) naphthalene; bis [2- (glycidyloxy) -1- Naphtyl] methane, 2,2-bis [2- (glycidyloxy) -1-naphthyl] propane, bis [2,7-bis (glycidyloxy) -1-naphthyl] methane, 2,2-bis [2,7 -Bis (glycidyloxy) -1-naphthyl] propane, [2,7-bis (glycidyloxy) -1-naphthyl] [2- (glycidyloxy) -1-naphthyl] methane, 2- [2,7-bis (Glysidyloxy) -1-naphthyl] -2- [2- (glycidyloxy) -1-naphthyl] A monomer-type condensed ring structure-containing epoxy resin having two condensed rings in one molecule such as propane can be mentioned. Be done.

(B-1-1) The monomer-type condensed ring structure-containing epoxy resin is preferably a monomer-type condensed ring structure-containing epoxy resin having one condensed ring in one molecule in one embodiment. , Particularly preferably 1,6-bis (glycidyloxy) naphthalene.

(B-1-1) In one embodiment, the monomer-type fused ring structure-containing epoxy resin is preferably a bifunctional to tetrafunctional epoxy resin, and is preferably a bifunctional or trifunctional epoxy resin. More preferably, it is a bifunctional epoxy resin.

The epoxy equivalent of the (B-1-1) monomer-type fused ring structure-containing epoxy resin is not particularly limited, but is preferably 50 g / eq. Above, more preferably 80 g / eq. Above, more preferably 100 g / eq. Above, even more preferably 120 g / eq. As mentioned above, particularly preferably 130 g / eq. That is all. The upper limit of the epoxy equivalent of the (B-1-1) monomer-type fused ring structure-containing epoxy resin is not particularly limited, but is preferably 1000 g / eq. Hereinafter, more preferably 500 g / eq. Hereinafter, more preferably, 300 g / eq. Hereinafter, even more preferably, 200 g / eq. Hereinafter, particularly preferably 160 g / eq. It is as follows. Epoxy equivalent is the mass of resin per equivalent of epoxy group. Epoxy equivalents can be measured according to JIS K7236.

The molecular weight of the (B-1-1) monomer-type condensed ring structure-containing epoxy resin is not particularly limited, but is preferably 2000 or less, more preferably 1000 or less, still more preferably 700 or less, and even more preferably. Is 600 or less, particularly preferably 500 or less.

(B-1-1) Commercially available products of the monomer-type fused ring structure-containing epoxy resin include, for example, "HP-4032D" and "HP-4032SS" manufactured by DIC Corporation (one naphthalene ring in one molecule). "EXA-4750", "HP-4770", "HP-4700", "HP-4710" (epoxy resin having two naphthalene rings in one molecule), etc. Can be mentioned.

(B-1-2) Examples of the repeating structure type fused ring structure-containing epoxy resin include naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, and naphthol aralkyl. Examples thereof include a repeating structure type fused ring structure-containing epoxy resin having three or more fused rings in one molecule, such as a type epoxy resin, a naphthalenediol aralkyl type epoxy resin, and a naphthylene ether type epoxy resin.

(B-1-2) The epoxy equivalent of the repeating structure type fused ring structure-containing epoxy resin is not particularly limited, but is preferably 50 g / eq. As mentioned above, more preferably 100 g / eq. Above, more preferably 200 g / eq. Above, even more preferably 250 g / eq. As mentioned above, particularly preferably 300 g / eq. That is all. (B-1-2) The upper limit of the epoxy equivalent of the repeating structure type fused ring structure-containing epoxy resin is not particularly limited, but is preferably 2000 g / eq. Hereinafter, more preferably 1000 g / eq. Below, more preferably 500 g / eq. Hereinafter, even more preferably, 400 g / eq. It is as follows.

(B-1-2) Examples of commercially available products of the repeating structure type condensed ring structure-containing epoxy resin include "ESN-155", "ESN-185V", and "ESN-175" manufactured by Nittetsu Chemical & Materials Co., Ltd. , "ESN-475V", "ESN-485", "TX-1507B" (naphthol aralkyl type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC. , "EXA-7311-G4S", "HP-6000", "HP-6000-L" (naphthylene ether type epoxy resin); "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Can be mentioned.

The resin composition may contain (B-2) or other epoxy resin in addition to the (B-1) fused ring structure-containing epoxy resin, but the (B-1) fused ring structure in the resin composition. The content of the contained epoxy resin is preferably 50% by mass or more, 60% by mass or more, and more, when the total epoxy resin in the resin composition is 100% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 70% by mass or more, 80% by mass or more, more preferably 90% by mass or more, 95% by mass or more, still more preferably 98% by mass or more, 99% by mass or more, and particularly preferably 100% by mass.

<(B-2) Other epoxy resins>
(B-2) Examples of other epoxy resins include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and dicyclopentadiene type epoxy resin. , Trisphenol type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin , Linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin , Tetraphenyl ethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, phenolphthalein type epoxy resin and the like. (B-2) Other epoxy resins may be used alone or in combination of two or more.

The resin composition preferably contains, as (B-2) another epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. (B-2) The ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass, based on 100% by mass of the non-volatile component of the other epoxy resin. As mentioned above, it is particularly preferably 70% by mass or more.

The epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) or a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). ). The resin composition of the present invention may contain only the liquid epoxy resin as the other epoxy resin (B-2), may contain only the solid epoxy resin, or may contain the liquid epoxy resin and the solid state. It may be contained in combination with an epoxy resin.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and alicyclic epoxy having an ester skeleton. Resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure are preferable.

Specific examples of the liquid epoxy resin include "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER807" manufactured by Mitsubishi Chemical Co., Ltd. , "1750" (bisphenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. ); "ED-523T" (glycirole type epoxy resin) manufactured by ADEKA; "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA; "EP-4088S" manufactured by ADEKA. (Dicyclopentadiene type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase Chemtex Co., Ltd. (glycidyl ester type) Epoxy resin); "Selokiside 2021P" manufactured by Daicel Co., Ltd. (Alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel Co., Ltd., "JP-100" manufactured by Nippon Soda Co., Ltd., "JP-200" (Epoxy resin having a butadiene structure); Examples thereof include "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation. These may be used individually by 1 type, and may be used in combination of 2 or more types.

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

Examples of the solid epoxy resin include bixilenol type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and phenol. Aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenolphthalimidine type epoxy resin, and phenolphthalein type epoxy resin are preferable.

Specific examples of the solid epoxy resin include "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP" manufactured by DIC. -7200 "," HP-7200HH "," HP-7200H "," HP-7200L "(dicyclopentadiene type epoxy resin);" EPPN-502H "(trisphenol type epoxy resin) manufactured by Nippon Kayakusha; Japan "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Kayakusha; "YX4000H", "YX4000", "YX4000HK", "YL7890" manufactured by Mitsubishi Chemical Co., Ltd. (Bixilenor type epoxy resin); "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "PG-100" manufactured by Osaka Gas Chemical Co., Ltd. , "CG-500"; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1010" (bisphenol A) manufactured by Mitsubishi Chemical Co., Ltd. Type epoxy resin); "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The epoxy equivalent of the other epoxy resin (B-2) is preferably 50 g / eq. ~ 5,000 g / eq. , More preferably 60 g / eq. ~ 2,000 g / eq. , More preferably 70 g / eq. ~ 1,000 g / eq. , Even more preferably 80 g / eq. ~ 500 g / eq. Is.

(B-2) The weight average molecular weight (Mw) of the other epoxy resin is preferably 100 to 5,000, more preferably 300 to 3,000, and even 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 60% by mass or less, more preferably 40. It is 0% by mass or less, more preferably 30% by mass or less, still more preferably 20% 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. It is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more.

The mass ratio of the epoxy resin (B) to the compound containing the repeating unit represented by the formula (1) in the resin composition (component (B) / component (A)) is not particularly limited. However, it is preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 20 or more. The upper limit of the mass ratio ((B) component / (A) component) of the (B) epoxy resin to the compound containing the repeating unit represented by the formula (1) in the resin composition is particularly limited. Although not, it is preferably 200 or less, more preferably 100 or less, still more preferably 50 or less, and particularly preferably 30 or less.

