CN115505313A

CN115505313A - Resin composition

Info

Publication number: CN115505313A
Application number: CN202210710178.XA
Authority: CN
Inventors: 川合贤司
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2021-06-23
Filing date: 2022-06-22
Publication date: 2022-12-23
Also published as: JP2023003393A; TW202307060A; KR20220170772A

Abstract

The present invention addresses the problem of providing a resin composition that enables the production of a cured product having excellent plating adhesion and a reduced dielectric loss tangent (Df). The solution of the present invention is a resin composition comprising (A) an aromatic nitrogen compound containing a phenolic hydroxyl group, (B) an epoxy resin, and (C) a reactive ester compound.

Description

Resin composition

Technical Field

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

Background

As a manufacturing technique of a printed wiring board, a manufacturing method using a stack (build up) method in which insulating layers and conductor layers are alternately stacked is known. The insulating layer of the printed wiring board is generally formed by curing a resin composition. It has been known that the use of an epoxy resin composition containing an active ester compound as a resin composition for forming an insulating layer can improve plating adhesion and reduce the dielectric loss tangent of the insulating layer (patent document 1).

Documents of the prior art

Patent literature

Patent document 1: japanese patent laid-open No. 2020-23714.

Disclosure of Invention

Problems to be solved by the invention

However, in recent years, further reduction in dielectric loss tangent of the insulating layer and further improvement in plating adhesion have been demanded.

The present invention addresses the problem of providing a resin composition that can provide a cured product that has excellent plating adhesion and a reduced dielectric loss tangent (Df).

Means for solving the problems

As a result of diligent studies to achieve the object of the present invention, the present inventors have found that: the present inventors have surprisingly found that a cured product having excellent plating adhesion and a reduced dielectric loss tangent (Df) can be obtained by using a resin composition containing (a) an aromatic nitrogen compound having a phenolic hydroxyl group, (B) an epoxy resin, and (C) an active ester compound, and have completed the present invention.

That is, the present invention includes the following;

[1] a resin composition comprising (A) a benzotriazole compound having a phenolic hydroxyl group, (B) an epoxy resin, and (C) an active ester compound.

[2] A resin composition comprising (A) a compound represented by the formula (1 a) or (1B), (B) an epoxy resin, and (C) an active ester compound,

[ chemical formula 1]

In the above formula, R represents

(1) An aryl group substituted with at least one hydroxyl group and further optionally having a substituent, or

(2) An aralkyl group substituted with a hydroxyl group on at least one aromatic carbon atom and further optionally having a substituent;

x and Y each independently represent CH or N;

ring Z represents an optionally substituted aromatic ring.

[3] The resin composition according to the above [2], wherein R is

(1) An aryl group which is substituted with at least one hydroxyl group, is further substituted with at least one alkyl group having 3 or more carbon atoms, and further optionally has a substituent, or

(2) An aralkyl group which is substituted with a hydroxyl group on at least one aromatic carbon atom, is further substituted with an alkyl group having 3 or more carbon atoms on at least one aromatic carbon atom, and further optionally has a substituent.

[4] The resin composition according to the above [1] or [2], wherein,

(A) Component (C) contains a compound represented by the formula (2 a) or (2 b),

[ chemical formula 2]

In the above-mentioned formula, the compound has the following formula,

a represents a single bond, or C (R) ^A ) ₂ ；

R ^A Each independently represents a hydrogen atom, or an alkyl group;

R ¹ and R ² Each independently represents a substituent;

a and b each independently represent an integer of 0 to 4.

[5]According to the above [4]]The resin composition, wherein R ² At least one of them is a secondary alkyl group having 3 to 10 carbon atoms or a tertiary alkyl group having 4 to 10 carbon atoms, and b is 1,2 or 3;

[6] the resin composition according to the above [1] or [2], wherein the component (A) contains a compound having a molecular weight of 300 or more;

[7] the resin composition according to the above [1] or [2], wherein the content of the component (A) is 0.001 to 5% by mass, based on 100% by mass of nonvolatile components in the resin composition;

[8] the resin composition according to the above [1] or [2], further comprising (D) a compound having a radical-reactive group;

[9] the resin composition according to the above [1] or [2], wherein the content of the component (B) is 0.1 to 30% by mass, based on 100% by mass of nonvolatile components in the resin composition;

[10] the resin composition according to the above [1] or [2], wherein the content of the component (C) is 10% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass;

[11] the resin composition according to the above [1] or [2], which further comprises (E) an inorganic filler;

[12] the resin composition according to the above [11], wherein the component (E) is silica;

[13] the resin composition according to the above [11], wherein the content of the component (E) is 40% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass;

[14] the resin composition according to the above [1] or [2], which further comprises (F) an organic filler;

[15] the resin composition according to the above [1] or [2], further comprising a phenol-based curing agent;

[16] the resin composition according to the above [1] or [2], wherein the minimum melt viscosity at 60 ℃ to 200 ℃ is 1400 poise or less;

[17] the resin composition according to the above [1] or [2], wherein a dielectric loss tangent (Df) of a cured product of the resin composition is 0.0026 or less as measured at 5.8GHz and 23 ℃;

[18] the resin composition according to the above [1] or [2], which is used for forming an insulating layer for forming a conductor layer;

[19] the resin composition according to the above [1] or [2], which is used for forming an insulating layer of a printed wiring board;

[20] a cured product of the resin composition according to [1] or [2 ];

[21] a sheet-like laminate comprising the resin composition according to [1] or [2 ];

[22] a resin sheet having: a support and a resin composition layer formed of the resin composition according to [1] or [2] above provided on the support;

[23] a printed wiring board, which comprises the [1] or [2] resin composition cured material formed by the insulating layer;

[24] a semiconductor device comprising the printed wiring board according to [23 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the resin composition of the present invention, a cured product having excellent plating adhesion and a reduced dielectric loss tangent (Df) can be obtained.

Detailed Description

The present invention will be described in detail below based on preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and can be implemented by arbitrarily changing the embodiments without departing from the scope of the claims and the equivalent scope thereof.

< resin composition >

The resin composition of the present invention comprises: an aromatic nitrogen compound containing a phenolic hydroxyl group, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product having excellent plating adhesion and a reduced dielectric loss tangent (Df) can be obtained. Further, in one embodiment, the resin composition of the present invention may have such a feature that the melt viscosity is low.

The resin composition of the present invention may further contain any component in addition to the aromatic nitrogen compound (a) containing a phenolic hydroxyl group, (B) an epoxy resin, and (C) an active ester compound. Examples of the optional components include (C') other curing agents, (D) compounds containing radical reactive groups, (E) inorganic fillers, (F) organic fillers, (G) curing accelerators, (H) other additives, and (I) organic solvents.

Hereinafter, each component contained in the resin composition will be described in detail.

< (A) an aromatic nitrogen compound having a phenolic hydroxyl group

In the first embodiment, the resin composition of the present invention contains a benzotriazole compound having a phenolic hydroxyl group as the component (a). (A) The component (A) may have a phenolic hydroxyl group as a substituent of the benzotriazole ring, or may have a phenolic hydroxyl group as a substituent of an aromatic ring other than the benzotriazole ring. (A) The component (a) is preferably a compound having an aromatic ring substituted with a hydroxyl group (phenolic hydroxyl group) and a benzotriazole ring different from the aromatic ring, more preferably a compound having an aromatic carbocyclic ring substituted with a hydroxyl group (phenolic hydroxyl group) and a benzotriazole ring, still more preferably a compound having an aromatic carbocyclic ring substituted with a hydroxyl group (phenolic hydroxyl group) and an alkyl group having 3 or more carbon atoms and a benzotriazole ring, particularly preferably a compound having a benzene ring substituted with a hydroxyl group (phenolic hydroxyl group) and an alkyl group having 3 or more carbon atoms and a benzotriazole ring. (A) The component (C) has 1 or 2 or more phenolic hydroxyl groups in 1 molecule, preferably 1 or 2. (A) The component (A) has 1 or 2 or more benzotriazole rings in 1 molecule, preferably 1 or 2. (A) The component (B) is preferably an alkyl group having 1 or 2 or more carbon atoms of 3 or more, particularly preferably 1 or 2, in 1 molecule on an aromatic carbocyclic ring (benzene ring) having a phenolic hydroxyl group. The alkyl group having 3 or more carbon atoms is preferably a secondary alkyl group having 3 to 10 carbon atoms or a tertiary alkyl group having 4 to 10 carbon atoms.

An aromatic ring refers to a ring following the Huckel's rule with a number of electrons contained in a pi-electron system on the ring of 4p +2 (p is a natural number). The aromatic ring may be an aromatic carbocyclic ring having only carbon atoms as ring-forming atoms, or an aromatic heterocyclic ring having not only carbon atoms but also hetero atoms such as oxygen atom, nitrogen atom, sulfur atom and the like as ring-forming atoms, and in one embodiment, an aromatic carbocyclic ring is preferable. In one embodiment, the aromatic ring is preferably a 5-to 14-membered aromatic ring, more preferably a 6-to 14-membered aromatic ring, and still more preferably a 6-to 10-membered aromatic ring. Preferred specific examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and the like, more preferred are benzene ring and naphthalene ring, and particularly preferred is benzene ring.

In a second embodiment, the resin composition of the present invention contains a compound represented by formula (1 a) or (1 b) as component (a).

[ chemical formula 3]

[ wherein R represents (1) an aryl group which is substituted with at least one hydroxyl group and further optionally has a substituent, or (2) an aralkyl group which is substituted with a hydroxyl group on at least one aromatic carbon atom and further optionally has a substituent; x and Y each independently represent CH or N; ring Z represents an aromatic ring optionally having a substituent. ]. In the present specification, the component (a) in the first embodiment and the component (a) in the second embodiment may be collectively referred to as "(a) an aromatic nitrogen compound containing a phenolic hydroxyl group". The (A) component may be in the form of a salt.

R represents (1) an aryl group which is substituted with at least one hydroxyl group and further optionally has a substituent, or (2) an aralkyl group which is substituted with a hydroxyl group on at least one aromatic carbon atom and further optionally has a substituent (on an aromatic carbon atom and on an aliphatic carbon atom).

Aryl refers to a 1-valent aromatic hydrocarbon radical formed by removing 1 hydrogen atom from an aromatic carbocyclic ring. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, particularly preferably an aryl group having 6 to 10 carbon atoms, unless otherwise specified. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

The aralkyl group means an alkyl group substituted with 1 or 2 or more (preferably 1) aryl groups. The aralkyl group is not particularly limited, but is preferably an aralkyl group having 7 to 15 carbon atoms, particularly preferably an aralkyl group having 7 to 11 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, a hydrocinnamyl group, an α -methylbenzyl group, an α -cumyl group (cumyl), a 1-naphthylmethyl group, a 2-naphthylmethyl group and the like.

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

The "substituent" included in the definition of the symbol of formula (1 a) or (1 b) is not particularly limited, and in one embodiment, for example, is a group formed of 1 or more (for example, 1 to 100, preferably 1 to 50) skeleton atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom, and may have a linear structure, a branched structure, and/or a cyclic structure, may be a group not including an aromatic ring, or may be a group including an aromatic ring. <xnotran> (1 a) (1 b) " " , (1) , (2) , (3) , (4) , , , (5) , , , , , (6) , , , , , (7) , , - , (8) , , , , - , (9) , , , , - , (10) , , - , (11) , , , , - , (12) , , - - , (13) , , , , - - , (14) , , </xnotran> And an alkyl-oxy-carbonyl group substituted with a group selected from the group consisting of a heterocyclic group, (15) an aryl-oxy-carbonyl group optionally substituted with a group selected from the group consisting of a hydroxyl group, a halogen atom, an alkyl group, an aryl group, and a heterocyclic group, and the like. Here, the heterocyclic group is further optionally substituted with a halogen atom, an alkyl group or the like. The heterocyclic group means a cyclic group having a heteroatom such as an oxygen atom, a nitrogen atom or a sulfur atom in addition to a carbon atom. The heterocyclic group is preferably a 5-to 14-membered heterocyclic group. The heterocyclic group may be an aromatic heterocyclic group or a non-aromatic heterocyclic group, and is preferably an aromatic heterocyclic group. Examples of the heterocyclic group include monocyclic aromatic heterocyclic groups such as pyrrolyl, imidazolyl, pyrazolyl, triazolyl and pyridyl; fused aromatic heterocyclic groups such as indolyl, isoindolyl, indazolyl, benzimidazolyl and benzotriazolyl, and the like.

The halogen atom means a fluorine atom, chlorine atom, bromine atom or iodine atom, preferably chlorine atom.

