KR20220170772A - Resin composition - Google Patents

Abstract

Provided is a resin composition capable of obtaining a cured product having excellent plating adhesion and a low dielectric loss tangent (Df). The resin composition contains (A) a phenolic hydroxyl group-containing aromatic nitrogen compound, (B) an epoxy resin and (C) an active ester compound.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition comprising an epoxy resin. Moreover, it is related with the hardened|cured material obtained using the said resin composition, sheet-like lamination material, a resin sheet, a printed wiring board, and a semiconductor device.

As a manufacturing technology of a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately piled up is known. The insulating layer of a printed wiring board is generally formed by hardening a resin composition. Until now, it is known that plating adhesion can be improved and the dielectric loss tangent of the insulating layer can be suppressed low by using an epoxy resin composition blended with an active ester compound as a resin composition for forming an insulating layer (Patent Document 1 ).

Japanese Unexamined Patent Publication No. 2020-23714

However, in recent years, it has been desired to further reduce the dielectric loss tangent of the insulating layer and to further improve plating adhesion.

An object of the present invention is to provide a resin composition capable of obtaining a cured product having excellent plating adhesion and having a low dielectric loss tangent (Df).

In order to achieve the object of the present invention, the inventors of the present invention, as a result of intensive examination, unexpectedly achieved by using a resin composition containing (A) a phenolic hydroxyl group-containing aromatic nitrogen compound, (B) an epoxy resin, and (C) an active ester compound. It was discovered that a cured product having excellent plating adhesion and a low dielectric loss tangent (Df) could be obtained, and the present invention was completed.

That is, the present invention includes the following contents.

[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) Formula (1a) or (1b):

[Formula (1a)]

[Formula (1b)]

[during expression,

R is

(1) an aryl group that is substituted with at least one hydroxyl group and may further have a substituent; or

(2) represents an aralkyl group which is substituted with a hydroxyl group on at least one aromatic carbon atom and may further have a substituent;

X and Y each independently represent CH or N;

Ring Z represents an aromatic ring which may have a substituent]

A resin composition comprising a compound represented by, (B) an epoxy resin and (C) an active ester compound.

[3] R is

(1) an aryl group substituted with at least one hydroxyl group, further substituted with at least one alkyl group having 3 or more carbon atoms, and which may further have a substituent; or

(2) The above [2] which is an aralkyl group substituted with a hydroxyl group on at least one aromatic carbon atom, further substituted with an alkyl group having 3 or more carbon atoms on at least one aromatic carbon atom, and may further have a substituent. ] The resin composition described in.

[4] Component (A) has formula (2a) or (2b):

[Formula (2a)]

[Formula (2b)]

[during expression,

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 represent a substituent;

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

The resin composition according to [1] or [2] above, containing the compound represented by

[5] The resin composition according to [4] above, wherein at least one of R ² 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 [1] or [2] above, wherein the component (A) contains a compound having a molecular weight of 300 or more.

[7] The resin composition according to [1] or [2] above, wherein the content of component (A) is 0.001% by mass to 5% by mass, when the non-volatile component in the resin composition is 100% by mass.

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

[9] The resin composition according to [1] or [2] above, wherein the content of component (B) is 0.1% by mass to 30% by mass, when the non-volatile component in the resin composition is 100% by mass.

[10] The resin composition according to [1] or [2] above, wherein the content of component (C) is 10% by mass or more when the non-volatile component in the resin composition is 100% by mass.

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

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

[13] The resin composition according to [11] above, wherein the content of the component (E) is 40% by mass or more when the non-volatile component in the resin composition is 100% by mass.

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

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

[16] The resin composition according to [1] or [2], wherein the minimum melt viscosity at 60°C to 200°C is 1,400 poise or less.

[17] The resin composition according to [1] or [2] above, wherein the cured product of the resin composition has a dielectric loss tangent (Df) of 0.0026 or less when measured at 5.8 GHz and 23°C.

[18] The resin composition according to [1] or [2] above, for forming an insulating layer for forming a conductor layer.

[19] The resin composition according to [1] or [2] above, for forming an insulating layer of a printed wiring board.

[20] A cured product of the resin composition according to [1] or [2] above.

[21] A sheet-like laminated material containing the resin composition according to [1] or [2] above.

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

[23] A printed wiring board provided with an insulating layer made of a cured product of the resin composition according to [1] or [2] above.

[24] A semiconductor device including the printed wiring board according to [23] above.

ADVANTAGE OF THE INVENTION According to the resin composition of this invention, the hardened|cured material which is excellent in plating adhesiveness and suppressed low dielectric loss tangent (Df) can be obtained.

Hereinafter, the present invention will be described in detail based on its preferred embodiment. However, the present invention is not limited to the following embodiments and examples, and can be implemented with arbitrary changes within a range not departing from the scope of the claims of the present invention and their equivalents.

<Resin composition>

The resin composition of the present invention contains (A) an aromatic nitrogen compound containing a phenolic hydroxyl group, (B) an epoxy resin, and (C) an active ester compound. According to such a resin composition, it is possible to obtain a cured product having excellent plating adhesion and a low dielectric loss tangent (Df). Further, in one embodiment, the resin composition of the present invention may have a low melt viscosity.

The resin composition of this invention may further contain arbitrary components other than (A) the aromatic nitrogen compound containing phenolic hydroxyl group, (B) epoxy resin, and (C) active ester compound. Examples of optional components include (C′) other curing agents, (D) radical reactive group-containing compounds, (E) inorganic fillers, (F) organic fillers, (G) curing accelerators, (H) other additives, and ( I) An organic solvent may be mentioned.