<(C) Active ester compound>
The resin composition of the present invention contains (C) an active ester compound. Generally, the (C) active ester compound may have a function of reacting with the (B) epoxy resin to cure the resin composition. The active ester compound (C) may be used alone or in combination of two or more at any ratio.

(C) As the active ester compound, generally, two or more ester groups having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are contained in one molecule. The compound to have 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 preferable, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Specifically, the (C) 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 a phenol novolac acetylated product, and a phenol novolac benzoyl compound. The active ester compound is preferable, and at least one selected from the dicyclopentadiene type active ester compound and the naphthalene type active ester compound is more preferable, and the dicyclopentadiene type active ester compound is further preferable. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

(C) Commercially available products of the active ester compound include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L" and "EXB-8000L-65M" as active ester compounds containing a dicyclopentadiene type diphenol structure. , "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM", (manufactured by DIC) ); As active ester compounds containing a naphthalene structure, "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC); "EXB9401" (manufactured by DIC) as a phosphorus-containing active ester compound, "DC808" (manufactured by Mitsubishi Chemical) as an active ester compound which is an acetylated product of phenol novolac. , "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound which is a benzoylated product of phenol novolac, and "PC1300-02-65MA" (air) as an active ester compound containing a styryl group and a naphthalene structure.・ Made by Water Co., Ltd.).

The active ester group equivalent of the (C) active ester compound 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 the active ester compound per 1 equivalent of the active ester group.

The content of the (C) 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 60% by mass or less, more preferably 60% by mass or less. It is 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The lower limit of the content of the (C) 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 0.1% by mass or more. , More preferably 1% by mass or more, still more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 10% by mass or more.

The mass ratio ((C) component / (A) component) of the (C) active ester compound to the compound containing the repeating unit represented by the formula (1) in the resin composition is not particularly limited. Although not, it is preferably 5 or more, more preferably 10 or more, still more preferably 30 or more, and particularly preferably 40 or more. The upper limit of the mass ratio ((C) component / (A) component) of the (C) active ester compound to the compound containing the repeating unit represented by the formula (1) in the resin composition is particularly limited. Although not, it is preferably 500 or less, more preferably 200 or less, still more preferably 100 or less, and particularly preferably 60 or less.

The mass ratio of the (C) active ester compound to the (B) epoxy resin in the resin composition ((C) component / (B) component) is not particularly limited, but is preferably 0.1 or more. It is preferably 0.5 or more, more preferably 1 or more, and particularly preferably 1.5 or more. The upper limit of the mass ratio ((C) component / (B) component) of the (C) active ester compound to the (B) epoxy resin in the resin composition is not particularly limited, but is preferably 10 or less. It is preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

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

(D) An inorganic compound is used as the material of the inorganic filler. Examples of the material of the inorganic filler (D) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, 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, zirconium tungstate phosphate and the like. Of these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (D) As the inorganic filler, one kind may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.

(D) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd .; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka Corporation; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-" manufactured by Tokuyama Corporation. 5N ”;“ SC2500SQ ”,“ SO-C4 ”,“ SO-C2 ”,“ SO-C1 ”manufactured by Admatex;“ DAW-03 ”,“ FB-105FD ”manufactured by Denka, and the like.

The average particle size of the inorganic filler (D) is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, still more preferably 1 μm or less, and particularly preferably 0. It is 7 μm or less. (D) 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. (D) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, the light source wavelengths used were blue and red, and the volume-based particle size distribution of the inorganic filler was measured by the flow cell method, and the obtained particle size distribution was used. The average particle size was calculated as the median diameter. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by HORIBA, Ltd.

The specific surface area of the inorganic filler (D) 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. The upper limit of the specific surface area of the inorganic filler (D) is not particularly limited, but is preferably 100 m ² / g or less, more preferably 70 m ² / g or less, still more preferably 50 m ² / g or less, and particularly preferably. Is 40 m ² / g or less. For the specific surface area of the inorganic filler, nitrogen gas is adsorbed on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and the specific surface area is calculated using the BET multipoint method. It can be obtained by.

The inorganic filler (D) is preferably surface-treated with an appropriate surface treatment agent. By surface treatment, the moisture resistance and dispersibility of the (D) inorganic filler can be enhanced. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxy-based silane coupling agents; p-styryltrimethoxysilane and other styryl-based Silane coupling agents; methacrylic silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane , 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N Amino-based silane coupling agents such as −phenyl-8-aminooctyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane; tris- (trimethoxysilylpropyl) isocyanurate, etc. Isocyanurate-based silane coupling agent; ureido-based silane coupling agent such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. An isocyanate-based silane coupling agent such as 3-isocyanoxide propyltriethoxysilane; an acid anhydride-based silane coupling agent such as 3-trimethoxysilylpropyl succinate; a silane coupling agent such as; methyltrimethoxysilane, Dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimeth Examples thereof include non-silane coupling-alkoxysilane compounds such as xysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, and trifluoropropyltrimethoxysilane. Further, the surface treatment agent may be used alone or in combination of two or more at an arbitrary ratio.

Examples of commercially available surface treatment agents include "KBM-1003" and "KBE-1003" (vinyl-based silane coupling agents) manufactured by Shin-Etsu Chemical Industry Co., Ltd .; "KBM-303", "KBM-402", and "KBM-402". KBM-403 "," KBE-402 "," KBE-403 "(epoxy-based silane coupling agent);" KBM-1403 "(styryl-based silane coupling agent);" KBM-502 "," KBM-503 " , "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-" 903 ”,“ KBE-903 ”,“ KBE-9103P ”,“ KBM-573 ”,“ KBM-575 ”(amino silane coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); "X" -12-967C "(acid anhydride-based silane coupling agent);" KBM-13 "," KBM-22 "," KBM-103 "," KBE-13 "," KBE-22 "," KBE-103 " , "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" ( Non-silane coupling-alkoxysilane compound) and the like.

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

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity at the melt viscosity or sheet form a resin composition, preferably from 1.0 mg / ^{m 2} or less, more preferably 0.8 mg / ^{m 2} or less, 0.5 mg / ^{m 2} The following is more preferable.

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

The content of the (D) inorganic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 98% by mass or less and 95% by mass. Hereinafter, it may be 90% by mass or less and 85% by mass or less. The lower limit of the content of the (D) inorganic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more and 1% by mass. % Or more, 5% by mass or more, 10% by mass or more, preferably 20% by mass or more, 30% by mass or more, more preferably 40% by mass or more, 50% by mass or more, still more preferably 55% by mass or more. It can be 60% by mass or more, particularly preferably 65% by mass or more, 70% by mass or more, and the like.

<(E) Radical polymerizable compound>
The resin composition of the present invention may further contain (E) a radically polymerizable compound as an optional component. The radically polymerizable compound (E) may be used alone or in any combination of two or more.

The radically polymerizable compound (E) can be, for example, a compound having a radically polymerizable unsaturated group. The radically polymerizable unsaturated group is not particularly limited as long as it can be radically polymerizable, but an ethylenically unsaturated group having a carbon-carbon double bond at the terminal or inside is preferable, and specifically, an allyl group. , Unsaturated aliphatic groups such as 3-cyclohexenyl group; unsaturated aliphatic group-containing aromatic groups such as p-vinylphenyl group, m-vinylphenyl group and styryl group; acryloyl group, methacryloyl group, maleoil group, fumaroyl It can be an α, β-unsaturated carbonyl group such as a group. The radically polymerizable compound (E) preferably has one or more radically polymerizable unsaturated groups, and more preferably two or more radically polymerizable unsaturated groups.

As the (E) radical-polymerizable compound, known radical-polymerizable compounds can be widely used, and the radical-polymerizable compound is not particularly limited, but for example, (E-1) maleimide-based radical-polymerizable compound, (E-). 2) Examples thereof include vinylphenyl-based radical-polymerizable compounds and (E-3) (meth) acrylic-based radical-polymerizable compounds.