In one embodiment, R is preferably (1) an aryl group which is substituted with at least one hydroxyl group and further substituted with at least one alkyl group having 3 or more carbon atoms and further optionally having a substituent, or (2) an aralkyl group which is substituted with a hydroxyl group on at least one aromatic carbon atom and further substituted with an alkyl group having 3 or more carbon atoms on at least one aromatic carbon atom and further optionally having a substituent; more preferably an aryl group which is substituted with at least one hydroxyl group, is further substituted with at least one alkyl group having 3 or more carbon atoms, and further optionally has a substituent; still more preferably, the aromatic group is substituted with at least one hydroxyl group, and further substituted with at least one secondary alkyl group having 3 to 10 carbon atoms or tertiary alkyl group having 4 to 10 carbon atoms, and further optionally has a substituent selected from the group consisting of (1) a halogen atom, (2) a heterocyclic group, (3) an alkyl group optionally substituted with a group selected from the group consisting of a hydroxyl group, a halogen atom, and a heterocyclic group, (4) an aryl group optionally substituted with a group selected from the group consisting of a hydroxyl group, a halogen atom, an alkyl group, an aryl group, and a heterocyclic group, and (5) an aralkyl group optionally substituted with a group selected from the group consisting of a hydroxyl group, a halogen atom, an alkyl group, an aryl group, and a heterocyclic group.

X and Y each independently represent CH or N. In one embodiment, it is preferred that at least one of X and Y is N, more preferably both are N.

Ring Z represents an aromatic ring optionally having a substituent. In one embodiment, ring Z is preferably a benzene ring optionally having a substituent, more preferably a benzene ring optionally substituted with a group selected from a hydroxyl group, a halogen atom, and an alkyl group, further more preferably a benzene ring optionally substituted with a halogen atom.

In a preferred embodiment, the resin composition of the present invention contains a compound represented by formula (2 a) or (2 b) as the component (a).

[ chemical formula 4]

[ wherein A represents a single bond, or C (R) ^A ) ₂ ；R ^A Each independently represents a hydrogen atom, or an alkyl group; r ¹ And R ² Each independently represents a substituent; a and b each independently represent an integer of 0 to 4.]。

The "substituent" included in the definition of the symbol of formula (2 a) or (2 b) includes the same groups as the "substituent" included in the definition of the symbol of formula (1 a) or (1 b).

A represents a single bond, or C (R) ^A ) ₂ 。

In one embodiment, a is particularly preferably a single bond. R ^A Each independently represents a hydrogen atom or an alkyl group. In one embodiment, R ^A Preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

R ¹ Each independently represents a substituent. In one embodiment, R ¹ Each independently is preferably a halogen atom.

R ² Each independently represents a substituent. In one embodiment, R ² It is preferred that each independently represents (1) a halogen atom, (2) a heterocyclic group, (3) an alkyl group optionally substituted with a group selected from the group consisting of a hydroxyl group, a halogen atom and a heterocyclic group, and (4) an alkyl group optionally substituted with a group selected from the group consisting of a hydroxyl group, a halogen atom and a heterocyclic groupA hydroxyl group, a halogen atom, an alkyl group, an aryl group, and an aryl group substituted with a group selected from a heterocyclic group, or (5) an aralkyl group optionally substituted with a group selected from a hydroxyl group, a halogen atom, an alkyl group, an aryl group, and a heterocyclic group.

a represents an integer of 0 to 4, and in one embodiment, is preferably 0, 1,2 or 3, more preferably 0, 1 or 2, and further more preferably 0 or 1.

b represents an integer of 0 to 4, and in one embodiment, is preferably 0, 1,2 or 3, more preferably 0, 1 or 2, and further more preferably 1 or 2.

In one embodiment, R is preferred ² At least one of them is an alkyl group having 3 or more carbon atoms, and b is an integer of 1 to 4; more preferably R ² At least one of them is a secondary alkyl group having 3 to 10 carbon atoms or a tertiary alkyl group having 4 to 10 carbon atoms, and b is 1,2 or 3; even more preferably R ² At least one of them is a tertiary alkyl group having 4 to 10 carbon atoms, and b is 1 or 2; particularly preferably R ² At least one of which is tert-butyl, tert-pentyl, tert-hexyl, tert-heptyl, or tert-octyl, and b is 1 or 2.

In a particularly preferred embodiment, the resin composition of the present invention contains a compound represented by formula (3 a) or (3 b) as the component (a).

[ chemical formula 5]

[ in the formula,

A ¹ represents a single bond, or C (R) ^A1 ) ₂ ；

R ^A1 Each independently represents a hydrogen atom, or an alkyl group;

R ^3a 、R ^3b 、R ^3c and R ^3d Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, or an alkyl group;

R ^4a 、R ^4b 、R ^4c 、R ^4d and R ^4e Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, a group represented by the formula (x), or a group represented by the formula (y 1) or (y 2)And (4) clustering.

[ chemical formula 6]

[ chemical formula 7]

And R is ^4a 、R ^4b 、R ^4c 、R ^4d And R ^4e At least one of which is a hydroxyl group;

A ² represents a single bond, O, or C (R) ^A2 ) ₂ ；

R ^A2 Each independently represents a hydrogen atom, or an alkyl group;

A ³ represents a single bond, or C (R) ^A3 ) ₂ ；

R ^A3 Each independently represents a hydrogen atom, or an alkyl group;

R ^5a 、R ^5b 、R ^5c 、R ^5d and R ^5e Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, or a group represented by the formula (y 1) or (y 2);

R ^6a 、R ^6b 、R ^6c and R ^6d Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, or an alkyl group;

* Indicates the binding site. ].

A ¹ Represents a single bond, or C (R) ^A1 ) ₂ . In one embodiment, A ¹ Particularly preferred is a single bond. R ^A1 Each independently represents a hydrogen atom or an alkyl group. In one embodiment, R ^A1 Preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

R ^3a 、R ^3b 、R ^3c And R ^3d Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, or an alkyl group. In one embodiment, R ^3a 、R ^3b 、R ^3c And R ^3d Preferably each independently represents hydrogenAn atom, or a halogen atom, more preferably R ^3a 、R ^3c And R ^3d Is a hydrogen atom and R ^3b Is a hydrogen atom, or a halogen atom; even more preferably R ^3a 、R ^3c And R ^3d Is a hydrogen atom and R ^3b Is a hydrogen atom or a chlorine atom.

R ^4a 、R ^4b 、R ^4c 、R ^4d And R ^4e Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, a group represented by the formula (x), or a group represented by the formula (y 1) or (y 2), and R ^4a 、R ^4b 、R ^4c 、R ^4d And R ^4e At least one of which is a hydroxyl group. In one embodiment, R ^4a 、R ^4b 、R ^4c 、R ^4d And R ^4e It is preferred that each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, or a group represented by the formula (x), and R ^4a 、R ^4b 、R ^4c 、R ^4d And R ^4e At least one of which is a hydroxyl group; more preferably R ^4a Is hydroxy, R ^4b Is a hydrogen atom, an alkyl group, or a group represented by the formula (x), and R ^4c 、R ^4d And R ^4e Each independently a hydrogen atom, or an alkyl group; more preferably R ^4a Is hydroxy, R ^4b Is a hydrogen atom, an alkyl group, or a group represented by the formula (x), R ^4c 、R ^4d And R ^4e Each independently is a hydrogen atom, or an alkyl group, and R ^4b 、R ^4c 、R ^4d And R ^4e At least one of the above (B) is a secondary alkyl group having 3 to 10 carbon atoms or a tertiary alkyl group having 4 to 10 carbon atoms; more preferably R ^4a Is hydroxy, R ^4b Is a hydrogen atom, an alkyl group, or a group represented by the formula (x), R ^4c And R ^4e Is a hydrogen atom, R ^4d Is a hydrogen atom, or an alkyl group, and R ^4b And R ^4d At least one of the alkyl group(s) is a tertiary alkyl group having 4 to 10 carbon atoms; particularly preferably R ^4a Is hydroxy, R ^4b Is a hydrogen atom, an alkyl group, or a group represented by the formula (x), R ^4c And R ^4e Is a hydrogen atom, R ^4d Is an alkyl radical, and R ^4b And R ^4d At least one of the tertiary butyl, tertiary amyl, tertiary hexyl and tertiaryHeptyl, or tert-octyl.

A ² Represents a single bond, O, or C (R) ^A2 ) ₂ . In one embodiment, A ² Preferably a single bond, or C (R) ^A2 ) ₂ Particularly preferably C (R) ^A2 ) ₂ 。R ^A2 Each independently represents a hydrogen atom or an alkyl group. In one embodiment, R ^A2 Preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. A. The ³ Represents a single bond, or C (R) ^A3 ) ₂ . In one embodiment, A ³ Particularly preferred is a single bond. R ^A3 Each independently represents a hydrogen atom or an alkyl group. In one embodiment, R ^A3 Preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

R ^5a 、R ^5b 、R ^5c 、R ^5d And R ^5e Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, or a group represented by the formula (y 1) or (y 2). In one embodiment, R ^5a 、R ^5b 、R ^5c 、R ^5d And R ^5e It is preferred that each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, or a group represented by the formula (y 1) or (y 2), and R ^5a 、R ^5b 、R ^5c 、R ^5d And R ^5e At least one of which is a hydroxyl group; more preferably R ^5a Is hydroxy, R ^5b Is a hydrogen atom, an alkyl group, or a group represented by the formula (y 1) or (y 2), and R ^5c 、R ^5d And R ^5e Each independently a hydrogen atom, or an alkyl group; even more preferably R ^5a Is hydroxy, R ^5b Is alkyl, or a group represented by the formula (y 1) or (y 2), R ^5c And R ^5e Is a hydrogen atom, and R ^5d Is an alkyl group.

R ^6a 、R ^6b 、R ^6c And R ^6d Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, or an alkyl group. In one embodiment, R ^6a 、R ^6b 、R ^6c And R ^6d Preferably, each is independently a hydrogen atom or a halogen atom, more preferably a hydrogen atom.

(A) The molecular weight of the component (B) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, particularly preferably 700 or less. (A) The lower limit of the molecular weight of the component (B) may be, for example, 150 or more. (A) The component (B) preferably contains a compound having a molecular weight of 230 or more, more preferably contains a compound having a molecular weight of 270 or more, and still more preferably contains a compound having a molecular weight of 300 or more.

Specific examples of the component (a) include: examples of the 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chloro-2H-benzotriazole (commercially available product: JF-79, manufactured by North City chemical industries), 2- (2-hydroxy-3, 5-di-tert-amylphenyl) -2H-benzotriazole (commercially available product: JF-80, manufactured by North City chemical industries), 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole (commercially available product: JF-83, manufactured by North City chemical industries), 2 '-methylenebis [6- (2H-benzotriazol-2-yl) -4-tert-octylphenol ] (commercially available product: JF-832, manufactured by North City chemical industries), 6- (2H-benzotriazol-2-yl) -4-tert-octyl-6' -tert-butyl-4 '-methyl-2, 2' -methylenebisphenol (commercially available product: BT-500, manufactured by North chemical industries), [ (2, 6-bis-1H-benzotriazol-1-yl) methyl ] -3704-methyl-phenol (commercially available product: BT-0, manufactured by North chemical industries).

The content of the aromatic nitrogen compound (a) having a phenolic hydroxyl group in the resin composition is not particularly limited, but is preferably 5% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, further preferably 0.5% by mass or less, particularly preferably 0.3% by mass or less, based on 100% by mass of the nonvolatile matter in the resin composition. The lower limit of the content of the aromatic nitrogen compound having a phenolic hydroxyl group (a) in the resin composition is not particularly limited, and from the viewpoint of more remarkably obtaining the desired effect of the present invention, the nonvolatile content of the resin composition is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, further preferably 0.01 mass% or more, further preferably 0.05 mass% or more, particularly preferably 0.1 mass% or more, based on 100 mass% of the resin composition.

(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.

Examples of the epoxy resin (B) include a bisxylenol type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolac type epoxy resin, a phenol novolac type epoxy resin, a t-butyl-catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic type epoxy resin, an epoxy resin containing a spiro ring, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, an isocyanurate type epoxy resin, a phenol phthalimide type epoxy resin, and the like. (B) The epoxy resin may be used alone or in combination of two or more.

The resin composition of the present invention preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule as the epoxy resin (B). The proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, based on 100% by mass of the nonvolatile component of the epoxy resin (B).

The epoxy resin includes an epoxy resin which is liquid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "liquid epoxy resin"), and an epoxy resin which is solid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "solid epoxy resin"). In the resin composition of the present invention, the epoxy resin may contain only a liquid epoxy resin, or may contain only a solid epoxy resin, or may contain both a liquid epoxy resin and a solid epoxy resin, and particularly preferably contains both a liquid epoxy resin and a solid epoxy resin.

The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.

As the liquid epoxy resin, preferred are a glycidyl (12464125221247112525125125251254023), a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane dimethanol type epoxy resin, a cyclic aliphatic glycidyl ether, and an epoxy resin having a butadiene structure.