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

<(A) Aromatic nitrogen compound containing phenolic hydroxyl group>

In the first embodiment, the resin composition of the present invention contains, as component (A), a benzotriazole compound having a phenolic hydroxyl group. Component (A) may have a phenolic hydroxyl group as a substituent on the benzotriazole ring, or may have it as a substituent on an aromatic ring different from the benzotriazole ring. 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 hydroxyl group (phenolic hydroxyl group) It is a compound having an aromatic carbocyclic ring and a benzotriazole ring substituted with, more preferably a compound having an aromatic carbocyclic ring and a benzotriazole ring substituted with a hydroxy group (phenolic hydroxyl group) and an alkyl group having 3 or more carbon atoms, particularly Preferably, it is a compound having a benzene ring and a benzotriazole ring substituted with a hydroxyl group (phenolic hydroxyl group) and an alkyl group having 3 or more carbon atoms. (A) Component has one or two or more phenolic hydroxyl groups in one molecule, preferably one or two. (A) Component has one or two or more benzotriazole rings in one molecule, preferably has one or two. Component (A) preferably has one or two or more alkyl groups having 3 or more carbon atoms on an aromatic carbocyclic ring (benzene ring) having a phenolic hydroxyl group in one molecule, and one or two or more alkyl groups are particularly preferred. desirable. 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 means a ring that follows Hückel's rule in which the number of electrons contained in the π electron system of the ring is 4p+2 (p is a natural number). The aromatic ring may be an aromatic carbocycle containing only carbon atoms as ring-constituting atoms, or an aromatic heterocyclic ring having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms in addition to carbon atoms as ring-constituting atoms, but in one embodiment , It is preferably an aromatic carbocyclic ring. In one embodiment, the aromatic ring is preferably a 5-14 membered aromatic ring, more preferably a 6-14 membered aromatic ring, and still more preferably a 6-10 membered aromatic ring. Preferable specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

In the second embodiment, the resin composition of the present invention, as component (A), has formula (1a) or (1b):

[Formula (1a)]

[Formula (1b)]

[Wherein, R is (1) an aryl group that is substituted with at least one hydroxyl group and may further have a substituent, or (2) is substituted with a hydroxyl group on at least one aromatic carbon atom and further has a substituent. represents a preferred aralkyl group; X and Y each independently represent CH or N; ring Z represents an aromatic ring which may have a substituent]. In addition, in this specification, component (A) in 1st Embodiment and component (A) in 2nd Embodiment may be collectively called "(A) phenolic hydroxyl group containing aromatic nitrogen compound". (A) Component may be in the form of a salt.

R is (1) an aryl group that is substituted with at least one hydroxy group and may further have a substituent, or (2) is substituted with a hydroxy group on at least one aromatic carbon atom and further (on an aromatic carbon atom and an aliphatic represents an aralkyl group which may have a substituent on the carbon atom).

An aryl (group) means a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbocyclic ring. Unless otherwise specified, the aryl (group) is preferably an aryl (group) of 6 to 14 carbon atoms, and particularly preferably an aryl (group) of 6 to 10 carbon atoms. As an aryl (group), a phenyl group, 1-naphthyl group, 2-naphthyl group etc. are mentioned, for example.

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

Alkyl (group) means a straight-chain, branched-chain and/or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl (group) is preferably an alkyl (group) of 1 to 14 carbon atoms, more preferably an alkyl (group) of 1 to 10 carbon atoms. Examples of the alkyl (group) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, Neopentyl group, tert-pentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, tert-octyl group, cyclopentyl group, cyclohexyl group and the like.

The "substituent" included in the definition of the symbol of the formula (1a) or (1b) is not particularly limited, but in one embodiment, for example, a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom selected from It is a group consisting of 1 or more (for example, 1 to 100, preferably 1 to 50) skeletal atoms, may include a straight-chain structure, a branched-chain structure and/or a cyclic structure, and does not contain an aromatic ring. It may be a group or a group containing an aromatic ring. Examples of the "substituent" included in the definition of the symbol of the formula (1a) or (1b) include (1) a hydroxyl group, (2) a halogen atom, (3) a heterocyclic group, (4) a hydroxyl group, a halogen atom, and an alkyl group which may be substituted with a group selected from a heterocyclic group, (5) an aryl group which may be substituted with a group selected from a hydroxyl group, a halogen atom, an alkyl group, an aryl group and a heterocyclic group, (6) a hydroxyl group, a halogen atom, an aralkyl group which may be substituted with a group selected from an alkyl group, an aryl group and a heterocyclic group, (7) an alkyl-oxy group which may be substituted with a group selected from a hydroxyl group, a halogen atom and a heterocyclic group, (8) a hydroxyl group, an aryl-oxy group which may be substituted with a group selected from a halogen atom, an alkyl group, an aryl group and a heterocyclic group; (9) an aralkyl group which may be substituted with a group selected from a hydroxyl group, a halogen atom, an alkyl group, an aryl group and a heterocyclic group; -oxy group, (10) an alkyl-carbonyl group which may be substituted with a group selected from a hydroxy group, a halogen atom and a heterocyclic group, (11) a group selected from a hydroxy group, a halogen atom, an alkyl group, an aryl group and a heterocyclic group An aryl-carbonyl group which may be substituted, (12) an alkyl-carbonyl-oxy group which may be substituted with a group selected from a hydroxy group, a halogen atom and a heterocyclic group, (13) a hydroxy group, a halogen atom, an alkyl group, an aryl group an aryl-carbonyl-oxy group which may be substituted with a group selected from a group and a heterocyclic group, (14) an alkyl-oxy-carbonyl group which may be substituted with a group selected from a hydroxy group, a halogen atom and a heterocyclic group, (15) Monovalent substituents, such as the aryl-oxy-carbonyl group which may be substituted by the group chosen from a hydroxyl group, a halogen atom, an alkyl group, an aryl group, and a heterocyclic group, are mentioned. Here, the heterocyclic group may be further substituted with a halogen atom, an alkyl group, or the like. A heterocyclic group is a cyclic group which has heteroatoms, such as an oxygen atom, a nitrogen atom, and 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, but an aromatic heterocyclic group is preferable. As a heterocyclic group, For example, monocyclic aromatic heterocyclic groups, such as a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, and a pyridyl group; and condensed aromatic heterocyclic groups such as indolyl group, isoindolyl group, indazolyl group, benzoimidazolyl group, and benzotriazolyl group.

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

In one embodiment, R is preferably (1) an aryl group that is substituted with at least one hydroxyl group, further substituted with at least one alkyl group of 3 or more carbon atoms, and may further have a substituent, or (2) an aralkyl group substituted with a hydroxyl group on at least one aromatic carbon atom, further substituted with an alkyl group of 3 or more carbon atoms on at least one aromatic carbon atom, and which may further have a substituent; More preferably, it is an aryl group substituted with at least one hydroxyl group, further substituted with at least one alkyl group having 3 or more carbon atoms, and which may further have a substituent; More preferably, it is substituted with at least one hydroxyl group, and is 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 (1 ) a halogen atom, (2) a heterocyclic group, (3) an alkyl group which may be substituted with a group selected from a hydroxyl group, a halogen atom and a heterocyclic group, (4) a hydroxyl group, a halogen atom, an alkyl group, an aryl group and a heterocyclic group An aryl group which may have a substituent selected from aryl groups which may be substituted with selected groups and (5) aralkyl groups which may be substituted with groups selected from hydroxyl groups, halogen atoms, alkyl groups, aryl groups and heterocyclic groups.