<(E-1) Maleimide-based radically polymerizable compound>
(E-1) The maleimide-based radically polymerizable compound has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-) in one molecule. It is an organic compound containing an ill group). (E-1) The maleimide-based radically polymerizable compound may be used alone or in combination of two or more at any ratio. The (E-1) maleimide-based radically polymerizable compound includes, for example, (E-1-1) maleimide-terminal polyimide compound, (E-1-2) aromatic maleimide compound, and (E-1--3) aliphatic maleimide. It preferably contains at least one maleimide compound selected from the compounds.

<(E-1-1) Maleimide-terminated polyimide compound>
(E-1-1) The maleimide-terminated polyimide compound is a chain-like polyimide having maleimide groups at both ends (a chain-like polymer containing two or more imide structures). The maleimide-terminated polyimide compound (E-1-1) can be a component that can be obtained, for example, by subjecting a component containing a diamine compound, maleic anhydride, and tetracarboxylic dianhydride to an imidization reaction.

In one embodiment, the (E-1-1) maleimide-terminated polyimide compound is, for example, the following formula (2):

[In the formula, A ¹ is independently selected from carbon atom, oxygen atom, nitrogen atom, and sulfur atom, and two or more (for example, 2 to 3000, 2 to 1000, 2 to 100, 2 to 2). Shows a divalent organic group consisting of (50) skeleton atoms (preferably a divalent ring (eg, aromatic ring or non-aromatic ring) -containing organic group); A ² is independently single-bonded or carbon. A divalent organic group consisting of one or more (for example, 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeleton atoms selected from an atom, an oxygen atom, a nitrogen atom, and a sulfur atom. Shown; R ^p and R ^q each independently indicate a substituent; n is an atom of 1 or more (preferably an atom of 1 to 100, more preferably an atom of 1 to 50, particularly preferably 1 to 20). Independently, m indicates 0 or 1, respectively; p and q independently indicate an atom of 0 to 3 (preferably 0). ]
It is a maleimide-terminated polyimide compound represented by.

A ¹ is independent of each other, preferably the following formula (Y1):

[In the formula, Y ¹¹ independently represents a single bond, an alkylene group or an alkaneylene group; Y ¹² independently represents a single bond, an alkylene group, an alkaneylene group, −O−, −CO−, respectively. _{-S -, - SO -, -} SO 2 -, - CONH -, - NHCO -, - COO-, or -OCO- indicates; ring ^{Z 1} are each independently have a substituent Indicates a good non-aromatic ring, or an aromatic ring which may have a substituent; y1 indicates 0 or an integer greater than or equal to 1 (preferably an integer of 0 or 1-5); * indicates a binding site. .. ]
It is a divalent group represented by.

The alkylene group refers to a linear or branched divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 14 carbon atoms. Examples of the alkylene group include a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group and a decamethylene group; _{(-CH (CH 3) -)} , propylidene _{(-CH (CH 2 CH 3)} -), isopropylidene group _{(-C (CH 3) 2 -} ), ethyl methyl methylene group (-C _(CH 3) ( CH ₂ CH ₃₎ -), diethyl methylene group _{(-C (CH 2 CH 3)} 2 -), 2- methyl tetramethylene group, 2,3-dimethyl tetramethylene group, 1,3-dimethyl tetramethylene group, 2 -Methylpentamethylene group, 2,2-dimethylpentamethylene group, 2,4-dimethylpentamethylene group, 1,3,5-methylpentamethylene group, 2-methylhexamethylene group, 2,2-dimethylhexamethylene group , 2,4-Dimethylhexamethylene group, 1,3,5-trimethylhexamethylene group, 2,2,4-trimethylhexamethylene group, 2,4,4-trimethylhexamethylene group, etc. Can be mentioned. The alkenylene group refers to a straight-chain or branched divalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenylene group is preferably an alkenylene group having 2 to 14 carbon atoms. Specific examples of the alkenylene group include a group formed by replacing an arbitrary carbon-carbon single bond with a carbon-carbon double bond in those specifically exemplified as an alkylene group.

Aromatic ring for ring Z ¹ of the formula (Y1) is the same as the aromatic ring for ring B or ring C of formula (1). Fused non-aromatic ring represented by the ring Z ¹ of the formula (Y1) means a ring other than aromatic ring, non-aromatic ring monocyclic, and the non-aromatic ring of the two or more monocyclic are fused Contains non-aromatic rings. The non-aromatic ring can be a carbocycle or a heterocycle, but in one embodiment it is preferably a carbocycle. The non-aromatic ring may be a saturated ring or an unsaturated ring, but in one embodiment, it is preferably a saturated ring. Examples of the non-aromatic ring include a cycloalkane ring; a cycloalkene ring; a pyrrolidine ring, a tetrahydrofuran ring, a dioxane ring, a tetrahydropyran ring and the like, and a monocyclic non-aromatic heterocycle (preferably 3 to 10 members); a norbornane ring. , A bicyclic or higher fused non-aromatic carbocycle (preferably 8 to 15 members) such as a decalin ring, an adamantan ring, a tetrahydrodicyclopentadiene ring and the like.

Specific examples of the divalent group represented by the formula (Y1) include, but are not limited to, a divalent organic group represented by the following:

[In the formula, * indicates a binding site. ].

A ² is independent of each other, preferably the formula (Y2) :.

Wherein, ^{Y 2} is each independently a single bond, an alkylene group, an alkenylene group, -O -, - CO -, - S -, - SO -, - SO 2 -, - CONH -, - NHCO- , -COO-, or -OCO-; Ring Z ² independently represents a non-aromatic ring which may have a substituent or an aromatic ring which may have a substituent; y2 indicates an integer of 0 or 1 or more (preferably an integer of 0 or 1 to 5); * indicates a binding site. ]
It is a divalent group represented by (including a single bond). ^{The aromatic ring and the non-aromatic ring represented by the ring Z 2} of the formula (Y2) are represented by the aromatic ring represented by the ring B or the ring C of the formula (1) and the ring Z ¹ of the formula (Y1), respectively. It is the same as the non-aromatic ring.

Specific examples of the divalent group represented by the formula (Y2) are not particularly limited, but -CH _2- , -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-,. -C (CH ₃ ) _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2- , -O-, -CO-, -S-, -SO-, And -SO _2- , as well as divalent organic groups represented by:

[In the formula, * indicates a binding site. ].

The weight average molecular weight (Mw) of the (E-1-1) maleimide-terminated polyimide compound is preferably 500 to 50,000, and more preferably 1,000 to 20,000. The functional group equivalent of the maleimide group of the (E-1-1) maleimide-terminated polyimide compound is preferably 300 g / eq. ~ 20000 g / eq. , More preferably 500 g / eq. 10000 g / eq. Is.

Examples of commercially available maleimide-terminated polyimide compounds include "BMI-1500", "BMI-1700", "BMI-3000J", and "BMI-6000" manufactured by Designer Moleculars. Examples thereof include "BMI-6100".

<(E-1-2) Aromatic maleimide compound>
The (E-1-2) aromatic maleimide compound is a maleimide compound that does not correspond to the component (E-1-1), and contains one or more aromatic rings in one molecule and two or more maleimides. It means a maleimide compound containing a group. In one embodiment, the (E-1-2) aromatic maleimide compound can be an addition polymerization type aromatic maleimide compound. (E-1-2) The aromatic maleimide compound is a maleimide compound having one aromatic ring such as N, N'-1,3-phenylenedi maleimide, N, N'-1,4-phenylenedi maleimide. It may be a maleimide compound having two or more aromatic rings, but a maleimide compound having two or more aromatic rings is preferable.