Specific examples of the liquid epoxy resin include: "EX-992L" manufactured by Nagase ChemteX, "YX7400" manufactured by Mitsubishi chemical, and "HP4032", "HP4032D" and "HP4032SS" manufactured by DIC (naphthalene type epoxy resin); "828US", "828EL", "825" and "EPIKOTE 828EL" (bisphenol A epoxy resin) manufactured by Mitsubishi chemical corporation; "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical corporation; "630", "630LSD" and "604" (glycidyl amine type epoxy resins) manufactured by Mitsubishi chemical company; "ED-523T" (GLYCIROL type epoxy resin) manufactured by ADEKA corporation; "EP-3950L" and "EP-3980S" (glycidylamine-type epoxy resins) manufactured by ADEKA; EP-4088S (dicyclopentadiene type epoxy resin) manufactured by ADEKA corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon iron chemical Co., ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "EX-991L" (epoxy resin containing an oxyalkylene skeleton and a butadiene skeleton) manufactured by Nagase ChemteX; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Dailuo corporation; "PB-3600" manufactured by Daxylonite, JP-100"," JP-200 "and" JP-400 "manufactured by Nippon Caoda (TM) (epoxy resin having butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resins) available from Nippon iron chemical materials; "EG-280" (epoxy resin containing fluorene structure) manufactured by osaka gas chemical company; "EX-201" (Cyclic aliphatic glycidyl ether) manufactured by Nagase ChemteX, inc.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.

The solid epoxy resin is preferably a bisxylenol type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a naphthol novolac type epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol a type epoxy resin, a bisphenol AF type epoxy resin, a phenol aralkyl type epoxy resin, a tetraphenylethane type epoxy resin, a phenol phthalimidine type epoxy resin.

Specific examples of the solid epoxy resin include: "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200", "HP-7200HH", "HP-7200H" and "HP-7200L" (dicyclopentadiene type epoxy resins) manufactured by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4S", "HP6000" and "HP6000L" (naphthylene ether type epoxy resins) manufactured by DIC corporation; EPPN-502H (a triphenol-type epoxy resin) manufactured by Nippon chemical company; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Chemicals); "NC3000H", "NC3000L", "NC3000FH", and "NC3100" (biphenyl type epoxy resin) manufactured by japan chemical company; "ESN475V" and "ESN4100V" (naphthalene type epoxy resins) manufactured by Nippon iron chemical materials Co., ltd; ESN485 (naphthol type epoxy resin) manufactured by Nippon chemical Co., ltd.; ESN375 (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon chemical Co., ltd.; "YX4000H", "YX4000HK", "YL7890" (bicresol-type epoxy resin) manufactured by Mitsubishi chemical company; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical corporation; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi chemical corporation; PG-100 and CG-500 manufactured by Osaka gas chemical company; "YX7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1010" (bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation; "WHR991S" (phenol-phthalimidine-type epoxy resin) manufactured by Nippon chemical Co., ltd. These may be used alone or in combination of two or more.

When a solid epoxy resin and a liquid epoxy resin are used in combination as the epoxy resin (B), the mass ratio thereof (solid epoxy resin: liquid epoxy resin) is preferably 10:1 to 1:50, more preferably 2:1 to 1:20, particularly preferably 1:1 to 1:10.

(B) The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5000g/eq, more preferably 60g/eq to 2000g/eq, still more preferably 70g/eq to 1000g/eq, and still more preferably 80g/eq to 500g/eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.

(B) The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, still more preferably from 400 to 1500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

The content of the epoxy resin (B) in the resin composition is not particularly limited, and is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass or less, particularly preferably 10% by mass or less, with respect to 100% by mass of nonvolatile components in the resin composition. The lower limit of the content of the epoxy resin (B) in the resin composition is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, further preferably 3% by mass or more, particularly preferably 5% by mass or more, with respect to 100% by mass of nonvolatile components in the resin composition.

The mass ratio of the epoxy resin (B) to the aromatic nitrogen compound (A) having a phenolic hydroxyl group in the resin composition ((B)/A) component) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and particularly preferably 10 or more. The mass ratio of the epoxy resin (B) to the aromatic nitrogen compound (A) having a phenolic hydroxyl group in the resin composition is not particularly limited, and the upper limit of ((B)/component (A)) is preferably 1000 or less, more preferably 500 or less, and particularly preferably 100 or less.

< (C) an active ester compound

The resin composition of the present invention contains (C) an active ester compound. (C) The active ester compounds may be used singly or in combination of two or more kinds at an arbitrary ratio. (C) The active ester compound may have a function as an epoxy resin curing agent which reacts with the (B) epoxy resin to cure it.

As the active ester compound (C), it is generally preferred to use a compound having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds. The active ester compound is preferably a compound obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl 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 hydroxyl 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, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac (phenol novolac) and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.

Specifically, as the active ester compound (C), a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetyl compound of a phenol novolac resin, and an active ester compound containing a benzoyl compound of a phenol novolac resin are preferable, and at least one selected from the dicyclopentadiene type active ester compound and the naphthalene type active ester compound is more preferable. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferred.

As the commercially available products of the active ester compound (C), examples of the active ester compound having a dicyclopentadiene type diphenol structure include "EXB9451", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", "HPC-8000H-65TM" (manufactured by DIC); examples of the active ester compound having a naphthalene structure include "HP-B-8151-62T", "EXB-8100L-65T", "EXB-9416-70BK", "HPC-8150-62T" and "EXB-8" (manufactured by DIC); the phosphorus-containing active ester compound may be "EXB9401" (manufactured by DIC corporation), the active ester compound of an acetylated phenol novolac resin may be "DC808" (manufactured by mitsubishi chemical corporation), the active ester compound of a benzoylate phenol novolac resin may be "YLH1026", "YLH1030", "YLH1048" (manufactured by mitsubishi chemical corporation), and the active ester compound having a styryl group and a naphthalene structure may be "PC1300-02-65MA" (manufactured by AIR WATER corporation).

(C) The active ester group equivalent (reactive group equivalent as a curing agent) of the active ester compound is preferably 50g/eq to 500g/eq, more preferably 50g/eq to 400g/eq, and still more preferably 100g/eq to 300g/eq. 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 active ester compound (C) in the resin composition is not particularly limited, and is preferably 0.1% by mass or more, more preferably 1% by mass or more, further more preferably 5% by mass or more, further more preferably 10% by mass or more, particularly preferably 12% by mass or more, when the nonvolatile content in the resin composition is assumed to be 100% by mass. The upper limit of the content of the active ester compound (C) in the resin composition is not particularly limited, and is preferably 50% by mass or less, more preferably 40% by mass or less, further more preferably 30% by mass or less, further more preferably 25% by mass or less, particularly preferably 20% by mass or less, with respect to 100% by mass of nonvolatile components in the resin composition.

The mass ratio of the active ester compound (C) to the aromatic nitrogen compound (A) having a phenolic hydroxyl group in the resin composition ((C)/A) component) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and particularly preferably 10 or more. The mass ratio of the active ester compound (C) to the aromatic nitrogen compound (A) having a phenolic hydroxyl group in the resin composition (component (C)/component (A)) is not particularly limited, but is preferably 1000 or less, more preferably 500 or less, and particularly preferably 100 or less.

< (C') other curing agent

The resin composition of the present invention may further contain a curing agent (C') other than the component (C) as an optional component. (C') the other curing agents may be used singly or in any combination of two or more. The other curing agent (C') described herein is a component which does not belong to the component (A). The other curing agent (C') may function as an epoxy resin curing agent which reacts with the epoxy resin (B) to cure the same, as in the case of the active ester compound (C).

The other curing agent (C') is not particularly limited, and examples thereof include a phenol curing agent, a carbodiimide curing agent, an acid anhydride curing agent, an amine curing agent, a benzoxazine curing agent, a cyanate curing agent, and a thiol curing agent. In the resin composition of the present invention, (C') other curing agent is preferably a curing agent selected from a phenol curing agent and a carbodiimide curing agent, and particularly preferably a phenol curing agent.

As the phenol curing agent, a phenol curing agent having a novolac structure (novolac structure) is preferred from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of adhesion to adherends, nitrogen-containing phenol-based curing agents are preferred, and phenol-based curing agents containing a triazine skeleton are more preferred. Among them, in view of satisfying heat resistance, water resistance, and adhesion at a high level, a phenol novolak resin (phenol novolak resin) having a triazine skeleton is preferable. Specific examples of the phenolic curing agent include: "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Minghe Kaisha, "NHN", "CBN", "GPH" manufactured by Japan Kasei, "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018-50P", "LA-1356", "TD2090", "KA-1160" manufactured by Nippon iron chemical Co., ltd.

Examples of the carbodiimide-based curing agent include those having 1 or more, preferably 2 or more carbodiimide structures in 1 molecule, and examples thereof include: aliphatic bis-carbodiimides such as tetramethylene-bis (t-butylcarbodiimide) and cyclohexane-bis (methylene-t-butylcarbodiimide); a bis-carbodiimide such as an aromatic bis-carbodiimide such as phenylene-bis (xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly (methylenedicyclohexylcarbodiimide), and poly (isophorone carbodiimide); polycarbodiimides such as aromatic polycarbodiimides including poly (phenylene carbodiimide), poly (naphthylene carbodiimide), poly (tolylene carbodiimide), poly (methyldiisopropylphenylene carbodiimide), poly (triethylphenylene carbodiimide), poly (diethylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide), poly (diisopropylphenylene carbodiimide), poly (xylylenecarbodiimide), poly (tetramethylxylylenecarbodiimide), poly (methylenediphenylcarbodiimide), and poly [ methylenebis (methylphenylene) carbodiimide ].

Commercially available products of carbodiimide-based curing agents include, for example: "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07" and "CARBODILITE V-09" manufactured by Riqing textile chemical company; stabaxol P, stabaxol P400, hycasyl 510, manufactured by Rhein-Chemie, inc.

Examples of the acid anhydride-based curing agent include a curing agent having 1 or more acid anhydride groups in 1 molecule, and preferably a curing agent having 2 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride-based curing agent include polymeric acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3'-4,4' -diphenylsulfone tetracarboxylic dianhydride, 1, 3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (anhydrotrimellitate), and styrene-maleic acid resins obtained by copolymerizing styrene and maleic acid. Commercially available acid anhydride curing agents include: "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Xinri Physics chemical company, "YH-306", "YH-307" manufactured by Mitsubishi chemical company, "HN-2200", "HN-5500" manufactured by Hitachi chemical company, "EF-30", "EF-40", "EF-60" and "EF-80" manufactured by Cray Valley company, and the like.

Examples of the amine-based curing agent include those having 1 or more, preferably 2 or more, amino groups in 1 molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like, and among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention. The amine-based curing agent is preferably a primary or secondary amine, more preferably a primary amine. <xnotran> , 4,4' - (2,6- ), 4,4' - ,4,4 ' - ,3,3 ' - , , , ,4,4 ' - ,3,3 ' - -4,4' - ,2,2 ' - -4,4' - ,3,3 ' - ,2,2- (3- -4- ) ,3,3- -5,5- -4,4- ,2,2- (4- ) ,2,2- (4- (4- ) ) ,1,3- (3- ) ,1,3- (4- ) ,1,4- (4- ) ,4,4 ' - (4- ) , (4- (4- ) ) , (4- (3- ) ) . </xnotran> As the amine-based curing agent, commercially available products can be used, and examples thereof include "SEIKACURE-S" manufactured by SEIKA, "KAYABOND C-200S" manufactured by Nippon Chemicals, KAYABOND C-100"," KAYAHARD A-A "," KAYAHARD A-B "," KAYAHARD A-S ", and" Epicure W "manufactured by Mitsubishi chemical corporation.

Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE chemical; "HFB2006M" manufactured by SHOWA POLYMER CORPORATION; "P-d" and "F-a" manufactured by four chemical industries, inc.

Examples of the cyanate ester-based curing agent include: bisphenol a dicyanate, polyphenol cyanate ester (oligo (3-methylene-1, 5-phenylene cyanate)), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyldicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate) phenylpropane, 1-bis (4-cyanate phenyl methane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate phenyl-1- (methylethylidene)) benzene, bis (4-cyanate phenyl) sulfide, and bis (4-cyanate phenyl) ether, etc. 2-functional cyanate ester resins, polyfunctional cyanate ester resins derived from phenol novolac resin, cresol novolac resin, etc., prepolymers in which a part of these cyanate ester resins is triazinized, etc. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both phenol novolac-type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (prepolymers in which a part or all of bisphenol a dicyanate ester is triazinated to form a trimer) manufactured by Lonza japan.

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

(C') the equivalent weight of the other curing agent is preferably 50 g/eq.about 3000g/eq, more preferably 100 g/eq.about 1000g/eq, still more preferably 100 g/eq.about 500g/eq, particularly preferably 100 g/eq.about 300g/eq. The reactive group equivalent is the mass of the curing agent per 1 equivalent of the reactive group. The reactive group is a group that reacts with the epoxy resin, and if it is a phenolic curing agent, it is a phenolic hydroxyl group, and varies depending on the type of the curing agent.