X and Y each independently represent CH or N. X and Y, in one embodiment, preferably, at least one is N, more preferably, both are N.

Ring Z represents an aromatic ring which may have a substituent. In one embodiment, ring Z is preferably a benzene ring which may have a substituent, more preferably a benzene ring which may be substituted with a group selected from a hydroxyl group, a halogen atom and an alkyl group, and still more preferably is a benzene ring which may be substituted with a halogen atom.

In a suitable embodiment, the resin composition of the present invention, as component (A), has formula (2a) or (2b):

[Formula (2a)]

[Formula (2b)]

[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 represent a substituent; a and b each independently represent an integer of 0 to 4]

Contains the compound represented by

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

A represents a single bond or C(R ^A ) ₂ . In one embodiment, A is particularly preferably a single bond. R ^A represents a hydrogen atom or an alkyl group each independently. RA is, in one embodiment, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

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

R ² represents a substituent each independently. In one embodiment, each R ² is independently, preferably, (1) a halogen atom, (2) a heterocyclic group, (3) an alkyl group which may be substituted with a group selected from a hydroxyl group, a halogen atom and a heterocyclic group. , (4) an aryl group which may be substituted with a group selected from a hydroxy group, a halogen atom, an alkyl group, an aryl group and a heterocyclic group, or (5) a group selected from a hydroxy group, a halogen atom, an alkyl group, an aryl group and a heterocyclic group. It is an aralkyl group which may be substituted.

A represents an integer from 0 to 4, and in one embodiment is preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, still 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, still more preferably 1 or 2 to be.

In one embodiment, preferably, at least one of R ² is an alkyl group having 3 or more carbon atoms, and b is an integer of 1 to 4; More preferably, at least one of R ² 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; More preferably, at least one of R ² is a tertiary alkyl group having 4 to 10 carbon atoms, and b is 1 or 2; Especially preferably, at least one of R ² is a tert-butyl group, a tert-pentyl group, a tert-hexyl group, a tert-heptyl group or a tert-octyl group, and b is 1 or 2.

In a particularly suitable embodiment, the resin composition of the present invention, as component (A), has formula (3a) or (3b):

[Formula (3a)]

[Formula (3b)]

[during expression,

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 represent a hydrogen atom, a hydroxyl group, a halogen atom or an alkyl group;

R ^4a , R ^4b , R ^4c , R ^4d and R ^4e are each independently a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, formula (x):

[Formula (x)]

A group or formula (y1) or (y2) represented by:

[Formula (y1)]

[Formula (y2)]

represents a group represented by , and at least one of R ^4a , R ^4b , R ^4c , R ^4d and R ^4e is a hydroxy 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 represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, or a group represented by formula (y1) or (y2);

R ^6a , R ^6b , R ^6c and R ^6d each independently represent a hydrogen atom, a hydroxyl group, a halogen atom or an alkyl group;

* indicates a binding site]

Contains the compound represented by

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

R ^3a , R ^3b , R ^3c and R ^3d each independently represent 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 are preferably each independently a hydrogen atom or a halogen atom, more preferably R ^3a , R ^3c and R ^3d are a hydrogen atom, , and R ^3b is a hydrogen atom or a halogen atom; More preferably, R ^3a , R ^3c and R ^3d are hydrogen atoms, and R ^3b is a hydrogen atom or a chlorine atom.

R ^4a , R ^4b , R ^4c , R ^4d and R ^4e are each independently a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, a group represented by formula (x), or represented by formula (y1) or (y2) and at least one of R ^4a , R ^4b , R ^4c , R ^4d and R ^4e is a hydroxy group. In one embodiment, R ^4a , R ^4b , R ^4c , R ^4d and R ^4e are preferably each independently a hydrogen atom, a hydroxyl group, an alkyl group or a group represented by formula (x), and also R at least one of ^4a , R ^4b , R ^4c , R ^4d and R ^4e is a hydroxyl group; More preferably, R ^4a is a hydroxyl group, R ^4b is a hydrogen atom, an alkyl group or a group represented by formula (x), and R ^4c , R ^4d and R ^4e are each independently a hydrogen atom or an alkyl group; More preferably, R ^4a is a hydroxyl group, R ^4b is a hydrogen atom, an alkyl group or a group represented by formula (x), R ^4c , R ^4d and R ^4e are each independently a hydrogen atom or an alkyl group, and at least one of R ^4b , R ^4c , R ^4d and R ^4e is a secondary alkyl group having 3 to 10 carbon atoms or a tertiary alkyl group having 4 to 10 carbon atoms; Even more preferably, R ^4a is a hydroxy group, R ^4b is a hydrogen atom, an alkyl group or a group represented by formula (x), R ^4c and R ^4e are a hydrogen atom, R ^4d is a hydrogen atom or an alkyl group, , and at least one of R ^4b and R ^4d is a tertiary alkyl group having 4 to 10 carbon atoms; Especially preferably, R ^4a is a hydroxyl group, R ^4b is a hydrogen atom, an alkyl group or a group represented by formula (x), R ^4c and R ^4e are a hydrogen atom, R ^4d is an alkyl group, and R ^4b is an alkyl group. and at least one of R ^4d is a tert-butyl group, a tert-pentyl group, a tert-hexyl group, a tert-heptyl group or a tert-octyl group.

A ² represents a single bond, O or C(R ^A2 ) ₂ . In one embodiment, A ² is preferably a single bond or C(R ^A2 ) ₂ , particularly preferably C(R ^A2 ) ₂ . R ^A2 represents a hydrogen atom or an alkyl group each independently. In one embodiment, R ^A2 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. A ³ represents a single bond or C(R ^A3 ) ₂ . In one embodiment, A ³ is particularly preferably a single bond. R ^A3 represents a hydrogen atom or an alkyl group each independently. In one embodiment, R ^A3 is 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 represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, or a group represented by formula (y1) or (y2). In one embodiment, R ^5a , R ^5b , R ^5c , R ^5d and R ^5e are preferably each independently a hydrogen atom, a hydroxyl group, an alkyl group, or a group represented by formula (y1) or (y2) and at least one of R ^5a , R ^5b , R ^5c , R ^5d and R ^5e is a hydroxyl group; More preferably, R ^5a is a hydroxy group, R ^5b is a hydrogen atom, an alkyl group or a group represented by the formula (y1) or (y2), and R ^5c , R ^5d and R ^5e are each independently hydrogen an atom or an alkyl group; More preferably, R ^5a is a hydroxy group, R ^5b is an alkyl group or a group represented by formula (y1) or (y2), R ^5c and R ^5e are hydrogen atoms, and R ^5d is an alkyl group.