In one embodiment, the (E-1-2) aromatic maleimide compound is described, for example, in formula (3):

Wherein, ^{R u} are each independently represents a substituent; ^{Y 3} are each independently a single bond, an alkylene group, an alkenylene group, -O -, - CO -, - S -, - SO -, -SO _2- , -CONH-, -NHCO-, -COO-, or -OCO- (preferably a single bond or an alkylene group); ring Z ³ each independently has a substituent. A non-aromatic ring which may have a substituent or an aromatic ring which may have a substituent (preferably an aromatic ring which may have a substituent, particularly preferably a benzene ring which may have a substituent). ; S represents an integer greater than or equal to 1 (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, even more preferably an integer of 1 to 20); t is independently 0 or Indicates an integer of 1 or more; u independently indicates an integer of 0 to 2 (preferably 0). ] Is a maleimide compound, and particularly preferably, the formula (3'):

[In the formula, s is the same as in the formula (3). ] Is a maleimide compound. Aromatic and non-aromatic ring represented by ring Z ³ of formula (3), respectively, the aromatic ring represented by the ring B or ring C of formula (1), represented by ring Z ¹ of the formula (Y1) It is the same as the non-aromatic ring.

In one embodiment, as the (E-1-2) aromatic maleimide compound, a novolac-type polymaleimide containing a repeating unit containing a combination of an N-phenylmaleimide skeleton and a methylene skeleton is preferable, and an N-phenylmaleimide skeleton and methylene are preferable. Aralkirnovolac-type polymaleimide containing a repeating unit containing alternating combinations of skeletons and aromatic carbocyclic skeletons and methylene skeletons is more preferred, with combinations of N-phenylmaleimide skeletons and methylene skeletons, biphenyl skeletons and methylene. More preferred are biphenylaralkylnovolac-type polymaleimides that contain repeating units that alternate with skeleton combinations.

The weight average molecular weight (Mw) of the aromatic maleimide compound (E-1-2) is preferably 150 to 5000, more preferably 300 to 2500. (E-1-2) The functional group equivalent of the maleimide group of the aromatic maleimide compound is preferably 50 g / eq. ~ 2000 g / eq. , More preferably 100 g / eq. ~ 1000 g / eq. More preferably, 150 g / eq. ~ 500 g / eq. , Particularly preferably 200 g / eq. ~ 300 g / eq. Is.

(E-1-2) Commercially available aromatic maleimide compounds include, for example, "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd .; "BMI-50P" manufactured by Keiai Kasei Co., Ltd .; "BMI-50P" manufactured by Daiwa Kasei Kogyo Co., Ltd. BMI-1000 "," BMI-1000H "," BMI-1100 "," BMI-1100H "," BMI-4000 "," BMI-5100 "; Keiai Kasei Co., Ltd." BMI-4,4'-BPE ", Examples thereof include "BMI-70" and "BMI-80" manufactured by Keiai Kasei Co., Ltd.

<(E-1-3) Aliphatic maleimide compound>
(E-1-3) The aliphatic maleimide compound has a non-aromatic hydrocarbon (preferably 2 to 50 carbon atoms) as a basic skeleton and has two or more (preferably two) maleimide groups in one molecule. It is a compound having.

In one embodiment, the (E-1-3) aliphatic maleimide compound is, for example, the following formula (4):

[In the formula, Y ⁴ independently represents a single bond, an alkylene group or an alkaneylene group (preferably an alkylene group or an alkaneylene group); ring Z ⁴ is independently selected from an alkyl group and an alkenyl group, respectively. Indicates a non-aromatic ring (preferably a cycloalkane ring or a cycloalkene ring which may have a group selected from an alkyl group and an alkenyl group); y4 is 0 or 1 or more. An alkene (preferably an integer of 1 or more, particularly preferably 1) is shown. ] Is a maleimide compound. ^{The non-aromatic ring represented by the ring Z 4} of the formula (4) is the same as the non-aromatic ring represented by the ring Z ¹ of the formula (Y1).

(E-1-3) Specific examples of the aliphatic maleimide compound include chain-like chains such as N, N'-ethylene dimaleimide, N, N'-tetramethylene dimaleimide, and N, N'-hexamethylene dimaleimide. Aliphatic bismaleimide compounds; 1-maleimide-3-maleimidemethyl-3,5,5-trimethylcyclohexane (IPBM), 1,1'-(cyclohexane-1,3-diylbismethylene) bis (1H-pyrrole-2) , 5-Dione) (CBM), 1,1'-(4,4'-methylenebis (cyclohexane-4,1-diyl)) Bis (1H-pyrrole-2,5-dione) (MBCM) and other aliquots Formula bismaleimide compound; bismaleimide containing a dimer acid skeleton and the like can be mentioned.

The dimeric acid skeleton-containing bismaleimide is a maleimide group or a maleimidemethyl group (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-ylmethyl group) in which two terminal carboxy groups (-COOH) of dimer acid are used. ) Means the bismaleimide compound. Dimeric acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably those having 11 to 22 carbon atoms, particularly preferably those having 18 carbon atoms), and its industrial production process is almost the same in the industry. It is standardized. As the dimer acid, a dimer acid having 36 carbon atoms as a main component, which is obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid and linoleic acid, which are particularly inexpensive and easily available, can be easily obtained. Further, the dimer acid may contain an arbitrary amount of monomeric acid, trimer acid, other polymerized fatty acids and the like depending on the production method, the degree of purification and the like. In addition, although double bonds remain after the polymerization reaction of unsaturated fatty acids, in the present specification, hydrogenated substances whose degree of unsaturation is lowered by further hydrogenation reaction are also included in dimer acid.

The molecular weight of the (E-1-3) aliphatic maleimide compound is preferably 150 to 5000, more preferably 300 to 1000. (E-1-3) The functional group equivalent of the maleimide group of the aliphatic maleimide compound is preferably 50 g / eq. ~ 2000 g / eq. , More preferably 100 g / eq. ~ 1000 g / eq. More preferably, 200 g / eq. ~ 600 g / eq. , Particularly preferably 300 g / eq. ~ 400 g / eq. Is.

Examples of commercially available products of the (E-1-3) aliphatic maleimide compound include "BMI-689" manufactured by Designer Moleculars.

<(E-2) Vinyl Phenyl Radical Polymerizable Compound>
(E-2) The vinylphenyl radically polymerizable compound is a radically polymerizable compound having a vinylphenyl group. The vinylphenyl radically polymerizable compound preferably has two or more vinylphenyl groups per molecule. The vinylphenyl radically polymerizable compound (E-2) is preferably a vinylbenzyl-modified polyphenylene ether having a vinylbenzyl group and a polyphenylene ether skeleton, and the formula (5)::

[In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group). ]
A vinylbenzyl-modified polyphenylene ether having a repeating unit represented by (the number of repeating units is preferably 2 to 300, more preferably 2 to 100) and a vinylbenzyl group (particularly, the hydrogen atoms of the hydroxyl groups at both ends of the polyphenylene ether are vinylbenzyl groups. It is particularly preferable that it is a bi-terminal vinylbenzyl-modified polyphenylene ether) replaced with.

The number average molecular weight of the (E-2) vinylphenyl radically polymerizable compound is preferably 500 to 10000, and more preferably 700 to 5000. (E-2) The functional group equivalent of the vinyl group of the vinyl phenyl radical polymerizable compound is preferably 200 g / eq. ~ 3000 g / eq. , More preferably 300 g / eq. ~ 2000 g / eq. Is.

Examples of commercially available products of the (E-2) vinylphenyl radically polymerizable compound include "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether) manufactured by Mitsubishi Gas Chemical Company, Inc. ..

<(E-3) (Meta) Acrylic Radical Polymerizable Compound>
The (meth) acrylic radical-polymerizable compound is a radical-polymerizable compound having an acryloyl group and / or a methacryloyl group. The (E-3) (meth) acrylic radically polymerizable compound preferably has two or more acryloyl groups and / or methacryloyl groups per molecule. The (meth) acrylic radically polymerizable compound is preferably a (meth) acrylic-modified polyphenylene ether having an acryloyl group and / or a methacryloyl group and a polyphenylene ether skeleton, and formula (6):

[In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group). ]
(The number of repeating units is preferably 2 to 300, more preferably 2 to 100) and a (meth) acrylic-modified polyphenylene ether having an acryloyl group and / or a methacryloyl group (particularly, the hydroxyl groups at both ends of the polyphenylene ether). Both terminal (meth) acrylic-modified polyphenylene ethers in which a hydrogen atom is replaced with an acryloyl group and / or a methacryloyl group) are particularly preferable.