The content of the other curing agent (C') in the resin composition is not particularly limited, and is preferably 15% by mass or less, more preferably 10% by mass or less, further more preferably 5% by mass or less, particularly preferably 3% by mass or less, with respect to 100% by mass of nonvolatile components in the resin composition. The lower limit of the content of the other curing agent (C') in the resin composition is not particularly limited, and may be, for example, 0 mass% or more, 0.01 mass% or more, 0.1 mass% or more, 1 mass% or more, or the like, assuming that the nonvolatile component in the resin composition is 100 mass%.

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

The ratio of the number of molar equivalents of epoxy groups in the epoxy resin (B) to the number of molar equivalents of the curing agent-reactive groups in the component (C) and the component (C') (curing agent-reactive groups/epoxy groups) in the resin composition is preferably in the range of 0.2 to 2, more preferably in the range of 0.5 to 1.8, and still more preferably in the range of 1 to 1.5.

< (D) Compound having radically reactive group

From the viewpoint of lowering the dielectric loss tangent, the resin composition of the present invention preferably contains (D) a compound having a radical-reactive group. (D) The compound having a radical-reactive group has 1 or more (preferably 2 or more) radical-reactive groups in 1 molecule. (D) The compound having a radical-reactive group may be used alone or in combination of two or more.

Examples of the radical-reactive group include, but are not particularly limited to, (1) acryloyl, (2) methacryloyl, (3) allyl, (4) methallyl group, (5) phenyl which is substituted with a group selected from vinyl and isopropenyl and which is further optionally substituted with alkyl (for example, vinylphenyl (i.e., 4-vinylphenyl, 3-vinylphenyl, 2-vinylphenyl), isopropenylphenyl (i.e., 4-isopropenylphenyl, 3-isopropenylphenyl, 2-isopropenylphenyl), etc.), (6) benzyl which is substituted with a group selected from vinyl and isopropenyl and which is further optionally substituted with alkyl (for example, vinylbenzyl (i.e., 4-vinylbenzyl, 3-vinylbenzyl, 2-vinylbenzyl), isopropenylbenzyl (i.e., 4-isopropenylbenzyl, 3-isopropenylbenzyl, 2-isopropenylbenzyl), etc.), (7) amido maleimide (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl), etc.

In the first embodiment, (D) the compound having a radical-reactive group is preferably a thermoplastic resin containing 2 or more radical-reactive groups (for example, number average molecular weight of 800 or more). The thermoplastic resin is not particularly limited, and examples thereof include phenoxy resins, polyvinyl acetal resins, polystyrene resins, polyethylene resins, polypropylene resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, polyester resins, and the like, and in this embodiment, (D) the compound having a radical reactive group contains a modified resin having 2 or more radical reactive groups of these resins.

In the first embodiment, (D) the compound having a radical-reactive group is more preferably a resin containing a compound selected from the group consisting of a modified polyphenylene ether resin having 2 or more radical-reactive groups and a modified polystyrene resin having 2 or more radical-reactive groups, still more preferably a modified polyphenylene ether resin having 2 or more radical-reactive groups, and in one embodiment, particularly preferably a resin represented by formula (4).

[ chemical formula 8]

[ in the formula,

R ¹¹ and R ¹² Each independently represents an alkyl group;

R ¹³ 、R ¹⁴ 、R ²¹ 、R ²² 、R ²³ and R ²⁴ Each independently represents a hydrogen atom, or an alkyl group;

R ^a and R ^b Each independently represents (1) an acryloyl group, (2) a methacryloyl group, (3) an allyl group, (4) a methallyl group, (5) a phenyl group substituted by a group selected from a vinyl group and an isopropenyl group and further optionally substituted by an alkyl group, or (6) a benzyl group substituted by a group selected from a vinyl group and an isopropenyl group and further optionally substituted by an alkyl group;

X ¹ represents a single bond, -C (R) ^c ) ₂ -, -O-, -CO-, -S-, -SO-, or-SO ₂ -；

R ^c Each independently represents a hydrogen atom, or an alkyl group;

s represents 0 or 1;

t and u each independently represent an integer of 1 or more. ]. The t unit and the u unit may be the same or different.

R ¹¹ And R ¹² Each independently represents an alkyl group, and in one embodiment, a methyl group is preferred. R ¹³ And R ¹⁴ Each independently represents a hydrogen atom or an alkyl group, and in one embodiment, a hydrogen atom is preferred. R is ²¹ And R ²² Each independently represents a hydrogen atom or an alkyl group, and in one embodiment, a hydrogen atom or a methyl group is preferred, and a methyl group is more preferred. R ²³ And R ²⁴ Each independently represents hydrogenAn atom or an alkyl group, and in one embodiment, a hydrogen atom or a methyl group is preferable.

R ^a And R ^b Each independently represents (1) an acryloyl group, (2) a methacryloyl group, (3) an allyl group, (4) a methallyl group, (5) a phenyl group substituted by a group selected from a vinyl group and an isopropenyl group and further optionally substituted by an alkyl group, or (6) a benzyl group substituted by a group selected from a vinyl group and an isopropenyl group and further optionally substituted by an alkyl group.

In one embodiment, R ^a And R ^b Each independently preferably (1) a phenyl group substituted with a group selected from the group consisting of a vinyl group and an isopropenyl group and further optionally substituted with an alkyl group, or (2) a benzyl group substituted with a group selected from the group consisting of a vinyl group and an isopropenyl group and further optionally substituted with an alkyl group; more preferably 4-vinylphenyl, 3-vinylphenyl, 2-vinylphenyl, 4-isopropenylphenyl, 3-isopropenylphenyl, 2-isopropenylphenyl, 4-vinylbenzyl, 3-vinylbenzyl, 2-vinylbenzyl, 4-isopropenylbenzyl, 3-isopropenylbenzyl, or 2-isopropenylbenzyl; particularly preferred is 4-vinylbenzyl, 3-vinylbenzyl or 2-vinylbenzyl.

X ¹ Represents a single bond, -C (R) ^c ) ₂ -, -O-, -CO-, -S-, -SO-, or-SO ₂ -, in one embodiment, preferably a single bond, -C (R) ^c ) ₂ -, or-O-. R ^c Each independently represents a hydrogen atom or an alkyl group, and in one embodiment, a hydrogen atom or a methyl group is preferred.

s represents 0 or 1, and in one embodiment is preferably 1.t and u each independently represent an integer of 1 or more, and in one embodiment, an integer of 1 to 200 is preferable, and an integer of 1 to 100 is more preferable.

The radical-reactive group equivalent of the compound having a radical-reactive group (D) in the first embodiment is preferably 300g/eq to 2500g/eq, more preferably 400g/eq to 2000g/eq. The radical-reactive group equivalent means the mass of the resin (compound) per 1 equivalent of radical-reactive group.

The number average molecular weight of the compound (D) having a radical reactive group in the first embodiment is preferably 800 to 10000, more preferably 900 to 5000. The number average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

Examples of commercially available products of the compound (D) having a radical-reactive group in the first embodiment include "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi gas chemical corporation; "SA9000" and "SA9000-111" (methacrylic modified polyphenylene ether resin) manufactured by Sabic Innovative Plastics (SABIC Innovative Plastics) Inc.

In a second embodiment, (D) the compound having a radical reactive group comprises a low molecular weight compound having 2 or more radical reactive groups (e.g., a molecular weight of less than 800). Examples of such a compound include a polyfunctional (meth) acryloyl group-containing compound having a molecular weight of less than 800, a polyfunctional vinylphenyl group-containing compound having a molecular weight of less than 800, and a polyfunctional (meth) allyl group-containing compound having a molecular weight of less than 800.

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

The polyfunctional vinylphenyl group-containing compound having a molecular weight of less than 800 is a compound having 2 or more vinylphenyl groups. Examples of the polyfunctional vinylphenyl group-containing compound having a molecular weight of less than 800 include 4,4' -divinylbiphenyl, 1, 2-bis (4-vinylphenyl) ethane, 2-bis (4-vinylphenyl) propane, bis (4-vinylphenyl) ether and the like.

The polyfunctional (meth) allyl group-containing compound having a molecular weight of less than 800 is a compound having 2 or more allyl groups or methallyl groups. Examples of the polyfunctional (meth) allyl group-containing compound having a molecular weight of less than 800 include aromatic carboxylic acid allyl ester compounds such as Diallyl bibenzoate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2, 6-naphthalate, diallyl 2, 3-naphthalate and the like; allyl isocyanurate compounds such as 1,3, 5-triallyl isocyanurate and 1, 3-diallyl-5-glycidyl isocyanurate; epoxy group-containing aromatic allyl compounds such as 2, 2-bis [ 3-allyl-4- (glycidyloxy) phenyl ] propane; benzoxazine-containing aromatic allyl compounds such as bis [ 3-allyl-4- (3, 4-dihydro-2H-1, 3-benzoxazin-3-yl) phenyl ] methane; ether-containing aromatic allyl compounds such as 1,3, 5-triallyl ether benzene; and allylsilane compounds such as diallyldiphenylsilane. Commercially available products of polyfunctional (meth) allyl group-containing compounds having a molecular weight of less than 800 include "TAIC" (1, 3, 5-triallyl isocyanurate) manufactured by Nisshoku Techno Fine Chemical company, "DAD" (diallyl dibenzoate) manufactured by Nisshoku Chemical company, "TRIAM-705" (triallyl trimellitate) manufactured by Wako pure Chemical industries, a product name "DAND" (diallyl 2, 3-naphthoate) manufactured by Nisshoku Chemical industries, ALP-d "(bis [ 3-allyl-4- (3, 4-dihydro-2H-1, 3-benzoxazin-3-yl) phenyl ] methane) manufactured by Sizhou Chemical industries, a" RE-810NM "(2, 2-bis [ 3-allyl-4- (glycidyloxy) phenyl ] propane) manufactured by Nippochemical industries), and" DA-IC "(1, 3-MGIC-5-glycidylisocyanurate) manufactured by Sizhou Chemical industries.

In one embodiment of the second embodiment, (D) the compound having a radical reactive group is particularly preferably a compound containing a low molecular weight represented by formula (5) (for example, a molecular weight of less than 800).

[ chemical formula 9]

[ in the formula,

R ^d and R ^e Each independently represents (1) acryloyl, (2) methacryloyl, (3) allyl, (4) methallyl, (5) phenyl substituted by a group selected from vinyl and isopropenyl and further optionally substituted by alkyl, or (6) benzyl substituted by a group selected from vinyl and isopropenyl and further optionally substituted by alkyl;

X ² and X ³ Represents a single bond or an alkylene group;

ring A represents a non-aromatic carbocyclic ring optionally having substituents, or a non-aromatic heterocyclic ring optionally having substituents. ].

The "substituent" included in the definition of the symbol of formula (5) is not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an aralkyl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an aralkyl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, and an aralkyl-carbonyl-oxy group.

R ^d And R ^e Each independently represents (1) an acryloyl group, (2) a methacryloyl group, (3) an allyl group, (4) a methallyl group, (5) a phenyl group substituted by a group selected from a vinyl group and an isopropenyl group and further optionally substituted by an alkyl group, or (6) a benzyl group substituted by a group selected from a vinyl group and an isopropenyl group and further optionally substituted by an alkyl group. In one embodiment, R ^d And R ^e Each independently is preferably an acryloyl group or a methacryloyl group.

X ² And X ³ Represents a single bond or an alkylene group. Alkylene means a straight and/or branched 2-valent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group include-CH ₂ -、-CH ₂ -CH ₂ -、-CH(CH ₃ )-、-CH ₂ -CH ₂ -CH ₂ -、-CH ₂ -CH(CH ₃ )-、-CH(CH ₃ )-CH ₂ -、-C(CH ₃ ) ₂ -、-CH ₂ -CH ₂ -CH ₂ -CH ₂ -、-CH ₂ -CH ₂ -CH(CH ₃ )-、-CH ₂ -CH(CH ₃ )-CH ₂ -、-CH(CH ₃ )-CH ₂ -CH ₂ -、-C(CH ₃ ) ₂ -CH ₂ -、-CH ₂ -C(CH ₃ ) ₂ -and the like. In one embodiment, X ² And X ³ Each independently is preferably an alkylene group.

Ring A represents a non-aromatic carbocyclic ring optionally having substituents, or a non-aromatic heterocyclic ring optionally having substituents.