R ^6a , R ^6b , R ^6c and R ^6d each independently represent 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 are each independently preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom.

The molecular weight of component (A) is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less, and particularly preferably 700 or less. The lower limit of the molecular weight of component (A) may be, for example, 150 or more. Component (A) preferably contains a compound with a molecular weight of 230 or more, more preferably contains a compound with a molecular weight of 270 or more, still more preferably contains a compound with a molecular weight of 300 or more.

As a specific example of component (A), 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chloro-2H-benzotriazole (commercial product example: "JF- 79”), 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole (commercial product example: “JF-80” manufactured by Johoku Chemical Industry Co., Ltd.), 2-( 2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole (commercial product example: "JF-83" manufactured by Johoku Chemical Industry Co., Ltd.), 2,2'-methylenebis[6-(2H-benzo Triazol-2-yl)-4-tert-octylphenol] (commercial product example: "JF-832" manufactured by Johoku Chemical Industry Co., Ltd.), 6-(2H-benzotriazol-2-yl)-4-tert -Octyl-6'-tert-butyl-4'-methyl-2,2'-methylenebisphenol (commercial product example: "JAST-500" manufactured by Johoku Chemical Industry Co., Ltd.), 2,6-bis[(1H-benzo Triazol-1-yl) methyl] -4-methylphenol (commercial product example: "BT-3700" manufactured by Johoku Chemical Industry Co., Ltd.); and the like.

The content of the (A) phenolic hydroxyl group-containing aromatic nitrogen compound in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or less, more preferably 2 % by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, particularly preferably 0.3% by mass or less. The lower limit of the content of the (A) phenolic hydroxyl group-containing aromatic nitrogen compound in the resin composition is not particularly limited, but from the viewpoint of obtaining the desired effect of the present invention more remarkably, when the non-volatile component in the resin composition is 100% by mass , preferably 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more.

<(B) Epoxy Resin>

The resin composition of the present invention contains (B) an epoxy resin. (B) An epoxy resin is a curable resin having an epoxy group.

(B) As the epoxy resin, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, tris Phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin , glycidyl ester type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin , Spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthal Imidine type epoxy resin etc. are mentioned. (B) An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

It is preferable that the resin composition of this invention contains the epoxy resin which has 2 or more epoxy groups in 1 molecule as (B) epoxy resin. (B) The ratio of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile component of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably is 70% by mass or more.

Epoxy resins include liquid epoxy resins at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and solid epoxy resins at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). there is The resin composition of the present invention may contain only a liquid epoxy resin as an epoxy resin, or may contain only a solid epoxy resin, or may contain both a liquid epoxy resin and a solid epoxy resin, but liquid epoxy What contains both resin and solid-state epoxy resin is especially preferable.

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

Examples of liquid epoxy resins include glycerol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, A phenol novolak type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane dimethanol type epoxy resin, an epoxy resin having a cyclic aliphatic glycidyl ether, and a butadiene structure are preferable.

Specific examples of the liquid epoxy resin include "EX-992L" manufactured by Nagase ChemteX Corporation, "YX7400" manufactured by Mitsubishi Chemical Corporation, "HP4032" manufactured by DIC Corporation, "HP4032D", and "HP4032SS" (naphthalene type epoxy resin); "828US", "828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin) by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "jER807", "1750" (bisphenol F-type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" by Mitsubishi Chemical Corporation, "630LSD", "604" (glycidylamine type|mold epoxy resin); "ED-523T" by ADEKA (a glycerol-type epoxy resin); "EP-3950L" by ADEKA, "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" by ADEKA (dicyclopentadiene type epoxy resin); "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "EX-721" by Nagase ChemteX Co., Ltd. (glycidyl ester type epoxy resin); "EX-991L" by Nagase ChemteX Co., Ltd. (alkyleneoxy skeleton and butadiene skeleton containing epoxy resin); "Celoxide 2021P" by Daicel Co., Ltd. (alicyclic epoxy resin having an ester skeleton); "PB-3600" by Daicel Corporation, "JP-100", "JP-200", and "JP-400" (epoxy resin having a butadiene structure) manufactured by Nippon Soda; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resins) manufactured by Nippon Steel Chemical &Materials; "EG-280" (fluorene structure containing epoxy resin) by the Osaka Gas Chemical Co., Ltd.; Nagase ChemteX Co., Ltd. "EX-201" (cyclic aliphatic glycidyl ether) etc. are mentioned.

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

Examples of solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol novolac-type epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, and trisphenol-type epoxy resins. , naphthol type epoxy resin, biphenyl type epoxy resin, naphthalene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol A phthalimidine type epoxy resin is preferable.

As a specific example of a solid-state epoxy resin, "HP4032H" by DIC Corporation (naphthalene-type epoxy resin); "HP-4700" by DIC Corporation, "HP-4710" (naphthalene type tetrafunctional epoxy resin); "N-690" by DIC Corporation (cresol novolak-type epoxy resin); "N-695" by DIC Corporation (cresol novolak-type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin) by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthalene ether type epoxy resin) manufactured by DIC; Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd. "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin); "ESN475V" and "ESN4100V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN375" (dihydroxy naphthalene type epoxy resin) by the Nippon-tsu Chemical & Material company; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical Corporation "YX8800" (anthracene-type epoxy resin); Mitsubishi Chemical Corporation "YX7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; Mitsubishi Chemical Corporation "YX7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical Corporation "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical Corporation "jER1010" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation "jER1031S" (tetraphenylethane type epoxy resin); "WHR991S" (phenolphthalimidine type epoxy resin) by Nippon Kayaku Co., Ltd., etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(B) As the epoxy resin, when a solid epoxy resin and a liquid epoxy resin are used in combination, their mass ratio (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 50 g/eq. to 5,000 g/eq., more preferably 60 g/eq. to 2,000 g/eq., more preferably 70 g/eq. to 1,000 g/eq., even more preferably 80 g/eq. to 500 g/eq. Epoxy equivalent is the mass of resin per 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

(B) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a 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, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 30% by mass or less, more preferably 25% by mass or less, and furthermore It is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of the (B) epoxy resin in the resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, when the non-volatile component in the resin composition is 100% by mass. , More preferably 1% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more.