The number average molecular weight of the (E-3) (meth) acrylic radical-polymerizable compound is preferably 500 to 10000, and more preferably 700 to 5000. The functional group equivalents of the acryloyl group and the methacryloyl group of the (meth) acrylic radically polymerizable compound are preferably 200 g / eq. ~ 3000 g / eq. , More preferably 300 g / eq. ~ 2000 g / eq. Is.

Examples of commercially available products of the (meth) acrylic radically polymerizable compound include "SA9000" and "SA9000-111" (methacryl-modified polyphenylene ether) manufactured by SABIC Innovative Plastics Co., Ltd.

The content of the radically polymerizable compound (E) in the resin composition is not particularly limited, but is preferably 40% by mass or less when the non-volatile component in the resin composition is 100% by mass.
It can be more preferably 20% 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 (E) radically polymerizable 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% by mass or more, 0. It can be 0.01% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more. could be.

<(F) Hardener>
The resin composition of the present invention may contain (F) a curing agent as an optional component. The (F) curing agent has a function of curing the resin composition (particularly, a function of reacting with (B) an epoxy resin and / or (E) a radically polymerizable compound to cure). The (F) curing agent referred to here is a component that does not correspond to the components (A) to (E).

The (F) curing agent is not particularly limited, but for example, (F-1) carbodiimide-based curing agent, (F-2) phenol-based curing agent and naphthol-based curing agent, (F-3) acid. Anhydride-based curing agent, (F-4) amine-based curing agent, (F-5) benzoxazine-based curing agent, (F-6) cyanate ester-based curing agent, and (F-7) thiol-based curing agent. Be done. (F) The curing agent may be used alone or in combination of two or more. In one embodiment, the (F) curing agent is one or more curing agents selected from the group consisting of (F-1) carbodiimide-based curing agents and (F-2) phenol-based curing agents and naphthol-based curing agents. It is preferably contained, and it is particularly preferable to contain (F-1) a carbodiimide-based curing agent. In one embodiment, the resin composition of the present invention particularly preferably contains a (F-1) carbodiimide-based curing agent from the viewpoint of obtaining the desired effect of the present invention particularly remarkably.

Examples of the (F-1) carbodiimide-based curing agent include a curing agent having one or more, preferably two or more carbodiimide structures in one molecule, and examples thereof include tetramethylene-bis (t-butylcarbodiimide). Aliphatic biscarbodiimides such as cyclohexanebis (methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis (xysilylcarbodiimide); polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylene Aliphatic polycarbodiimides such as carbodiimide, poly (methylenebiscyclohexylene carbodiimide), poly (isophorone carbodiimide); poly (phenylene carbodiimide), poly (naphthylene carbodiimide), poly (trilencarbodiimide), poly (methyldiisopropylphenylene carbodiimide) , Poly (triethylphenylene carbodiimide), poly (diethylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide), poly (diisopropylphenylene carbodiimide), poly (xylylene carbodiimide), poly (tetramethylxylylene carbodiimide), poly (methylenediimide) Examples thereof include polycarbodiimides such as aromatic polycarbodiimides such as phenylene carbodiimide) and poly [methylenebis (methylphenylene) carbodiimide].

Examples of commercially available carbodiimide-based curing agents include "carbodilite V-02B", "carbodilite V-03", "carbodilite V-04K", and "carbodilite V-07" manufactured by Nisshinbo Chemical Co., Ltd. "Carbodilite V-09"; "Stavaxol P", "Stavaxol P400", "Hycazil 510" and the like manufactured by Rheinchemy Co., Ltd. can be mentioned.

(F-2) As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. (F-2) Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kayaku Co., Ltd., and manufactured by Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485" manufactured by Nittetsu Chemical & Materials Co., Ltd. , "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-3018-50P" manufactured by DIC Corporation. "LA-1356", "TD2090", "TD-2090-60M" and the like can be mentioned.

Examples of the (F-3) acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule, and having two or more acid anhydride groups in one molecule. A hardener is preferred. Specific examples of the (F-3) acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnadic acid anhydride. Methylnadic hydride anhydride, trialkyltetrahydrophthalic anhydride, succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'- 4,4'-Diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1,2- C] Examples include polymer-type acid anhydrides such as furan-1,3-dione, ethylene glycol bis (anhydrotrimeritate), and styrene / maleic acid resin in which styrene and maleic acid are copolymerized. (F-3) Commercially available acid anhydride-based curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA", and Mitsubishi manufactured by Shin Nihon Rika Co., Ltd. Examples thereof include "YH-306" and "YH-307" manufactured by Chemical Corporation, and "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.

Examples of the (F-4) amine-based curing agent include curing agents having one or more, preferably two or more amino groups in one molecule, and examples thereof include aliphatic amines, polyether amines, and fats. Examples thereof include cyclic amines and aromatic amines. Among them, aromatic amines are preferable from the viewpoint of achieving the desired effects of the present invention. The (F-4) amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the (F-4) amine-based curing agent include 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3. '-Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl -4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 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. (F-4) A commercially available product may be used as the amine-based curing agent. For example, "SEIKACURE-S" manufactured by Seika Co., Ltd., "KAYABOND C-200S" manufactured by Nippon Kayaku Co., Ltd., "KAYABOND C-100", "KAYABOND C-100", " Examples thereof include "Kayahard AA", "Kayahard AB", "Kayahard AS", and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

(F-5) Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd .; "HFB2006M" manufactured by Showa High Polymer Co., Ltd .; "HFB2006M" manufactured by Shikoku Chemicals Corporation. Examples include "P-d" and "FA".

Examples of the (F-6) cyanate ester-based curing agent include bisphenol A cyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), and 4,4'-methylenebis (2,6-dimethylphenyl). Cyanate), 4,4'-Etilidendiphenyl disyanate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate) -3,5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, etc. Examples thereof include bifunctional cyanate resins, polyfunctional cyanate resins derived from phenol novolac, cresol novolak and the like, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the (F-6) cyanate ester-based curing agent include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (bisphenol) manufactured by Lonza Japan. A prepolymer in which a part or all of A-disyanate is triazined to form a trimer) and the like can be mentioned.

Examples of the (F-7) thiol-based curing agent include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptopropyl) isocyanurate, and the like. Be done.

The reaction group equivalent of the (F) curing agent is preferably 50 g / eq. ~ 3000 g / eq. , More preferably 100 g / eq. ~ 1000 g / eq. , More preferably 100 g / eq. ~ 500 g / eq. , Particularly preferably 100 g / eq. ~ 300 g / eq. Is. The reaction group equivalent is the mass of the curing agent per reaction group equivalent.

The content of the (F) 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 preferably 10. It is mass% or less, more preferably 5 mass% or less, and particularly preferably 3 mass% or less. The lower limit of the content of the (F) 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. It can be 01% by mass or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, and the like.

<(G) Curing accelerator>
The resin composition of the present invention may contain (G) a curing accelerator as an optional component.

Examples of the curing accelerator include (G-1) imidazole-based curing accelerator, (G-2) phosphorus-based curing accelerator, (G-3) urea-based curing accelerator, and (G-4) guanidine-based curing accelerator. Agents, (G-5) metal-based curing accelerators, (G-6) amine-based curing accelerators and the like can be mentioned. In one embodiment, the (G) curing accelerator preferably contains a (G-1) imidazole-based curing accelerator. The curing accelerator (G) may be used alone or in combination of two or more.

Examples of the (G-1) imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 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 trimerite , 1-Cyanoethyl-2-phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [ 2'-Undecylimidazolyl- (1')] -ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine , 2,4-Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxy Methylimidazole, 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 (G-1) imidazole-based curing accelerator, a commercially available product may be used. For example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Chemicals Corporation, and "2PHZ-PW" manufactured by Mitsubishi Chemical Corporation. Examples thereof include "P200-H50".