Non-aromatic carbocyclic rings mean only that in the entire ringA ring having a carbon atom having no aromatic character as a ring-constituting atom. The nonaromatic carbocyclic ring may be a monocyclic nonaromatic carbocyclic ring or a polycyclic nonaromatic carbocyclic ring. The non-aromatic carbocyclic ring may be a saturated carbocyclic ring composed of only a single bond, or may be an unsaturated carbocyclic ring having a double bond in addition to a single bond. The non-aromatic carbocyclic ring is preferably a 3-to 21-membered non-aromatic carbocyclic ring, more preferably a 4-to 18-membered non-aromatic carbocyclic ring, and further more preferably a 5-to 14-membered non-aromatic carbocyclic ring. Preferable specific examples of the non-aromatic carbocyclic ring include monocyclic saturated carbocyclic rings such as cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, and cyclododecane ring; bicyclo [2.2.1]Heptane ring (norbornane ring), bicyclo [4.4.0]Decane ring (decaline ring), bicyclo [5.3.0]Decane ring, bicyclo [4.3.0]Nonane ring (hexahydroindane ring), bicyclo [3.2.1]Octane ring, bicyclo [5.4.0 ]]Undecane ring, bicyclo [3.3.0 ]]Octane ring, bicyclo [3.3.1]Saturated carbocyclic rings of bicyclic systems such as nonane ring; tricyclic [5.2.1.0 ^2,6 ]Decane ring (tetrahydrodicyclopentadiene ring), tricyclo [3.3.1.1 ^3,7 ]Decane ring (adamantane ring), tricyclo [6.2.1.0 ^2,7 ]Saturated carbocyclic rings of tricyclic systems such as an undecane ring, and the like.

The non-aromatic heterocyclic ring is a ring having no aromatic character in the entire ring, and having, as ring-forming atoms, heteroatoms such as oxygen atom, nitrogen atom, and sulfur atom in addition to carbon atom. The nonaromatic heterocyclic ring may be a monocyclic nonaromatic heterocyclic ring or a polycyclic nonaromatic heterocyclic ring. The non-aromatic heterocyclic ring may be a saturated heterocyclic ring composed of only a single bond, or may be an unsaturated heterocyclic ring having a double bond in addition to a single bond. The non-aromatic heterocyclic ring is preferably a 3-to 21-membered non-aromatic heterocyclic ring, more preferably a 4-to 18-membered non-aromatic heterocyclic ring, and further more preferably a 5-to 14-membered non-aromatic heterocyclic ring. Preferable specific examples of the non-aromatic heterocyclic ring include a 1, 3-dioxane ring, a 1, 3-dioxolane ring, a tetrahydropyran ring, a tetrahydrofuran ring and the like.

In one embodiment, ring a is preferably a non-aromatic carbocyclic ring optionally substituted with alkyl, or a non-aromatic heterocyclic ring optionally substituted with alkyl; more preferred is a tetrahydrodicyclopentadiene ring optionally substituted with alkyl, or a 1, 3-dioxane ring optionally substituted with alkyl.

The radical-reactive group equivalent of the compound having a radical-reactive group (D) in the second embodiment is preferably 30g/eq to 400g/eq, more preferably 50g/eq to 300g/eq, and still more preferably 75g/eq to 200g/eq.

The molecular weight of the compound having a radical-reactive group (D) in the second embodiment is preferably 100 to 700, more preferably 200 to 400, and still more preferably 250 to 500.

In the third embodiment, (D) the compound having a radical-reactive group is preferably a maleimide compound having a partial structure represented by the formula (6').

[ chemical formula 10]

[ in the formula,

ring B represents an optionally substituted monocycloalkane ring or an optionally substituted monocycloalkene ring;

i and j each independently represent an integer of 0 or 1 or more, and the sum of i and j is 6 or more;

* Indicates the binding site. ]

The maleimide compound means a compound containing at least one maleimide group (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl) in 1 molecule. The number of maleimide groups in the molecule of the maleimide compound 1 in the third embodiment is preferably 2 or more, particularly preferably 2. The maleimide compounds in the third embodiment may be used singly or in combination of two or more kinds at an arbitrary ratio.

Examples of the "substituent" in the ring B of the formula (6') include the same ones as those contained in the definition of the symbol of the formula (5).

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

Ring B represents a monocyclic hydrocarbon ring optionally having a substituent, or a monocyclic olefin ring optionally having a substituent. Ring B is preferably a monocycloalkane ring optionally substituted with a group selected from alkyl and alkenyl; or a monocyclic olefin ring optionally substituted with a group selected from alkyl and alkenyl. The ring B is more preferably a monocycloalkane ring optionally substituted with a group selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms; or a monocyclic olefin ring optionally substituted with a group selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms.

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

In the third embodiment, (D) the compound having a radical-reactive group particularly preferably contains a maleimide compound represented by formula (6).

[ chemical formula 11]

[ in the formula,

R ¹⁰ each is independentRepresents a substituent group immediately;

each ring C independently represents an aromatic ring optionally having a substituent;

D ¹ and D ² Each independently represents a single bond, -C (R) ^x ) ₂ -、-O-、-CO-、-S-、-SO-、-SO ₂ -, -CONH-, -NHCO-, -COO-, or-OCO-;

R ^x each independently represents a hydrogen atom, or an alkyl group;

c each independently represents 0 or 1;

d each independently represents an integer of 0 or 1 or more;

e each independently represents 0, 1 or 2;

n represents an integer of 0 or 1 or more;

other symbols are the same as described above. ]. The d unit, the e unit, and the n unit may be the same or different.

R as formula (6) ¹⁰ The "substituent" in (1) and the "substituent" in the ring C include the same groups as those "substituents" contained in the definitions of the symbols in the formula (5).

Each ring C independently represents an aromatic ring optionally having a substituent, preferably a benzene ring optionally substituted with a group selected from alkyl groups. D ¹ And D ² Each independently represents a single bond, -C (R) ^x ) ₂ -、-O-、-CO-、-S-、-SO-、-SO ₂ -, -CONH-, -NHCO-, - -COO-, or-OCO-, preferably a single bond, -C (R) ^x ) ₂ -, or-O-. R ^x Each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. c each independently represents 0 or 1, preferably 0.d independently represents an integer of 0 or 1 or more, preferably 0, 1,2 or 3, more preferably 0, 1 or 2.e independently of one another represents 0, 1 or 2, preferably 0.n represents 0 or an integer of 1 or more, preferably 0.

The partial structure represented by the formula (D) contained in the formula (6) is not particularly limited, and examples thereof include partial structures represented by the formulae (D-1) to (D-3).

[ chemical formula 12]

[ in the formula, [ denotes a binding site; other symbols are the same as described above. ].

[ chemical formula 13]

[ in the formula, the same applies to the above. ].

The radical polymerizable group equivalent of the compound having a radical reactive group (D) in the third embodiment is preferably 200g/eq to 2500g/eq, more preferably 250g/eq to 2000g/eq, and still more preferably 300g/eq to 1500g/eq. (D) The radical polymerizable group equivalent of the compound having a radical reactive group represents the mass of the resin per 1 equivalent of the radical polymerizable group.

The weight average molecular weight of the compound (D) having a radical reactive group in the third embodiment is preferably 400 to 10000, more preferably 500 to 7000, particularly preferably 600 to 5000.

Examples of commercially available products of the compound having a radical reactive group (D) in the third embodiment include "BMI-689", "BMI-1500", "BMI-1700", "BMI-3000J", manufactured by Designer polymers, and "SLK-6895-T90", manufactured by shin-Etsu chemical industries, for example.

In the fourth embodiment, (D) the compound having a radical-reactive group preferably contains a maleimide compound represented by formula (7).

[ chemical formula 14]

[ in the formula,

R ²⁰ each independently represents a hydrogen atom, or an alkyl group;

ring E, ring F and ring G each independently represent an aromatic ring optionally having a substituent;

Z ¹ each of which isIndependently represents a single bond, -C (R) ^z ) ₂ -、-O-、-CO-、-S-、-SO-、-SO ₂ -, -CONH-, or-NHCO-;

R ^z each independently represents a hydrogen atom, or an alkyl group;

f represents an integer of 1 or more;

g each independently represents 0 or 1;

h each independently represents 0, 1,2 or 3.]. The f unit and the h unit may be the same or different. The maleimide compounds in the fourth embodiment may be used singly or in combination of two or more kinds at an arbitrary ratio.

Examples of the "substituent" of ring E, ring F and ring G of formula (7) include the same groups as those of the "substituent" contained in the definition of the symbol of formula (5).

R ²⁰ Each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

Ring E, ring F and ring G each independently represent an optionally substituted aromatic ring, preferably an optionally substituted benzene ring, more preferably a benzene ring optionally substituted with a group selected from alkyl and aryl, particularly preferably an (unsubstituted) benzene ring.

Z ¹ Each independently represents a single bond, -C (R) ^z ) ₂ -、-O-、-CO-、-S-、-SO-、-SO ₂ -, -CONH-, or-NHCO-, preferably a single bond. R ^z Each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

f represents an integer of 1 or more, preferably an integer of 1 to 10. Each g independently represents 0 or 1, preferably 1.h independently of one another denotes 0, 1,2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 1.

The radical polymerizable group equivalent of the compound having a radical reactive group (D) in the fourth embodiment is preferably 150g/eq to 1000g/eq, more preferably 200g/eq to 500g/eq.

The weight average molecular weight of the compound (D) having a radical reactive group in the fourth embodiment is preferably 100 to 10000, more preferably 150 to 5000, particularly preferably 200 to 3000.

Examples of commercially available products of the compound having a radical reactive group (D) in the fourth embodiment include "MIR-3000-70MT" and "MIR-5000-60T" manufactured by Nippon chemical Co., ltd.

In the fifth embodiment, (D) the compound having a radical-reactive group preferably contains a maleimide compound represented by formula (8).

[ chemical formula 15]

[ in the formula,

R ³⁰ each independently represents an alkyl group;

ring H and ring I each independently represent an optionally substituted aromatic ring;

m represents an integer of 1 or more. ]. The m units may be the same or different. The maleimide compounds in the fifth embodiment may be used singly or in combination of two or more kinds at an arbitrary ratio.

Examples of the "substituent" of ring H and ring I of formula (8) include the same groups as those included in the definition of the symbol of formula (5).

R ³⁰ Each independently represents an alkyl group, and in one embodiment, a methyl group is preferred. Each ring H independently represents an optionally substituted aromatic ring, and in one embodiment, preferably an optionally substituted benzene ring, more preferably a benzene ring optionally substituted with a group selected from alkyl groups, and still more preferably a benzene ring substituted with a group selected from alkyl groups. Each of rings I independently represents an optionally substituted aromatic ring, and in one embodiment, preferably an optionally substituted benzene ring, more preferably a benzene ring optionally substituted with a group selected from alkyl groups, and further more preferably a (unsubstituted) benzene ring. m represents an integer of 1 or more, preferably an integer of 1 to 20.

The compound (D) having a radical reactive group in the fifth embodiment can be produced, for example, by the method described in japanese patent application laid-open publication No. 2020-500211 or a method based on the method.

(D) The compound having a radical reactive group may contain any one of the preferred resin in the first embodiment, the preferred compound in the second embodiment, the preferred compound in the third embodiment, the preferred compound in the fourth embodiment, or the preferred compound in the fifth embodiment alone, or 2 or more of them may be contained in combination at an arbitrary ratio.

(D) The radical-reactive group equivalent of the compound having a radical-reactive group is preferably 30g/eq.

The content of the compound having a radical-reactive group (D) in the resin composition is not particularly limited, and is preferably 30% by mass or less, more preferably 20% by mass or less, further more preferably 10% by mass or less, further more preferably 5% by mass or less, particularly preferably 2% by mass or less, based on 100% by mass of nonvolatile components in the resin composition. The lower limit of the content of the compound having a radical-reactive group (D) in the resin composition is not particularly limited, but is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, further preferably 0.05 mass% or more, further preferably 0.1 mass% or more, particularly preferably 0.5 mass% or more, based on 100 mass% of nonvolatile components in the resin composition.

< (E) inorganic filling Material

The resin composition of the present invention may contain (E) an inorganic filler as an optional component. (E) The inorganic filler is contained in the resin composition in a particulate state.

As the material of the (E) inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler (E) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium 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, calcium zirconate titanate, zirconium phosphate, zirconium phosphotungstate and the like. Among them, silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as the silica, spherical silica is preferable. (E) The inorganic filler may be used alone or in combination of two or more kinds at an arbitrary ratio.

Examples of commercially available products of the inorganic filler (E) include "SP60-05" and "SP507-05" manufactured by Nichika chemical Co., ltd; "YC100C", "YA050C-MJE", "YA010C" manufactured by Yatoma corporation; "UFP-30" manufactured by Denka corporation; "Silfil (1247112523125011245112523)," Silfil NSS-3N "," Silfil NSS-4N "," Silfil NSS-5N ", manufactured by Deshan corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Yatoma; "DAW-03" and "FB-105FD" manufactured by Denka corporation, and the like.