The mass ratio of the (B) epoxy resin to the (A) phenolic hydroxyl group-containing aromatic nitrogen compound in the resin composition (component (B)/component (A)) is not particularly limited, but is preferably 1 or more, more preferably is 5 or more, particularly preferably 10 or more. The upper limit of the mass ratio (component (B)/component (A)) of the (B) epoxy resin to the (A) phenolic hydroxyl group-containing aromatic nitrogen compound in the resin composition is not particularly limited, but is preferably 1,000 or less, and more It is preferably 500 or less, particularly preferably 100 or less.

<(C) active ester compound>

The resin composition of the present invention contains (C) an active ester compound. (C) An active ester compound may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios. (C) The active ester compound may have a function as an epoxy resin curing agent that reacts with and cures the (B) epoxy resin.

(C) As the active ester compound, generally two or more ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are used in one molecule. A compound having is preferably used. It is preferable that the said active ester compound is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester compound obtained from a carboxylic acid compound, 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 phenolic 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, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, etc. are mentioned. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensation of two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, as the (C) active ester compound, a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, benzoyl of phenol novolac Active ester compounds containing a cargo are preferred, and among these, at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable.

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

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

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

The mass ratio of the (C) active ester compound to the (A) phenolic hydroxyl group-containing aromatic nitrogen compound in the resin composition (component (C) / component (A)) is not particularly limited, but is preferably 1 or more, more preferably It is preferably 5 or more, particularly preferably 10 or more. The upper limit of the mass ratio (component (C)/component (A)) of the (C) active ester compound to the (A) phenolic hydroxyl group-containing aromatic nitrogen compound in the resin composition is not particularly limited, but is preferably 1,000 or less; More preferably, it is 500 or less, and particularly preferably 100 or less.

<(C') Other Curing Agents>

The resin composition of the present invention may further contain a (C') curing agent other than the component (C) as an optional component. (C') Other curing agents may be used alone or in combination of two or more. The (C') other curing agent described here is a component that does not correspond to the component (A). (C') Other curing agents, like the active ester compound (C), may have a function as an epoxy resin curing agent that reacts with and cures the (B) epoxy resin.

(C') Examples of the other curing agent include, but are not particularly limited to, a phenol-based curing agent, a carbodiimide-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and a thiol-based curing agent. A curing agent is mentioned. The resin composition of the present invention preferably contains, as (C′) other curing agent, a curing agent selected from the group consisting of a phenol-based curing agent and a carbodiimide-based curing agent, and particularly preferably contains a phenol-based curing agent.

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

Examples of the carbodiimide-based curing agent include a curing agent having at least one carbodiimide structure, preferably at least two carbodiimide structures in one molecule, such as tetramethylene-bis(t-butylcarbodiimide), aliphatic biscarbodiimides such as cyclohexanebis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); Aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide) ; Poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylenecarbodiimide) Ethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly polycarbodiimides such as aromatic polycarbodiimides such as (methylenediphenylenecarbodiimide) and poly[methylenebis(methylphenylene)carbodiimide].

Examples of commercially available carbodiimide-based curing agents include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K" and "Carbodilite" manufactured by Nisshinbo Chemical Co., Ltd. V-07” and “Carbodilite V-09”; "Stavaczol P", "Stavaczol P400", "Hycardil 510", etc. manufactured by Rhein Chemistry are mentioned.

Examples of the acid anhydride-based curing agent include a curing agent having at least one acid anhydride group in one molecule, and a curing agent having at least two acid anhydride groups in one molecule is preferable. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, and trialkyltetrahydrophthalic anhydride. , dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromelli anhydride Triacic acid, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfotetracarboxylic dianhydride, 1,3, 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis (anhydrotrimellitate), and polymeric acid anhydrides such as styrene maleic acid resin obtained by copolymerization of styrene and maleic acid. Examples of commercially available acid anhydride-based curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shinnippon Rica Co., Ltd., and "YH-306" manufactured by Mitsubishi Chemical Co., Ltd. , "YH-307", "HN-2200", "HN-5500" manufactured by Hitachi Kasei, "EF-30", "EF-40", "EF-60", "EF-80" manufactured by Clay Vale etc. can be mentioned.

Examples of the amine-based curing agent include a curing agent having one or more, preferably two or more amino groups in one molecule, examples of which include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred from the viewpoint of exhibiting the desired effect of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'- Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diamino ratio Phenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3 -Dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane , 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis ( 4-aminophenoxy) biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. are mentioned. Amine-based curing agent may use a commercial item, for example, "SEIKACURE-S" by Seika Corporation, "KAYABOND C-200S" by Nippon Kayaku Corporation, "KAYABOND C-100", "Kaya Hard A-A", "Kaya Hard AB", "Kaya Hard A-S", Mitsubishi Chemical Corporation's "Epicure W", etc. are mentioned.

As a specific example of a benzoxazine system hardening|curing agent, "JBZ-OP100D" by the JFE Chemical company, "ODA-BOZ"; "HFB2006M" by Showa Kobunshi Co., Ltd.; "P-d" and "F-a" manufactured by Shikoku Kasei Kogyo Co., Ltd., etc. are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylencyanate)), 4,4'-methylenebis (2,6 -Dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4 -Cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4- Bifunctional cyanate resins such as cyanatephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolaks and cresol novolacs, etc., and these cyanate resins partially triazinated A prepolymer etc. are mentioned. As specific examples of the cyanate ester curing agent, "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate ester resins) manufactured by Lonza Japan, "BA230", "BA230S75" (part of bisphenol A dicyanate or a prepolymer)) in which all were triazated to form a trimer.

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

(C') The reactor equivalent of the other curing agent is preferably 50 g/eq. to 3,000 g/eq., more preferably 100 g/eq. to 1,000 g/eq., more preferably 100 g/eq. to 500 g/eq., particularly preferably 100 g/eq. to 300 g/eq. The reactor equivalent is the mass of the curing agent per 1 equivalent of the reactor. A reactive group means a group that reacts with an epoxy resin, and in the case of a phenolic curing agent, it is a phenolic hydroxyl group, and varies depending on the type of curing agent.