Examples of the (G-2) phosphorus-based curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, and bis (tetrabutylphosphonium) pyromeritate. , Tetributylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate, etc. Aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-triltriphenylphosphonium tetra-p- Triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrap-trilborate, triphenylethylphosphonium tetraphenylborate, tris (3-methylphenyl) ethylphosphonium tetraphenylborate, tris (2-methoxyphenyl) ethylphosphonium tetra Arophenylphosphine salts such as phenylborate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complex such as triphenylphosphine / triphenylborane; triphenyl Arophenylphosphine quinone addition reactants such as phosphine p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-Methyl-2-butenyl) phosphine, tricyclohexphinephosphine and other aliphatic phosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclophenylphosphine, triphenyl Hosphine, tri-o-triphenylphosphine, tri-m-trilphosphine, tri-p -Trill phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-isopropylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (4-tert-butylphenyl) phosphine , Tris (2,4-dimethylphenyl) phosphine, tris (2,5-dimethylphenyl) phosphine, tris (2,6-dimethylphenyl) phosphine, 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 (diphenylphosphine) propane, 1,4-bis (diphenylphosphine) Examples thereof include aromatic phosphines such as fino) butane, 1,2-bis (diphenylphosphino) acetylene, and 2,2'-bis (diphenylphosphino) diphenyl ether.

Examples of the urea-based curing accelerator (G-3) include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-. Dimethylurea such as dimethylurea, 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, 3-( 3,4-Dichlorophenyl) -1,1-dimethylurea, 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea, 3- (2-methylphenyl) -1,1-dimethylurea, 3- (4-Methylphenyl) -1,1-dimethylurea, 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) bis (N', N'-dimethylurea), N, N- (4-methyl-1,3-phenylene) bis (N', N'-dimethylurea) [toluenebis dimethylurea], etc. Aromatic dimethylurea and the like.

Examples of the (G-4) guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, and diphenyl. Guanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4] 4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1 -Cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biganide and the like can be mentioned.

Examples of the (G-5) metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include organic zinc 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 the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

Examples of the (G-6) amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and the like. 1,8-diazabicyclo (5,4,0) -undesen and the like can be mentioned.

As the (G-6) amine-based curing accelerator, a commercially available product may be used, and examples thereof include “MY-25” manufactured by Ajinomoto Fine-Techno Co., Ltd.

The content of the (G) curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably 15% by mass or less. It is 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less. The lower limit of 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, for example, 0% by mass or more, 0. It can be 001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, and the like.

<(H) Other additives>
The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyether sulfone resins, and the like. Thermoplastic resins such as polycarbonate resin, polyether ether ketone resin, polyester resin; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, phthalocyanine green, and iodin Colorants such as green, diazo yellow, crystal violet, titanium oxide, carbon black; polymerization prohibitive agents such as hydroquinone, catechol, pyrogallol, phenothiazine; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; Benton, montmorillonite, etc. Thickeners; silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, vinyl resin-based defoaming agents and other defoaming agents; benzotriazole-based ultraviolet absorbers and other ultraviolet absorbers; ureasilane and the like Adhesion improver; Adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; Antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants Agents: Fluorescent whitening agents such as stillben derivatives; Surfactants such as fluorine-based surfactants and silicone-based surfactants; Phosphorus-based flame retardants (for example, phosphoric acid ester compounds, phosphazenic compounds, phosphinic acid compounds, red phosphorus), Flame retardants such as nitrogen-based flame retardants (eg melamine sulfate), halogen-based flame retardants, inorganic flame retardants (eg antimony trioxide); phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicones Dispersants such as system dispersants, anionic dispersants, cationic dispersants; borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, etc. Examples thereof include stabilizers such as carboxylic acid anhydride-based stabilizers. (H) As the other additives, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio. The content of (H) 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 an arbitrary organic solvent as a volatile component in addition to the above-mentioned non-volatile component. As the organic solvent (I), known ones can be appropriately used, and the type thereof is not particularly limited. (I) Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-. Ester solvents such as butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol and ethylene glycol; 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, methyl 2-hydroxyisobutyrate Ester alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) and other ether alcohol solvents; N, N-dimethylformamide, N , N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide solvents; dimethylsulfoxide and other sulfoxide solvents; acetonitrile, propionitrile and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane and other fats Group hydrocarbon-based solvent; Examples thereof include aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (I) As the organic solvent, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

In one embodiment, the content of the organic solvent (I) is not particularly limited, but when all the components in the resin composition are 100% by mass, for example, 60% by mass or less and 40% by mass or less. , 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, and the like.

<Manufacturing method of resin composition>
The resin composition of the present invention is, for example, a compound containing a repeating unit represented by the formula (A) (1) in an arbitrary preparation container, an epoxy resin (B), an active ester compound (C), if necessary ( D) Inorganic filler, (E) radically polymerizable compound if necessary, (F) curing agent if necessary, (G) curing accelerator if necessary, (H) other additives if necessary , And, if necessary, (I) organic solvents can be added and mixed in any order and / or partly or all at the same time. Further, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or from beginning to end. Further, the resin composition may be uniformly dispersed by stirring or shaking using, for example, a stirring device such as a mixer or a shaking device in the process of adding and mixing, or thereafter. Further, at the same time as stirring or shaking, defoaming may be performed under low pressure conditions such as under vacuum.

<Characteristics of resin composition>
The resin composition of the present invention contains (A) a compound containing a repeating unit represented by the formula (1), (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, it is possible to obtain a cured product in which unevenness after lamination is suppressed. The unevenness after lamination represents the unevenness that may appear in the resin composition layer when the sheet-like laminated material such as a resin sheet and the interior substrate are laminated to form the resin composition layer on the inner layer substrate. This unevenness can usually appear in a portion where the thickness of the resin composition layer becomes uneven. This unevenness often appeared near the edge of the resin composition layer, but the present inventor has surprisingly found that this unevenness can be suppressed by using the resin composition of the present invention. Further, in a specific embodiment, a cured product having a low dielectric loss tangent (Df) can be obtained. Further, in a specific embodiment, a cured product having good plating adhesion can be obtained.

In one embodiment, the cured product of the resin composition of the present invention may be characterized by 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 preferably 0.02 or less and 0.01 or less. , More preferably 0.005 or less, 0.004 or less, still more preferably 0.003 or less, 0.0028 or less, and particularly preferably 0.0027 or less, 0.0026 or less.

In one embodiment, the cured product of the resin composition of the present invention can exhibit good plating adhesion. Therefore, in one embodiment, the peel strength of the plated conductor layer of the cured resin composition measured as in Test Example 4 below is preferably 0.1 kgf / cm or more, more preferably 0.2 kgf / cm or more. More preferably, it can be 0.3 kgf / cm or more. The upper limit may be 10 kgf / cm or less.

In one embodiment, the cured product of the resin composition of the present invention may be characterized by a low arithmetic mean roughness (Ra). Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment measured as in Test Example 3 below is preferably 200 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less. Is. The lower limit is not particularly limited and may be, for example, 1 nm or more and 2 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Further, in one embodiment, the relative permittivity (Dk) of the cured product of the resin composition of the present invention is preferably 5.0 or less when measured at 5.8 GHz and 23 ° C. as in Test Example 1 below. It can be more preferably 4.5 or less, still more preferably 4.0 or less, and particularly preferably 3.5 or less.

<Use of resin composition>
The resin composition of the present invention can be suitably used as a resin composition for insulating use, particularly as a resin composition for forming an insulating layer. Specifically, a resin composition for forming the insulating layer for forming the conductor layer (including the rewiring layer) formed on the insulating layer (resin for forming the insulating layer for forming the conductor layer). It can be suitably used as a composition). Further, in a printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention also requires a resin composition such as a resin sheet, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin. Can be used in a wide range of applications.

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

Further, since the resin composition of the present invention provides an insulating layer having good component embedding property, it can be suitably used even when the printed wiring board is a component-embedded circuit board.