(E) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, further preferably 1 μm or less, particularly preferably 0.7 μm or less. (E) 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, particularly preferably 0.2 μm or more. (E) The average particle diameter of the inorganic filler can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, it can be determined by: the particle size distribution of the inorganic filler was prepared on a volume basis by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size was defined as an average particle size. The measurement sample may be a sample obtained by: 100mg of the inorganic filler and 10g of methyl ethyl ketone were weighed into a vial, and dispersed for 10 minutes by ultrasonic waves. For the measurement sample, the volume-based particle size distribution of the inorganic filler was measured by a flow cell method using a laser diffraction type particle size distribution measuring apparatus with the wavelength of the light source used being blue and red, and the average particle size was calculated from the obtained particle size distribution as the median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, ltd.

(E) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1m ² More than g, preferably 0.5m ² More preferably 1m or more per gram ² More than g, particularly preferably 3m ² More than g. (E) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100m ² A ratio of less than g, preferably 70m ² A value of less than/g, more preferably 50m ² A specific ratio of the total amount of the components is 40m or less ² The ratio of the carbon atoms to the carbon atoms is below g. The specific surface area of the inorganic filler material can be obtained by: according to the BET method, the specific surface area was calculated by a BET multipoint method by adsorbing nitrogen gas on the surface of the sample using a specific surface area measuring apparatus (Macsorb HM-1210, mountech).

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

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

The degree of the 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, the 100 mass% inorganic filler is preferably surface-treated with 0.2 to 5 mass% of a surface treatment agent, more preferably 0.2 to 3 mass% of a surface treatment agent, and still more preferably 0.3 to 2 mass% of a surface treatment agent.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of the inorganic filler is preferably 0.02mg/m ² Above, preferably 0.1mg/m ² The content of the above is more preferably 0.2mg/m ² As described above. On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition and the melt viscosity in the form of a sheet from increasing, it is preferably 1.0mg/m ² The concentration is preferably 0.8mg/m or less ² More preferably 0.5mg/m or less ² The following.

(E) The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after surface treatment is washed with a solvent (e.g., methyl Ethyl Ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning was performed at 25 ℃ for 5 minutes. The supernatant liquid was removed, the solid components were dried, and then the amount of carbon per unit surface area of the inorganic filler material was measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, ltd., can be used.

The content of the inorganic filler (E) in the resin composition is not particularly limited, and when the nonvolatile content in the resin composition is 100 mass%, it is preferably 90 mass% or less, more preferably 85 mass% or less, still more preferably 80 mass% or less, and particularly preferably 75 mass% or less. The lower limit of the content of the inorganic filler (E) in the resin composition is not particularly limited, and when the nonvolatile content in the resin composition is set to 100 mass%, it may be, for example, 0 mass% or more, 1 mass% or more, 10 mass% or more, preferably 20 mass% or more, or 30 mass% or more, more preferably 40 mass% or more, or 50 mass% or more, further preferably 50 mass% or more, or 55 mass% or more, still more preferably 60 mass% or more, or 65 mass% or more, particularly preferably 68 mass% or more, or 70 mass% or more.

(F) organic filling Material

The resin composition of the present invention may further contain (F) an organic filler as an optional component.

(F) The organic filler is present in the resin composition in the form of particles. As the organic filler (F), rubber particles are preferably used from the viewpoint of remarkably obtaining the desired effect of the present invention. (F) The organic filler may be used alone or in combination of two or more kinds at an arbitrary ratio.

Examples of the rubber component contained in the rubber particles include silicone elastomers such as polydimethylsiloxane; olefinic thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-isobutylene copolymers, acrylonitrile-butadiene copolymers, isoprene-isobutylene copolymers, isobutylene-butadiene copolymers, ethylene-propylene-diene terpolymers and ethylene-propylene-butylene terpolymers; and thermoplastic elastomers such as acrylic thermoplastic elastomers such as polypropylene (meth) acrylate, polybutylene (meth) acrylate, polycyclohexyl (meth) acrylate, and octyl (meth) acrylate. The rubber component may further contain a silicone rubber such as polyorganosiloxane rubber. The glass transition temperature of the rubber component contained in the rubber particles is, for example, 0 ℃ or lower, preferably-10 ℃ or lower, more preferably-20 ℃ or lower, and still more preferably-30 ℃ or lower.

From the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferable that the (F) organic filler is core-shell type rubber particles. The core-shell type rubber particles are particulate organic fillers formed of core particles containing the above-mentioned rubber components and 1 or more shell portions covering the core particles. Further, the core-shell type particles are preferably core-shell type graft copolymer rubber particles formed of core particles containing the above-mentioned rubber components and a shell portion obtained by graft-copolymerizing a monomer component copolymerizable with the rubber component contained in the core particles. The core-shell type as used herein does not necessarily mean only those in which the core particle and the shell are clearly distinguished from each other, and includes those in which the boundary between the core particle and the shell is unclear, and the core particle may not be completely covered with the shell.

The rubber component is preferably contained in the core-shell type rubber particles in an amount of 40 mass% or more, more preferably 50 mass% or more, and still more preferably 60 mass% or more. The upper limit of the content of the rubber component in the core-shell type rubber particles is not particularly limited, but is, for example, preferably 95 mass% or less and 90 mass% or less from the viewpoint of sufficiently coating the core particles with the shell portion.

The monomer components forming the shell portion of the core-shell type rubber particle include, for example: (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and glycidyl (meth) acrylate; (meth) acrylic acid; n-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; a maleimide; α, β -unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene and α -methylstyrene; (meth) acrylonitrile, etc., and among them, a (meth) acrylate is preferably contained, and methyl (meth) acrylate is more preferably contained.

Examples of commercially available products of the core-shell type rubber particles include "CHT" manufactured by Chemil Industries, inc.; "B602" manufactured by UMGABS corporation; "PARALOID EXL-2602", "PARALOID EXL-2603", "PARALOID EXL-2655", "PARALOID EXL-2311", "PARALOID-EXL2313", "PARALOID EXL-2315", "PARALOID KM-330", "PARALOID KM-336P" and "PARALOID KCZ-201" manufactured by Dow chemical Japan; "METABLEN C-223A", "METABLEN E-901", "METABLEN S-2001", "METABLEN W-450A", "METABLEN SRK-200", manufactured by Mitsubishi Yang (Rayon); "Kane Ace M-511", "Kane Ace M-600", "Kane Ace M-400", "Kane Ace M-580", and "Kane Ace MR-01", manufactured by Kaneka corporation.

(F) The average particle diameter (average primary particle diameter) of the organic filler is not particularly limited, but is preferably 20nm or more, more preferably 30nm or more, and still more preferably 50nm or more. (F) The upper limit of the average particle diameter (average primary particle diameter) of the organic filler is not particularly limited, but is preferably 5000nm or less, more preferably 2000nm or less, and still more preferably 1000nm or less. (F) The average particle diameter (average primary particle diameter) of the organic filler can be measured using a Zeta potential particle size distribution measuring instrument or the like.

The content of the organic filler (F) in the resin composition is not particularly limited, and is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass. The lower limit of the content of the organic filler (F) in the resin composition is not particularly limited, and may be, for example, 0 mass% or more and 0.01 mass% or more, preferably 0.1 mass% or more, and more preferably 0.5 mass% or more, when the nonvolatile content in the resin composition is 100 mass%.

(G) curing Accelerator

The resin composition of the present invention may contain (G) a curing accelerator as an optional component. The curing accelerator (G) described here is a component which does not belong to the component (A). (G) The curing accelerator functions as a curing catalyst for accelerating curing of the epoxy resin (B).

Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Among them, amine-based curing accelerators are preferred. (G) The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium 2, 6-bis [ (2-hydroxy-5-methylphenyl) methyl ] -4-methylphenolate and di-t-butyldimethylanilinium borate; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris (3-methylphenyl) ethylphosphonium tetraphenylborate, tris (2-methoxyphenyl) ethylphosphonium tetraphenylborate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; an aromatic phosphine-benzoquinone addition reaction product such as a triphenylphosphine-p-benzoquinone addition reaction product; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexylphosphine; dibutylphenylphosphine, di-t-butylphenyl phosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri (4-ethylphenyl) phosphine, tri (4-propylphenyl) phosphine, tri (4-isopropylphenyl) phosphine, tri (4-butylphenyl) phosphine, tri (4-t-butylphenyl) phosphine, tri (2, 4-dimethylphenyl) phosphine, tri (2, 5-dimethylphenyl) phosphine, tri (2, 6-dimethylphenyl) phosphine, tri (3, 5-dimethylphenyl) phosphine, tri (2, 4, 6-trimethylphenyl) phosphine, tri (2, 6-dimethyl-4-ethoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, tri (4-ethoxyphenyl) phosphine, tri (4-t-butoxyphenyl) phosphine, diphenyl-2-pyridylphosphine, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (4-diphenylphosphino) propane, bis (2, 2' -diphenylacetylene, and the like.

Examples of the urea-based curing accelerator include: 1, 1-dimethylurea; aliphatic dimethylureas such as 1, 3-trimethylurea, 3-ethyl-1, 1-dimethylurea, 3-cyclohexyl-1, 1-dimethylurea and 3-cyclooctyl-1, 1-dimethylurea; 3-phenyl-1, 1-dimethylurea, 3- (4-chlorophenyl) -1, 1-dimethylurea, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea, 3- (2-methylphenyl) -1, 1-dimethylurea, 3- (4-methylphenyl) -1, 1-dimethylurea, 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- (1, 4-phenylene) bis (N ', N ' -bis (N ' -dimethylphenyl) urea), N ' -bis (N ', N ' -dimethylurea, N ' -bis (4-methylphenyl) phenyl) urea, N ' -dimethylurea, N ' -bis (3, N ' -bis (4-methylphenyl) urea, N ' -dimethylurea, and the like.

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') -methyl-4 ' -isocyanato-triazine, 2' -diamino-6- [2' -methylimidazolyl- (1 ') ] -methyl-imidazolyl- (1 '),4 ' -isocyanato-methyl-triazine, 2' -isocyanato-triazine, imidazole compounds such as 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins.

As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include "1B2PZ", "2MZA-PW", "2PHZ-PW", "C11Z-A" manufactured by four chemical industries, and "P200-H50" manufactured by Mitsubishi chemical corporation.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic 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, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

As the amine-based curing accelerator, commercially available products such as "MY-25" manufactured by Aomoto Chemicals, inc. can be used.

The content of the curing accelerator (G) in the resin composition is not particularly limited, but is preferably 15% by mass or less, more preferably 10% by mass or less, further more preferably 5% by mass or less, particularly preferably 2% by mass or less, when the nonvolatile content in the resin composition is assumed to be 100% by mass. The lower limit of the content of the curing accelerator (G) in the resin composition is not particularly limited, and may be, for example, 0 mass% or more, 0.001 mass% or more, 0.01 mass% or more, 0.1 mass% or more, or the like, when the nonvolatile component in the resin composition is taken as 100 mass%.

< (H) other additives

The resin composition of the present invention may further contain an optional additive as a nonvolatile component. Examples of such additives include: radical polymerizable compounds having 4-vinylphenyl group, acryloyl group, methacryloyl group, maleimide group (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl group), etc.; radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; thermosetting resins other than epoxy resins such as epoxy acrylate resins, urethane acrylate resins, polyurethane resins, cyanate ester resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, and silicone resins; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, and the like; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as Benton and montmorillonite; defoaming agents such as silicone defoaming agents, acrylic defoaming agents, fluorine defoaming agents, and vinyl resin defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improving agents such as urea silane; an adhesion-imparting agent such as a triazole-based adhesion-imparting agent, a tetrazole-based adhesion-imparting agent, or a triazine-based adhesion-imparting agent; antioxidants such as hindered phenol antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen flame retardants (e.g., melamine sulfate), halogen flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate dispersants, polyoxyalkylene dispersants, acetylene (acetylene) dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic acid anhydride stabilizers. (H) The other additives may be used singly or in combination of two or more thereof at an arbitrary ratio. The content of the other additives (H) can be appropriately set by those skilled in the art.

Organic solvent (I)

The resin composition of the present invention may contain an arbitrary organic solvent as a volatile component in addition to the nonvolatile component. As the organic solvent (I), known organic solvents can be suitably used, and the kind thereof is not particularly limited. Examples of the organic solvent (I) include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ -butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1, 4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; 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, gamma-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (I) One kind of the organic solvent may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.

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

< method for producing resin composition >

The resin composition of the present invention can be produced, for example, by: in an arbitrary preparation vessel, (a) an aromatic nitrogen compound containing a phenolic hydroxyl group, (B) an epoxy resin, (C) a reactive ester compound, (C') another curing agent used as needed, (D) a compound having a radical reactive group used as needed, (E) an inorganic filler used as needed, (F) an organic filler used as needed, (G) a curing accelerator used as needed, (H) another additive used as needed, and (I) an organic solvent used as needed are added and mixed in an arbitrary order and/or in a part or all at the same time. In addition, the temperature may be appropriately set during the addition and mixing of the components, and heating and/or cooling may be performed temporarily or throughout. In addition, during or after the addition and mixing, the resin composition may be uniformly dispersed by stirring or shaking using a stirring device or a shaking device such as a mixer. Further, defoaming can be performed under low pressure conditions such as vacuum simultaneously with stirring or shaking.