The content of the (C′) other curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, More preferably, it is 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of the (C′) other curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0.01% by mass or more, or 0.1% by mass. It may be mass % or more, 1 mass % or more, and the like.

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

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

<(D) a compound having a radical reactive group>

From the viewpoint of suppressing the dielectric loss tangent to a lower level, 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 one or more (preferably two or more) radical reactive groups in one molecule. (D) The compound which has a radical reactive group may be used individually by 1 type, and may be used in combination of 2 or more types.

The radical reactive group is a group having a radically polymerizable ethylenically unsaturated bond, and examples thereof include, but are not particularly limited to, (1) acryloyl group, (2) methacryloyl group, (3) allyl group, and (4) methallyl group. , (5) a phenyl group which is substituted with a group selected from a vinyl group and an isopropenyl group and may be further substituted with an alkyl group (for example, a vinylphenyl group (ie, 4-vinylphenyl group, 3-vinylphenyl group, 2-vinylphenyl group)) , isopropenylphenyl group (i.e., 4-isopropenylphenyl group, 3-isopropenylphenyl group, 2-isopropenylphenyl group), etc.), (6) a group selected from a vinyl group and an isopropenyl group, and furthermore an alkyl group Benzyl group which may be substituted with (e.g., vinylbenzyl group (i.e. 4-vinylbenzyl group, 3-vinylbenzyl group, 2-vinylbenzyl group), isopropenylbenzyl group (i.e. 4-isopropenylbenzyl group) , 3-isopropenylbenzyl group, 2-isopropenylbenzyl group), etc.), (7) maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group), etc. can be heard

(D) In the first embodiment, the compound having a radical reactive group preferably includes a thermoplastic resin (for example, number average molecular weight of 800 or more) having two or more radical reactive groups. The thermoplastic resin is not particularly limited, and examples thereof include phenoxy resin, polyvinyl acetal resin, polystyrene resin, polyethylene resin, polypropylene resin, polybutadiene resin, polyimide resin, polyamideimide resin, and polyetherimide resin. , polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyether ether ketone resins, polyester resins, and the like, and (D) the compound having a radical reactive group, in the above embodiment, of these resins Modified resins having two or more radical reactive groups are included.

(D) In the first embodiment, the compound having a radical reactive group is more preferably a resin selected from modified polyphenylene ether resins having two or more radical reactive groups and modified polystyrene resins having two or more radical reactive groups. and, more preferably, a modified polyphenylene ether resin having two or more radical reactive groups, particularly preferably, in one embodiment, formula (4):

[Formula (4)]

[during expression,

R ¹¹ and R ¹² each independently represent an alkyl group;

R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group;

R ^a and R ^b are each independently a group selected from (1) acryloyl group, (2) methacryloyl group, (3) allyl group, (4) methallyl group, (5) vinyl group and isopropenyl group. represents a phenyl group which may be further substituted with an alkyl group or (6) a benzyl group which may be further substituted with a group selected from a vinyl group and an isopropenyl group and which may be further substituted with 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]

Contains the resin represented by The t unit and the u unit may be the same or different for each unit, respectively.

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

R ^a and R ^b are each independently a group selected from (1) acryloyl group, (2) methacryloyl group, (3) allyl group, (4) methallyl group, (5) vinyl group and isopropenyl group. represents a phenyl group which may be substituted and further substituted with an alkyl group; or (6) a benzyl group which may be substituted with a group selected from a vinyl group and an isopropenyl group and which may be further substituted with an alkyl group.

In one embodiment, each of R ^a and R ^b is independently, preferably, (1) a phenyl group which is substituted with a group selected from a vinyl group and an isopropenyl group, which may further be substituted with an alkyl group, or (2) a vinyl group. a benzyl group which may be substituted with a group selected from groups and isopropenyl groups and may be further substituted with an alkyl group; More preferably, 4-vinylphenyl group, 3-vinylphenyl group, 2-vinylphenyl group, 4-isopropenylphenyl group, 3-isopropenylphenyl group, 2-isopropenylphenyl group, 4-vinylbenzyl group, 3-vinyl a benzyl group, 2-vinylbenzyl group, 4-isopropenylbenzyl group, 3-isopropenylbenzyl group or 2-isopropenylbenzyl group; Especially preferably, it is a 4-vinylbenzyl group, 3-vinylbenzyl group, or 2-vinylbenzyl group.

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

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

The radical reactive group equivalent of the compound having a radical reactive group (D) in the first embodiment is preferably 300 g/eq. to 2,500 g/eq., more preferably 400 g/eq. to 2,000 g/eq. The radical reactive group equivalent represents the mass of the resin (compound) per 1 equivalent of the radical reactive group.

The number average molecular weight of the compound having a radical reactive group (D) in the first embodiment is preferably 800 to 10,000, more preferably 900 to 5,000. The number average molecular weight of the resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

Examples of commercial products of the compound having a (D) 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 Co., Ltd. ); "SA9000" by the SABIC Innovative Plastics company, "SA9000-111" (methacryl modified polyphenylene ether resin), etc. are mentioned.

(D) The compound having a radical reactive group includes, in the second embodiment, a low molecular weight compound having two or more radical reactive groups (for example, a molecular weight of less than 800). Examples of such a compound include a polyfunctional (meth)acryloyl group-containing compound with a molecular weight of less than 800, a polyfunctional vinylphenyl group-containing compound with a molecular weight of less than 800, and a polyfunctional (meth)allyl group-containing compound with a molecular weight of less than 800. can

A polyfunctional (meth)acryloyl group-containing compound having a molecular weight of less than 800 is a compound having two 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 cyclohexane-1,4-dimethanol di(meth)acrylate and cyclohexane-1,3-dimethanol di(meth)acrylate. rate, tricyclodecane dimethanol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1 ,8-Octanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane aliphatic (meth)acrylic acid ester compounds such as tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; Dioxane glycoldi(meth)acrylate, 3,6-dioxa-1,8-octanedioldi(meth)acrylate, 3,6,9-trioxaundecane-1,11-dioldi(meth) Acrylates, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di ether-containing (meth)acrylic acid ester compounds such as (meth)acrylate and propoxylated bisphenol A di(meth)acrylate; Tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate Isocyanurate-containing (meth)acrylic acid ester compounds, such as these, etc. are mentioned. As a commercial item of a polyfunctional (meth)acryloyl group-containing compound with a molecular weight of less than 800, for example, "A-DOG" (dioxane glycol diacrylate) manufactured by Shin Nakamura Chemical Industry Co., Ltd., manufactured by Kyoeisha Chemical Co., Ltd. "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate), Nippon Kayaku Co., Ltd. "KAYARAD R-684" (tricyclodecane Dimethanol diacrylate), "KAYARAD R-604" (dioxane glycol diacrylate), etc. are mentioned.