<Sheet-like laminated material>
The resin composition of the present invention can be applied and used in a varnished state, but industrially, it is generally preferable to use the resin composition in the form of a sheet-like laminated material containing the resin composition.

As the sheet-like laminated material, the following resin sheets and prepregs 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 from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product having excellent insulating properties even if the cured product of the resin composition is a thin film. It is preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may 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 paper pattern, 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, the plastic material may be, for example, polyethylene terephthalate (hereinafter, may be abbreviated as "PET") or polyethylene naphthalate (hereinafter, abbreviated as "PEN"). ) And other polyesters, polycarbonates (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyimides. Of these, 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, and copper foil is preferable. 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 another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The support may be matted, corona-treated, or antistatic-treated on the surface to be joined to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples thereof include "AL-5" and "AL-7", "Lumilar T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Ltd., and "Unipee" manufactured by Unitika Ltd.

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

In one embodiment, the resin sheet may further contain any layer, if desired. Examples of such an arbitrary layer include a protective film similar to the support provided on a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support). Be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust and the like to the surface of the resin composition layer and scratches.

For the resin sheet, for example, a liquid resin composition is used as it is, or a resin varnish in which the resin composition is dissolved in an organic solvent is prepared, which is applied onto a support using a die coater or the like, and further dried. It can be produced by forming a resin composition layer.

Examples of the organic solvent include the same organic solvents as those described as the components of the resin composition. The organic solvent may be used alone or in combination of two or more.

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. Depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when a resin composition or resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the temperature is 50 ° C to 150 ° C for 3 minutes to 10 to 10. The resin composition layer can be formed by drying for a minute.

The resin sheet can be rolled up 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-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for the prepreg such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-shaped 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-shaped fiber base material is not particularly limited. Usually, it is 10 μm or more.

The prepreg can be produced 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-shaped 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 (printed). It can be more preferably used for the interlayer insulating layer of the wiring board).

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

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

The "inner layer substrate" used in the step (I) is a member that becomes a substrate of a printed wiring board, and is, 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. And so on. Further, the substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board". Further, an intermediate product in which an insulating layer and / or a conductor layer should be formed when the printed wiring board is manufactured is also included in the "inner layer substrate" 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 inner layer substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The inner layer substrate and the resin sheet may be laminated by a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 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 performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

After laminating, the laminated resin sheet may be smoothed by pressing the heat-bonded member from the support side under normal pressure (under atmospheric pressure), for example. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

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

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

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

Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is placed 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. Preheating may be preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes.

In manufacturing the printed wiring board, (III) a step of drilling a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a 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 used for manufacturing a printed wiring board. When the support is removed after the step (II), the support is removed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step ( It may be carried out between IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) 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 when a resin sheet is used.

The step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) may be carried out by using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the resin composition used for forming 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. Usually, smear removal is also performed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

The swelling solution used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include "Swelling Dip Security SBU" and "Swelling Dip Security 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 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, and 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. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.

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

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

The step (V) is a step of forming a conductor layer, and a 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 is 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, nickel-chromium alloy, copper, etc.). A layer formed of a nickel alloy and a copper / titanium alloy) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a monometal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable. A metal layer is more preferred.

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

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

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

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

In other embodiments, the conductor layer may be formed using metal foil. When the conductor layer is formed using the metal foil, it is preferable that the step (V) is carried out between the steps (I) and the steps (II). For example, after step (I), the support is removed and a metal foil is laminated on the surface of the exposed resin composition layer. Lamination of the resin composition layer and the metal foil may be carried out by a vacuum laminating method. The laminating conditions may be the same as the conditions described for step (I). Then, step (II) is carried out to form an insulating layer. After that, the metal foil on the insulating layer can be used to form a conductor layer having a desired wiring pattern by a conventionally known technique such as a subtractive method or a modified semi-additive method.

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

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

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. When no temperature is specified, the temperature and pressure conditions are room temperature (25 ° C.) and atmospheric pressure (1 atm).

<Synthesis example 1>
In a four-necked flask, 894.96 mmol of dichloropyrimidine, 900.00 mmol of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1.2 mol of potassium carbonate, N-methyl-2. -Pyrrolidone (450 g) was added. After replacing the inside of the flask with nitrogen, the contents of the flask were heated at 130 ° C. for 6 hours, and water generated during heating was removed from the Dean-Stark tube at any time. After cooling the contents of the flask to room temperature, the precipitated solids are filtered off, methanol is added to the filtrate, the precipitated solids are washed with methanol, and these solids are dried by the following formula (1'). The polymer compound represented (weight average molecular weight (Mw); 87,000 (polystyrene conversion value)) was obtained. The obtained compound ^{was measured by 13} C-NMR, and the product was confirmed.

<Example 1>
Two parts of the polymer compound (cyclohexanone solution having a non-volatile component ratio of 20%) obtained in Synthesis Example 1, naphthalene-type epoxy resin (“HP-4032-SS” manufactured by DIC, 1,6-bis (glycidyloxy) naphthalene, Epoxy equivalent about 145 g / eq.) 10 parts, active ester compound (DIC "HPC-8000-65T", active ester group equivalent about 223 g / eq., Toluene solution with non-volatile component ratio 65%), silane cup 90 parts of spherical silica ("SO-C2" manufactured by Admatex, average particle size 0.5 μm, specific surface area 5.8 m ^{2 / g) surface-treated with a ring agent (“KBM-573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.)} , Triazine skeleton-containing phenolic curing agent ("LA-3018-50P" manufactured by DIC, active group equivalent of about 151 g / eq., 2-methoxypropanol solution having a non-volatile component ratio of 50%), 2 parts, carbodiimide-based curing agent (Nisshinbo) Chemical company "V-03", active group equivalent about 216 g / eq., Toluene solution with non-volatile component ratio 50%) 5 parts, imidazole-based curing accelerator (Shikoku Kasei Kogyo Co., Ltd. "1B2PZ", 1-benzyl-2 -Finylimidazole) 0.1 part was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin composition.

<Example 2>
Instead of 30 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC), the active ester compound ("HPC-8150-62T" manufactured by DIC), the active ester group equivalent of about 220 g / eq., The non-volatile component ratio 62 A resin composition was prepared in the same manner as in Example 1 except that 30 parts of a mass% toluene solution was used.

<Example 3>
The amount of spherical silica ("SO-C2" manufactured by Admatex Co., Ltd.) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 90 parts to 92 parts, and biphenyl aralkyl. A resin composition was prepared in the same manner as in Example 2 except that two parts of novolak type maleimide (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., MEK / toluene mixed solution having a non-volatile component ratio of 70%) were used. bottom.

<Example 4>
The amount of spherical silica (“SO-C2” manufactured by Admatex) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 90 parts to 93 parts, and imidazole-based curing was performed. Except for changing the amount of accelerator (“1B2PZ” manufactured by Shikoku Chemicals Corporation) from 0.1 part to 0.5 part and using 1 part of maleimide-terminated polyimide compound (“BMI-1500” manufactured by DMI). Prepared a resin composition in the same manner as in Example 2.

<Example 5>
The amount of spherical silica (“SO-C2” manufactured by Admatex) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 90 parts to 93 parts, and further methacryl-modified. A resin composition was prepared in the same manner as in Example 2 except that two parts of polyphenylene ether (“SA9000-111” manufactured by SABIC Innovative Plastics Co., Ltd.) were used.

<Example 6>
The amount of spherical silica ("SO-C2" manufactured by Admatex Co., Ltd.) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 90 parts to 93 parts, and imidazole-based curing was performed. The amount of accelerator ("1B2PZ" manufactured by Shikoku Chemicals Corporation) was changed from 0.1 part to 0.5 part, and vinylbenzyl-modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Company, Inc.), a non-volatile component. A resin composition was prepared in the same manner as in Example 2 except that two parts (toluene solution having a ratio of 65%) were used.