< Property of resin composition >

The resin composition of the present invention comprises (A) an aromatic nitrogen compound having a phenolic hydroxyl group, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product having excellent plating adhesion and a reduced dielectric loss tangent (Df) can be obtained. Further, in one embodiment, the resin composition of the present invention may have such a feature that the melt viscosity is low.

The cured product of the resin composition of the present invention can have such a characteristic that it is excellent in plating adhesion. Therefore, in one embodiment, for example, as in the following test example 2, the copper plating peel strength calculated from the load when the copper plating conductor layer is peeled off in the vertical direction by forming the copper plating conductor layer on the cured product may be preferably 0.2kgf/cm or more, more preferably 0.25kgf/cm or more, still more preferably 0.3kgf/cm or more and 0.35kgf/cm or more, and particularly preferably 0.4kgf/cm or more and 0.45kgf/cm or more. The upper limit is not particularly limited, and may be, for example, 10kgf/cm or less.

The cured product of the resin composition of the present invention can have a low dielectric loss tangent (Df). Therefore, in one embodiment, the dielectric loss tangent (Df) of a cured product of the resin composition measured under the conditions of 5.8GHz and 23 ℃ as in test example 1 described below is preferably 0.0200 or less and 0.0100 or less, more preferably 0.0070 or less and 0.0050 or less, still more preferably 0.0040 or less and 0.0030 or less, and particularly preferably 0.0028 or less and 0.0026 or less.

In one embodiment, the resin composition of the present invention may have such a feature that the melt viscosity is low. Therefore, the resin composition is excellent in circuit embeddability in lamination. In one embodiment, the resin composition as measured in test example 3 described below may have a minimum melt viscosity of preferably 5000 poise or less, more preferably 3000 poise or less, still more preferably 2000 poise or less, still more preferably 1600 poise or less, particularly preferably 1400 poise or less at 60 ℃ to 200 ℃. The lower limit is not particularly limited, and from the viewpoint of maintaining the thickness stability of the resin composition layer, it is preferably 50 poise or more, more preferably 100 poise or more, still more preferably 200 poise or more, still more preferably 300 poise or more, particularly preferably 400 poise or more.

< use of resin composition >

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

For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as "a resin composition for a rewiring-forming layer which is an insulating layer for forming a rewiring layer" (a resin composition for forming a rewiring-forming layer) and "a resin composition for sealing a semiconductor chip" (a resin composition for sealing a semiconductor chip). In manufacturing the semiconductor chip package, a rewiring layer may be further formed on the sealing layer;

(1) A step of laminating a temporary fixing film on the base material,

(2) A step of temporarily fixing the semiconductor chip to the temporary fixing film,

(3) A step of forming a sealing layer on the semiconductor chip,

(4) A step of peeling the base material and the temporary fixing film from the semiconductor chip,

(5) A step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled, and

(6) And forming a rewiring layer as a conductor layer on the rewiring-forming layer.

The resin composition of the present invention can be suitably used in the case where a printed wiring board is a component-embedded circuit board because it provides an insulating layer having good component embeddability.

< sheet-like laminated Material >

The resin composition of the present invention can be used by coating in the form of varnish, but is generally industrially suitable for use in the form of a sheet-like laminate containing the resin composition.

As the sheet-like laminate, a resin sheet or a prepreg as shown below is preferred.

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.

From the viewpoint of making the printed wiring board thin and providing a cured product excellent in insulation even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more 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 and 10 μm or more.

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

When a film made of a plastic material is used as the support, examples of the plastic material include: polyesters such as polyethylene terephthalate (hereinafter sometimes referred to simply as "PET") and polyethylene naphthalate (hereinafter sometimes referred to simply as "PEN"); polycarbonate (hereinafter sometimes simply referred to as "PC"); acrylic polymers such as polymethyl methacrylate (PMMA); a cyclic polyolefin; triacetyl cellulose (TAC); polyether sulfide (PES); a polyether ketone; polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and particularly, inexpensive polyethylene terephthalate is 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 preferred. As the copper foil, a foil formed of a single metal of copper may be used, and a foil formed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, or the like) may also be used.

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

Further, as the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include at least one selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support having a releasing layer, commercially available products can be used, and examples thereof include "SK-1", "AL-5" and "AL-7" manufactured by Lindeke, which are PET films having a releasing layer mainly composed of an alkyd resin-based releasing agent, "Lumiror T60" manufactured by Dongli, a "Purex" manufactured by Diita, and a "Unipel" manufactured by UNITIKA.

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

In one embodiment, the resin sheet may further include an arbitrary layer, as necessary. Examples of the optional layer include a protective film provided on a surface of the resin composition layer not bonded to the support (i.e., a surface opposite to the support) and selected for the support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust or the like to the surface of the resin composition layer or generation of damage on the surface of the resin composition layer.

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

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.

The drying can be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. The drying conditions vary depending on the boiling point of the organic solvent in the resin composition, and for example, when a resin composition containing 30 to 60 mass% of the organic solvent is used, the resin composition layer can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes.

The resin sheet may be wound into a roll and stored. When the resin sheet has a protective film, the protective film can be peeled off for use.

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

The sheet-like fibrous base material used in the prepreg is not particularly limited, and materials commonly used as a base material for the prepreg, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning of the printed wiring board, the thickness of the fibrous base material in sheet form is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited. Usually 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 may be in the same range as the resin composition layer in the resin sheet described above.

The sheet-like layered material of the present invention can be preferably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and more preferably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).

< printed wiring board >

The printed wiring board of the present invention includes an insulating layer formed of a cured product obtained by curing the resin composition of the present invention.

The printed wiring board can be produced, for example, by a method comprising the steps (I) and (II) described below using the above-mentioned resin sheet,

(I) Laminating a resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate,

(II) a step of forming an insulating layer by curing (for example, thermosetting) the resin composition layer.

The "inner layer substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductor layer on one or both surfaces thereof, and the conductor layer may be subjected to patterning. An inner layer substrate having a conductor layer (circuit) formed on one surface or both surfaces of a substrate is sometimes referred to as an "inner layer circuit substrate". In addition, an intermediate product in which an insulating layer and/or a conductor layer is to be further formed at the time of manufacturing a printed wiring board is also included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate in which components are embedded may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressure-bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressure bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "heat-pressure bonding member") include a heated metal plate (SUS end plate or the like) and a metal roll (SUS roll). It is preferable that the heat-pressure bonding member is not directly pressed against the resin sheet, but is pressed via an elastic material such as heat-resistant rubber so that the resin sheet sufficiently conforms to the surface irregularities of the inner layer substrate.

The lamination of the inner substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heating and press-bonding temperature is preferably in the range of 60 to 160 ℃, more preferably 80 to 140 ℃, the heating and press-bonding pressure is preferably in the range of 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the heating and press-bonding time is preferably in the range of 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably carried out under reduced pressure of 26.7hPa or less.

The lamination can be carried out by means of a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Nikko-Materials, a vacuum applicator (vacuum applicator) manufactured by Nikko-Materials, and a batch vacuum pressure laminator.

After the lamination, the heat and pressure bonding member is pressed at normal pressure (atmospheric pressure), for example, from the support side, whereby the smoothing treatment of the laminated resin sheets can be performed. The pressing conditions for the smoothing treatment may be set to the same conditions as the above-described conditions for the heat and pressure bonding of the laminate. The smoothing treatment may be performed by a commercially available laminator. The lamination and smoothing treatment can be continuously performed using a commercially available vacuum laminator as described above.

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

In the step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer formed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions generally employed in forming an insulating layer of a printed wiring board can be used.

For example, although the conditions for heat curing the resin composition layer vary depending on the kind of the resin composition, in one embodiment, the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, and still more preferably 170 to 210 ℃. The curing time is preferably 5 to 120 minutes, more preferably 10 to 100 minutes, and still more preferably 15 to 100 minutes.

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, before the resin composition layer is thermally cured, the resin composition layer is preheated at a temperature of 50 to 120 ℃, preferably 60 to 115 ℃, more preferably 70 to 110 ℃ for 5 minutes or longer, preferably 5 to 150 minutes, more preferably 15 to 120 minutes, still more preferably 15 to 100 minutes.

In the production of the printed wiring board, (III) a step of forming 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 performed. These steps (III) to (V) can be carried out by various methods known to those skilled in the art, which can be used for manufacturing printed wiring boards. When the support is removed after the step (II), the removal of the support may be performed between the steps (II) and (III), between the steps (III) and (IV), or between the steps (IV) and (V). If necessary, the insulating layer and the conductor layer may be formed by repeating the steps (II) to (V) 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 the case of using the resin sheet.

In the step (III), a hole such as a via hole or a through hole can be formed in the insulating layer by forming the hole in the insulating layer. The step (III) can be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the hole may be determined as appropriate according to the design of the printed wiring board.

The step (IV) is a step of roughening the insulating layer. In general, in this step (IV), stain is also removed. The step and conditions of the roughening treatment are not particularly limited, and known steps and conditions generally used in forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer may be subjected to roughening treatment by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order.

The swelling solution used in the roughening treatment is not particularly limited, but an alkali solution, a surfactant solution and the like can be mentioned, and an alkali solution is preferred, and a sodium hydroxide solution and a potassium hydroxide solution are more preferred as the alkali solution. Examples of commercially available Swelling liquids include "spinning Dip securigant P" and "spinning Dip securigant SBU" manufactured by Ameter (ATOTECH) japan. The swelling treatment with the swelling solution is not particularly limited, and may be performed, for example, by immersing the insulating layer in the swelling solution at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40 to 80 ℃ for 5 to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment by an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution securigant P" manufactured by amett japan.

The neutralizing Solution used for the roughening treatment is preferably an acidic aqueous Solution, and examples of commercially available products include "Reduction Solution securiganteh P" manufactured by ammett japan.

The treatment with the neutralizing solution may be performed by immersing the treated surface on which the roughening treatment with the oxidizing agent is performed in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. From the viewpoint of handling, etc., it is preferable to immerse the object subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.

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

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

The conductor layer may have a single-layer structure, or may have a multilayer structure in which 2 or more layers of single metal layers or alloy layers made of different metals or alloys are stacked. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

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

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

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer in accordance with a desired wiring pattern. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed.

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

The metal foil can be produced by a known method such as an electrolytic method or a rolling method. As commercially available products of the metal foil, for example, HLP foil manufactured by JX Nissie Metal Co., ltd, JXUT-III foil, 3EC-III foil manufactured by Mitsui Metal mining Co., ltd, TP-III foil, and the like can be cited.

< semiconductor device >

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

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

Examples

The present invention will be specifically described below with reference to examples. The present invention is not limited by these examples. In the following, unless otherwise explicitly stated, "part" and "%" representing amounts represent "part by mass" and "% by mass", respectively. The temperature condition when the temperature is not specified is room temperature (23 ℃), and the pressure condition when the pressure is not specified is atmospheric pressure (1 atm).

< example 1 >

3 parts of a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin ("ZX-1059" manufactured by Nippon iron chemical Co., ltd., epoxy equivalent 170 g/eq.), 4 parts of a naphthalene skeleton epoxy resin ("HP-4032-SS" manufactured by DIC Co., ltd., epoxy equivalent 144 g/eq.), 3 parts of a biphenyl skeleton epoxy resin ("NC-3000L" manufactured by Nippon chemical Co., ltd., epoxy equivalent 272 g/eq.), 4 parts of an active ester curing agent ("HPC-8150-62T" manufactured by DIC Co., ltd., a toluene solution containing 62 mass% of a nonvolatile component, and an active ester group equivalent 234 g/eq.), 22.6 parts of an amino triazine-containing cresol novolak resin ("LA-3018-50P" manufactured by DIC Co., a 1-methoxy-2-propanol solution containing 50 mass% of a nonvolatile component), and an inorganic filler (spherical silica surface-treated with an amine-based alkoxysilane compound ("KBM 573" manufactured by shin iron chemical Co., ltd., SO-2 m ", and a specific surface area of 0.5 μm ² (g))) 75 parts, 1 part of an organic filler (EXL-2655, manufactured by DOW corporation), 0.2 part of a curing accelerator (4-dimethylaminopyridine, manufactured by Wako pure chemical industries), 0.2 part of a benzotriazole compound having a phenolic hydroxyl group (JF-79, manufactured by North City chemical industries), 10 parts of MEK, and 10 parts of toluene were mixed, and the mixture was subjected to a high-speed rotary mixerThe resulting mixture was uniformly dispersed to obtain a varnish-like resin composition.