A polyfunctional vinylphenyl group-containing compound having a molecular weight of less than 800 is a compound having two 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, and 2,2-bis(4-vinylphenyl). Propane, bis(4-vinylphenyl) ether, etc. are mentioned.

A polyfunctional (meth)allyl group-containing compound having a molecular weight of less than 800 is a compound having two 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 diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and di-2,6-naphthalenedicarboxylic acid. aromatic carboxylic acid allyl ester compounds such as allyl and 2,3-naphthalenecarboxylic acid diallyl; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-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 etherbenzene; Allylsilane compounds, such as diallyldiphenylsilane, etc. are mentioned. As a commercial item of a polyfunctional (meth)allyl group-containing compound having a molecular weight of less than 800, "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Chemical Co., Ltd., "DAD" manufactured by Nisshoku Technofine Chemical Co., Ltd. (diallyl diphenate), "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., trade name "DAND" (diallyl 2,3-naphthalenecarboxylate) manufactured by Nippon Zoryu Chemical Industry Co., Ltd., Shikoku Ka "ALP-d" manufactured by Seiko Corporation (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Nippon Kayaku Co., Ltd. RE-810NM” (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane), manufactured by Shikoku Chemical Co., Ltd. “DA-MGIC” (1,3-diallyl-5-glycyl diisocyanurate) and the like.

(D) the compound having a radical reactive group, in one embodiment of the second embodiment, particularly preferably, formula (5):

[Formula (5)]

[during expression,

R ^d and R ^e are each independently a group selected from (1) acryloyl group, (2) methacryloyl group, (3) allyl group, (4) methallyl group, (5) vinyl group and isopropenyl group. represents a phenyl group which may be further substituted with an alkyl group or (6) a benzyl group which may be further substituted with a group selected from a vinyl group and an isopropenyl group and which may be further substituted with an alkyl group;

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

Ring A represents a non-aromatic carbocyclic ring which may have a substituent or a non-aromatic heterocycle which may have a substituent]

It includes a compound of low molecular weight represented by (for example, a molecular weight of less than 800).

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

R ^d and R ^e are each independently a group selected from (1) acryloyl group, (2) methacryloyl group, (3) allyl group, (4) methallyl group, (5) vinyl group and isopropenyl group. represents a phenyl group which may be substituted and further substituted with an alkyl group; or (6) a benzyl group which may be substituted with a group selected from a vinyl group and an isopropenyl group and which may be further substituted with an alkyl group. R ^d and R ^e in one embodiment are each independently preferably an acryloyl group or a methacryloyl group.

X ² and X ³ represent a single bond or an alkylene group. An alkylene group represents a linear and/or branched divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 6 carbon atoms. As an alkylene group, for example -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 - etc. can be mentioned. X ² and X ³ are each independently, preferably, in one embodiment, an alkylene group.

Ring A represents a non-aromatic carbocycle which may have a substituent or a non-aromatic heterocycle which may have a substituent.

A non-aromatic carbocyclic ring represents a ring in which only carbon atoms that do not have aromaticity in the entire ring are ring-constituting atoms. The non-aromatic carbocycle may be a monocyclic non-aromatic carbocycle or a polycyclic non-aromatic carbocycle. The non-aromatic carbocycle may be a saturated carbocycle composed only of single bonds or an unsaturated carbocycle having a double bond in addition to a single bond. The non-aromatic carbocycle is preferably a 3-21 membered non-aromatic carbocyclic ring, more preferably a 4-18 membered non-aromatic carbocyclic ring, and still more preferably a 5-14 membered non-aromatic carbocyclic ring. Preferable specific examples of the non-aromatic carbocyclic ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, and the like. Summons; Bicyclo[2.2.1]heptane ring (norbornane ring), bicyclo[4.4.0]decane ring (decalin ring), bicyclo[5.3.0]decane ring, bicyclo[4.3.0]nonane ring (hydrin ring) monocyclic), bicyclo[3.2.1]octane ring, bicyclo[5.4.0]undecane ring, bicyclo[3.3.0]octane ring, bicyclo[3.3.1]nonane ring, and the like; Tricyclo[5.2.1.0 ^2,6 ]decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 ^3,7 ]decane ring (adamantane ring), tricyclo[6.2.1.0 ^2,7 ] and tricyclic saturated carbocyclic rings such as undecane rings.

A non-aromatic heterocycle means a ring which does not have aromaticity in the whole ring and which has heteroatoms, such as an oxygen atom, a nitrogen atom, and a sulfur atom, in addition to a carbon atom as a ring-constituting atom. The non-aromatic heterocycle may be a monocyclic non-aromatic heterocycle or a polycyclic non-aromatic heterocycle. The non-aromatic heterocycle may be a saturated heterocycle composed only of single bonds or an unsaturated heterocycle having a double bond in addition to a single bond. The non-aromatic heterocycle is preferably a 3-21 membered non-aromatic heterocycle, more preferably a 4-18 membered non-aromatic heterocycle, and still more preferably a 5-14 membered non-aromatic heterocycle. A 1,3-dioxane ring, a 1,3-dioxolane ring, a tetrahydropyran ring, a tetrahydrofuran ring etc. are mentioned as a suitable specific example of a non-aromatic heterocyclic ring.

In one embodiment, ring A is preferably a non-aromatic carbocyclic ring which may be substituted with an alkyl group or a non-aromatic heterocyclic ring which may be substituted with an alkyl group; More preferably, it is the tetrahydrodicyclopentadiene ring which may be substituted by the alkyl group, or the 1, 3- dioxane ring which may be substituted by the alkyl group.

The radical reactive group equivalent of the compound having a radical reactive group (D) in the second embodiment is preferably 30 g/eq. to 400 g/eq., more preferably 50 g/eq. to 300 g/eq., more preferably 75 g/eq. to 200 g/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, still more preferably 250 to 500.