<Comparative example 1>
Instead of 2 parts of the polymer compound (cyclohexanone solution having a non-volatile component ratio of 20%) obtained in Synthesis Example 1, a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK having a non-volatile component ratio of 30% and cyclohexanone 1: 1) The same as in Example 1 except that 1.5 parts of the solution) was used and the amount of the imidazole-based curing accelerator (“1B2PZ” manufactured by Shikoku Chemicals Corporation) was changed from 0.1 part to 0.5 part. To prepare a resin composition.

<Comparative example 2>
Instead of 2 parts of the polymer compound (cyclohexanone solution having a non-volatile component ratio of 20%) obtained in Synthesis Example 1, a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK having a non-volatile component ratio of 30% and cyclohexanone 1: 1) The same as in Example 2 except that 1.5 parts of the solution) was used and the amount of the imidazole-based curing accelerator (“1B2PZ” manufactured by Shikoku Chemicals Corporation) was changed from 0.1 part to 0.5 part. To prepare a resin composition.

<Test Example 1: Measurement of Relative Permittivity and Dissipation Factor>
(1) Preparation of Resin Sheet A with a Resin Composition Layer Thickness of 40 μm A polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared as a support. The resin compositions obtained in Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying was 40 μm. Then, the resin composition was dried at 80 ° C. to 100 ° C. (average 90 ° C.) for 4 minutes to obtain a resin sheet A containing a support and a resin composition layer.

(2) Preparation of Cured Product B for Evaluation The resin sheet A was cured in an oven at 190 ° C. for 90 minutes. By peeling the support from the resin sheet A taken out from the oven, a cured product of the resin composition layer was obtained. The cured product was cut into a length of 80 mm and a width of 2 mm and used as a cured product B for evaluation.

(3) Measurement of Relative Permittivity and Dissipation Factor For the cured product B for evaluation, a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. were performed by the cavity resonance perturbation method using "HP8362B" manufactured by Asilent Technologies. The relative permittivity value (Dk value) and the dielectric loss tangent value (Df value) were measured. Measurements were carried out using two test pieces, and the average was calculated.

<Test Example 2: Evaluation of unevenness after laminating>
(1) Preparation of inner layer substrate Both sides of the glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic “R1515A”) on which the inner layer circuit is formed are microscopic. The copper surface was roughened by etching 1 μm with an etching agent (“CZ8101” manufactured by MEC).

(2) Lamination of Resin Sheet A Using a batch type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700"), the resin sheet A obtained in Test Example 1 (1) is resinified. Both sides of the inner layer substrate were laminated so that the composition layer was in contact with the inner layer substrate. Lamination was carried out by reducing the pressure for 30 seconds, adjusting the atmospheric pressure to 13 hPa or less, and then crimping at 120 ° C. and a pressure of 0.74 MPa for 30 seconds. Then, heat pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Evaluation of unevenness after laminating After laminating, those in which dents in the resin were observed along the periphery of the inner layer substrate were evaluated as "yes", and those in which no dents were observed were evaluated as "none".

<Test Example 3: Arithmetic Mean Roughness (Ra) Measurement>
(1) Thermosetting of Resin Composition Layer The inner layer substrate on which the resin sheet A was laminated in Test Example 2 (2) was put into an oven at 130 ° C. and heated for 30 minutes, and then transferred to an oven at 170 ° C. for 30. The resin composition layer was heat-cured by heating for a minute to form an insulating layer. Then, the support was peeled off to obtain a cured substrate A having an insulating layer, an inner layer substrate, and an insulating layer in this order.

(2) Roughing Treatment The cured substrate A was subjected to desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out.

(Wet desmear treatment)
The cured substrate A is immersed in a swelling solution (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, and then an oxidizing agent solution (Atotech Japan). It was immersed in "Concentrate Compact CP" manufactured by the same company (an aqueous solution having a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C. for 20 minutes. Then, it was immersed in a neutralizing solution (“Reduction Solution Securigant P” manufactured by Atotech Japan, sulfuric acid aqueous solution) at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes.

(3) Measurement of Arithmetic Mean Roughness (Ra) of Insulation Layer Surface After Roughing Treatment The arithmetic mean roughness (Ra) of the insulation layer surface after roughening treatment is measured by a non-contact surface roughness meter (manufactured by Bruker). Using WYKO NT3300), the measurement range was determined by the numerical value obtained as 121 μm × 92 μm with a VSI mode and a 50x lens. It was measured by obtaining the average value of 10 points for each.

<Test Example 4: Measurement of peel strength>
(1) Formation of Conductor Layer A conductor layer was formed on the roughened surface of the insulating layer in the cured substrate A roughened in Test Example 3 (2) according to the semi-additive method. That is, the roughened substrate was _{immersed in an electroless plating solution containing PdCl 2} at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. Then, after heating at 150 ° C. for 30 minutes to perform annealing treatment, an etching resist was formed and a pattern was formed by etching. Then, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 25 μm, and annealing treatment was performed at 190 ° C. for 60 minutes. The obtained substrate is referred to as "evaluation substrate B".

(2) Measurement of Peel Strength of Plated Conductor Layer The peel strength of the insulating layer and the conductor layer was measured in accordance with the Japanese Industrial Standards (JIS C6481). Specifically, a notch having a width of 10 mm and a length of 100 mm is made in the conductor layer of the evaluation substrate B, one end of the notch is peeled off, and the conductor layer is grasped with a gripper. The load (kgf / cm) when the 35 mm was peeled off was measured, and the peeling strength was determined. A tensile tester (“AC-50C-SL” manufactured by TSE) was used for the measurement.

Table 1 below shows the amounts of non-volatile components used in the resin compositions of Examples and Comparative Examples, the measurement results and evaluation results of Test Examples.

By using the compound containing the repeating unit represented by the formula (A), the epoxy resin (B), and the active ester compound (C), the dielectric loss tangent (Df) is low and the peel strength is good. It was found that a cured product with suppressed unevenness after laminating can be obtained.

Claims (20)

Equation (A):

[In the formula, ring A represents a nitrogen-containing aromatic ring which may have a substituent; ring B and ring C each independently represent an aromatic ring which may have a substituent; X represents a single bond or divalent non-aromatic hydrocarbon group. ]
A resin composition containing a compound containing a repeating unit represented by (B), an epoxy resin (B), and an active ester compound (C). The component (A) is of the formula (1A) or (1B):

[In the formula, X ¹ , X ² , X ³ and X ⁴ each independently indicate N, CH or CR ^a , and at least one of ^{X 1} , X ² , X ³ and X ^{4 is N.} R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an alkenyl group, or R ¹ and R ² are bonded together together and are selected from an alkyl group and an alkenyl group. It forms a cycloalkane ring which may have a group or a cycloalkane ring which may have a group selected from an alkyl group and an alkenyl group; ^Ra , R ^b and R ^c are independent of each other. , B and c each independently represent an integer of 0-3. ]
The resin composition according to claim 1, which is a compound containing a repeating unit represented by. The resin composition according to claim 1 or 2, wherein the content of the component (A) is 0.01% by mass to 3% 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 3, wherein the component (B) contains (B-1) a fused ring structure-containing epoxy resin. The resin composition according to claim 4, wherein the component (B-1) is a monomer-type condensed ring structure-containing epoxy resin. The resin composition according to any one of claims 1 to 5, wherein the content of the component (B) is 1% by mass to 30% 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 6, wherein the mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 10 to 50. The resin composition according to any one of claims 1 to 7, wherein the content of the component (C) is 5% by mass to 30% 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 8, wherein the mass ratio of the component (C) to the component (A) (component (C) / component (A)) is 30 to 100. The resin composition according to any one of claims 1 to 9, further comprising (D) an inorganic filler. The resin composition according to claim 10, wherein the component (D) is silica. The resin composition according to claim 10 or 11, wherein the content of the component (D) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 12, wherein the content of the component (D) is 70% 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 13, further comprising (E) a radically polymerizable compound. The resin composition according to any one of claims 1 to 14, further comprising (F-1) a carbodiimide-based curing agent. The cured product of the resin composition according to any one of claims 1 to 15. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 15. A resin sheet having a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 15 provided on the support. A printed wiring board provided with an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 15. A semiconductor device including the printed wiring board according to claim 19.