< example 2 >

A varnish-like resin composition was obtained in the same manner as in example 1 except that 0.2 part of the benzotriazole compound having a phenolic hydroxyl group (JF-80, manufactured by North City chemical industry Co., ltd.) was used in place of 0.2 part of the benzotriazole compound having a phenolic hydroxyl group (JF-79, manufactured by North City chemical industry Co., ltd.).

< example 3 >

A varnish-like resin composition was obtained in the same manner as in example 1 except that 0.2 part of the benzotriazole compound having a phenolic hydroxyl group ("JF-83" manufactured by North City chemical industry Co., ltd.) was used instead of 0.2 part of the benzotriazole compound having a phenolic hydroxyl group ("JF-79" manufactured by North City chemical industry Co., ltd.).

< example 4 >

A varnish-like resin composition was obtained in the same manner as in example 1 except that 0.2 part of the benzotriazole compound having a phenolic hydroxyl group ("JF-832" manufactured by North City chemical industry Co., ltd.) was used instead of 0.2 part of the benzotriazole compound having a phenolic hydroxyl group ("JF-79" manufactured by North City chemical industry Co., ltd.).

< example 5 >

A varnish-like resin composition was obtained in the same manner as in example 1 except that 0.2 part of the benzotriazole compound having a phenolic hydroxyl group (JAST-500, manufactured by North City chemical industry Co., ltd.) was used in place of 0.2 part of the benzotriazole compound having a phenolic hydroxyl group (JF-79, manufactured by North City chemical industry Co., ltd.).

< example 6 >

A maleimide compound a represented by the following formula (8 ') (Mw/Mn =1.81, m' =1.47 (mainly 1,2 or 3), and a MEK solution having a nonvolatile content of 70 mass%) synthesized by the method described in synthetic example 1 of japanese patent publication No. 2020-500211 was prepared.

[ chemical formula 16]

A varnish-like resin composition was obtained in the same manner as in example 3, except that the amount of the inorganic filler used was changed from 75 parts to 80 parts, and 2.9 parts of the prepared maleimide compound a (MEK solution having a solid content of 70%) were further added.

< example 7 >

A varnish-like resin composition was obtained in the same manner as in example 6 except that 3.1 parts of a styrene-based modified polyphenylene ether resin ("OPE-2 St-1200" manufactured by Mitsubishi gas chemical corporation and a toluene solution having a nonvolatile content of 65%) was used in place of the maleimide compound A.

< example 8 >

A varnish-like resin composition was obtained in the same manner as in example 6, except that 2 parts of a dimer acid skeleton-containing maleimide compound ("BMI-689" manufactured by Designer Molecules) was used in place of the maleimide compound A.

< example 9 >

A varnish-like resin composition was obtained in the same manner as in example 6 except that 2 parts of dioxane diol diacrylate ("A-DOG" manufactured by Newzhongmura chemical industries, ltd.) was used in place of the maleimide compound A.

< comparative example 1 >

A varnish-like resin composition was obtained in the same manner as in example 1, except that the benzotriazole compound having a phenolic hydroxyl group (product of Tokyo chemical industries, ltd. "JF-79") was not used.

< comparative example 2 >

The varnish was obtained in the same manner as in example 1 except that the amount of the benzotriazole compound having a phenolic hydroxyl group (JF-79, manufactured by north chemical industry, city) and the active ester compound (HPC-8150-62T, manufactured by DIC) were changed from 4 parts to 16 parts, the amount of the aminotriazine-containing cresol novolak resin (LA-3018-50P, manufactured by DIC) was changed from 3 parts to 5 parts, the amount of the mixture of the bisphenol a-type epoxy resin and the bisphenol F-type epoxy resin (ZX-1059, manufactured by diurnal chemical company, epoxy equivalent 170 g/eq) was changed from 4 parts to 8 parts, the amount of the biphenyl skeleton epoxy resin (NC-3000L, manufactured by japan chemical company, epoxy equivalent 272 g/eq) was changed from 3 parts to 5 parts, and the amount of the curing accelerator (4-dimethylaminopyridine, manufactured by mitsunpur chemical industry) was changed from 0.2 parts to 0.1 part, and the amount of the epoxy resin was changed from 3 parts to 5 parts.

< test example 1: measurement of dielectric loss tangent (Df) >

As a support, a polyethylene terephthalate film (AL 5, manufactured by Lindeke) having a release layer was prepared, and the thickness thereof was 38 μm. The varnish-like resin compositions obtained in examples and comparative examples were uniformly applied to the release layer of the support so that the thickness of the dried resin composition layer was 40 μm. Then, the resin composition layer was dried at 80 ℃ to 100 ℃ (average 90 ℃) for 4 minutes to obtain a resin sheet including the support and the resin composition layer.

The resulting resin sheet was heated at 190 ℃ for 90 minutes to thermally cure the resin composition layer. Then, the support was peeled off to obtain a cured product of the resin composition. The cured product was cut into test pieces having a width of 2mm and a length of 80 mm. For the test piece, the dielectric loss tangent (Df) was measured by the resonance cavity perturbation method at a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃ using "HP8362B" manufactured by Agilent Technologies. The measurement was carried out for 3 test pieces.

< test example 2: peel strength of copper plating

(1) Base treatment of inner layer circuit substrate

As an inner layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil 18 μm thick, substrate 0.4mm thick, "R1515A" manufactured by Sonar corporation) having inner layer circuits (copper foil) on both sides was prepared. Both surfaces of the inner layer circuit board were subjected to roughening treatment of copper surface by etching for 1 μm with "CZ8101" manufactured by meige corporation.

(2) Lamination of resin sheets

The resin sheets obtained in the same manner as in test example 1 were laminated on both sides of the inner layer circuit board using a batch vacuum press Laminator (2-Stage build Laminator, CVP700, manufactured by Nikko Materials). The lamination is performed in such a manner that the resin composition layer of the resin sheet is in contact with the inner circuit substrate. Further, the lamination is carried out by: the pressure was reduced for 30 seconds to 13hPa or less, and the pressure was applied at 130 ℃ and 0.74MPa for 45 seconds. Next, hot pressing was performed at 120 ℃ for 75 seconds under a pressure of 0.5 MPa.

(3) Curing of resin compositions

The laminated resin sheet and inner layer circuit board were heated at 130 ℃ for 30 minutes, followed by heating at 170 ℃ for 30 minutes to cure the resin composition, thereby forming an insulating layer. Then, the support is peeled off to obtain a laminated substrate having the insulating layer, the inner-layer circuit substrate, and the insulating layer in this order.

(4) Roughening treatment

The laminated substrate was immersed in a Swelling solution (a Swelling Dip securigant P (an aqueous solution of glycol ethers or sodium hydroxide) containing diethylene glycol monobutyl ether manufactured by amett japan) at 60 ℃ for 10 minutes. Next, the laminated substrate was placed in a roughening solution (Concentrate Compact P (KMnO) manufactured by Amatt Japan K.K.) ₄ 60g/L aqueous solution of NaOH 40 g/L) at 80 ℃ for 20 minutes, and then the laminated substrate was immersed in a neutralization solution (Reduction solution securiganteh P (aqueous solution of sulfuric acid) manufactured by Amett Japan) at 40 ℃ for 5 minutes. Then, the laminated substrate was dried at 80 ℃ for 30 minutes to obtain "evaluation substrate a".

(5) Plating using semi-additive process

Evaluation substrate A was coated with PdCl ₂ The electroless copper plating solution of (1) is immersed at 40 ℃ for 5 minutes, and then immersed at 25 ℃ for 20 minutes in an electroless copper plating solution. Then, the resultant was heated at 150 ℃ for 30 minutes to carry out annealing treatment. Then, a resist layer was formed, and patterning by etching was performed. Then, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20 μm. Subsequently, annealing treatment was performed at 190 ℃ for 60 minutes to obtain "evaluation substrate B".

(6) Determination of peeling Strength of copper plating

A cut was formed in the conductor layer of the evaluation substrate B so as to surround a rectangular portion having a width of 10mm and a length of 100 mm. One end of the rectangular portion was peeled off and clamped by a jig (AUTO COM model tester "AC-50C-SL" manufactured by t.s.e.). The rectangular portion was torn off at a speed of 50 mm/min at room temperature by a jig in the vertical direction, and the load (kgf/cm) at 35mm of tearing was measured as the copper plating peel strength.

< test example 3: measurement of minimum melt viscosity >

The melt viscosity of the resin composition layer in the resin sheet obtained in the same manner as in test example 1 was measured using a dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" manufactured by UBM corporation). The measurement was performed using parallel plates having a diameter of 18mm for a 1g sample taken from the resin composition layer. The measurement conditions were set as follows: the temperature was raised from the initial temperature of 60 ℃ to 200 ℃ at a rate of 5 ℃/min so that the measurement temperature interval became 2.5 ℃ and the vibration became 1Hz/deg. The lowest melt viscosity (poise) was determined from the measured value of the melt viscosity.

The contents of nonvolatile components in the resin compositions of examples and comparative examples and the measurement results of the test examples are shown in table 1 below.

[ Table 1]

As shown in Table 1, in the use of containing phenolic hydroxyl aromatic nitrogen compounds in comparative examples 1 and 2, copper plating peel strength is low, dielectric loss tangent is high. On the other hand, it is found that these problems can be overcome when a resin composition containing (A) an aromatic nitrogen compound having a phenolic hydroxyl group, (B) an epoxy resin, and (C) an active ester compound is used. Further, it is known that the melt viscosity of such a resin composition is low. Further, it is found that in examples 6 to 9 including the compound (D) having a radical reactive group, the dielectric loss tangent is further reduced as compared with the other examples and comparative examples.

Claims

1. A resin composition comprising: a benzotriazole compound having a phenolic hydroxyl group (A), an epoxy resin (B), and an active ester compound (C).

2. A resin composition comprising: a compound represented by the formula (1 a) or (1B), (B) an epoxy resin, and (C) an active ester compound,

in the formula (I), the compound is shown in the specification,

r represents

(1) Aryl substituted with at least one hydroxyl group and further optionally having a substituent, or

(2) An aralkyl group substituted on at least one aromatic carbon atom with a hydroxyl group and further optionally having a substituent;

x and Y each independently represent CH or N;

ring Z represents an optionally substituted aromatic ring.

3. The resin composition of claim 2, wherein R is

(1) An aryl group which is substituted with at least one hydroxyl group, further substituted with at least one alkyl group having 3 or more carbon atoms and further optionally substituted, or

4. The resin composition according to claim 1 or 2, wherein,

in the formula (I), the compound is shown in the specification,

a represents a single bond, or C (R) ^A ) ₂ ；

R ^A Each independently represents a hydrogen atomA bond or an alkyl group;

R ¹ and R ² Each independently represents a substituent;

a and b each independently represent an integer of 0 to 4.

5. The resin composition of claim 4, wherein R ² At least one of them is a secondary alkyl group having 3 to 10 carbon atoms or a tertiary alkyl group having 4 to 10 carbon atoms, and b is 1,2 or 3.

6. The resin composition according to claim 1 or 2, wherein the component (a) contains a compound having a molecular weight of 300 or more.

7. The resin composition according to claim 1 or 2, wherein the content of the component (A) is 0.001 to 5% by mass, based on 100% by mass of nonvolatile components in the resin composition.

8. The resin composition according to claim 1 or 2, further comprising (D) a compound having a radical reactive group.

9. The resin composition according to claim 1 or 2, wherein the content of the component (B) is from 0.1 to 30% by mass, based on 100% by mass of nonvolatile components in the resin composition.

10. The resin composition according to claim 1 or 2, wherein the content of the component (C) is 10% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass.

11. The resin composition according to claim 1 or 2, further comprising (E) an inorganic filler.

12. The resin composition according to claim 11, wherein the component (E) is silica.

13. The resin composition according to claim 11, wherein the content of the component (E) is 40% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

14. The resin composition according to claim 1 or 2, further comprising (F) an organic filler.

15. The resin composition according to claim 1 or 2, further comprising a phenolic curing agent.

16. The resin composition according to claim 1 or 2, wherein the minimum melt viscosity at 60 ℃ to 200 ℃ is 1400 poise or less.

17. The resin composition according to claim 1 or 2, wherein a cured product of the resin composition has a dielectric loss tangent (Df) of 0.0026 or less as measured at 5.8GHz and 23 ℃.

18. The resin composition according to claim 1 or 2, which is used for forming an insulating layer that is an insulating layer for forming a conductor layer.

19. The resin composition according to claim 1 or 2, which is used for forming an insulating layer of a printed wiring board.

20. A cured product of the resin composition according to claim 1 or 2.

21. A sheet-like laminate comprising the resin composition according to claim 1 or 2.

22. A resin sheet having:

a support, and

a resin composition layer formed of the resin composition according to claim 1 or 2, provided on the support.

23. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to claim 1 or 2.

24. A semiconductor device comprising the printed wiring board of claim 23.