(D) In the third embodiment, the compound having a radical reactive group is preferably Formula (6'):

[Formula (6')]

[during expression,

ring b represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent;

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

* indicates a binding site]

It includes a maleimide compound having a partial structure represented by A maleimide compound means a compound containing at least one maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) in one molecule. The number of maleimide groups in one molecule of the maleimide compound in the third embodiment is preferably two or more, and particularly preferably two. The maleimide compound in 3rd Embodiment may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

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

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

Ring B represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent. Ring B is preferably a monocycloalkane ring which may be substituted with a group selected from an alkyl group and an alkenyl group, or a monocycloalkene ring which may be substituted with a group selected from an alkyl group and an alkenyl group. Ring B is more preferably a monocycloalkane ring which may be substituted with a group selected from an alkyl group of 1 to 14 carbon atoms and an alkenyl group of 2 to 14 carbon atoms, or an alkyl group of 1 to 14 carbon atoms and an alkenyl group of 2 to 14 carbon atoms. It is a monocycloalkene ring which may be substituted with a group selected from 14 alkenyl groups.

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

(D) The compound having a radical reactive group, in the third embodiment, particularly preferably, formula (6):

[Formula (6)]

[during expression,

R ¹⁰ each independently represents a substituent;

ring C each independently represents an aromatic ring which may have a substituent;

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

R ^x 's each independently represent 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 greater;

e each independently represents 0, 1 or 2;

n represents 0 or an integer greater than or equal to 1;

Other symbols are the same as above]

It includes a maleimide compound represented by The d unit, the e unit, and the n unit may be the same or different for each unit, respectively.

Examples of the "substituent" in R ¹⁰ and the "substituent" in ring C in the formula (6) include the same ones as the "substituents" included in the definition of symbols in the formula (5).

Ring C each independently represents an aromatic ring which may have a substituent, and is preferably a benzene ring which may be substituted with a group selected from alkyl groups. D ¹ and D ² are each independently a single bond, -C(R ^x ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO- , -COO- or -OCO-, and is preferably a single bond, -C(R ^x ) ₂ - or -O-. Each R ^x independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group. c each independently represents 0 or 1, and is preferably 0. d each independently represents 0 or an integer greater than or equal to 1, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2; e each independently represents 0, 1 or 2, and is preferably 0. n represents 0 or an integer greater than or equal to 1, and is preferably 0.

Formula (D) contained in Formula (6):

[Formula (D)]

[Wherein, * represents a binding site; Other symbols are the same as above]

The partial structure represented by is not particularly limited, but includes, for example, formulas (D-1) to (D-3):

[In the formula, * is the same as above]

substructures represented by .

The radical polymerizable group equivalent of the compound having a radical reactive group (D) in the third embodiment is preferably 200 g/eq. to 2,500 g/eq., more preferably 250 g/eq. to 2,000 g/eq., more preferably 300 g/eq. to 1,500 g/eq. (D) The radical polymerizable group equivalent of a compound having a radical reactive group represents the mass of resin per 1 equivalent of the radical polymerizable group.

The weight average molecular weight of the compound having a radical reactive group (D) in the third embodiment is preferably 400 to 10,000, more preferably 500 to 7,000, and particularly preferably 600 to 5,000.

Examples of commercial products of the compound having a (D) radical reactive group in the third embodiment include "BMI-689", "BMI-1500", "BMI-1700" and "BMI-3000J" manufactured by Designer Molecules. ”, and “SLK-6895-T90” manufactured by Shin-Etsu Chemical Co., Ltd.

(D) The compound having a radical reactive group, in the fourth embodiment, preferably has formula (7):

[Formula (7)]

[during expression,

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

ring E, ring F and ring G each independently represents an aromatic ring which may have a substituent;

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

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

f represents an integer of 1 or greater;

g each independently represents 0 or 1;

h each independently represents 0, 1, 2 or 3]

It includes a maleimide compound represented by The f unit and the h unit may be the same or different for each unit, respectively. The maleimide compound in 4th Embodiment may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

Examples of the "substituents" in the rings E, F and G of the formula (7) include the same ones as the "substituents" included in the definition of symbols of the formula (5).

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

Ring E, ring F and ring G each independently represent an aromatic ring which may have a substituent, preferably a benzene ring which may have a substituent, more preferably substituted with a group selected from an alkyl group and an aryl group. It is a benzene ring which may be, and is particularly preferably a (unsubstituted) benzene ring.

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

f represents an integer greater than or equal to 1, and is preferably an integer of 1 to 10. g each independently represents 0 or 1, and is preferably 1. h each independently represents 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, particularly preferably 1.

The radical polymerizable group equivalent of the compound having a radical reactive group (D) in the fourth embodiment is preferably 150 g/eq. to 1,000 g/eq., more preferably 200 g/eq. to 500 g/eq.

The weight average molecular weight of the compound having a radical reactive group (D) in the fourth embodiment is preferably 100 to 10,000, more preferably 150 to 5,000, and particularly preferably 200 to 3,000.

As a commercial item of the compound which has (D) radical reactive group in 4th Embodiment, Nippon Kayaku Co., Ltd. "MIR-3000-70MT", "MIR-5000-60T" etc. are mentioned, for example.

(D) The compound having a radical reactive group, in the fifth embodiment, preferably has formula (8):

[Formula (8)]

[during expression,

R ³⁰ each independently represents an alkyl group;

ring H and ring I each independently represent an aromatic ring which may have a substituent;

m represents an integer of 1 or more]

It includes a maleimide compound represented by The m unit may be the same or different for each unit. The maleimide compound in the fifth embodiment may be used singly or in combination of two or more at an arbitrary ratio.

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

R ³⁰ each independently represents an alkyl group, and in one embodiment, is preferably a methyl group. Ring H each independently represents an aromatic ring which may have a substituent, in one embodiment, is preferably a benzene ring which may have a substituent, more preferably may be substituted with a group selected from alkyl groups. It is a benzene ring, More preferably, it is a benzene ring substituted with the group chosen from an alkyl group. Each ring I independently represents an aromatic ring which may have a substituent, and in one embodiment, is preferably a benzene ring which may have a substituent, more preferably may be substituted with a group selected from alkyl groups. It is a benzene ring, More preferably, it is a (unsubstituted) benzene ring. m represents an integer greater than or equal to 1, and is preferably an integer of 1 to 20.

The compound having a (D) radical reactive group in the fifth embodiment can be produced using, for example, the method described in Japanese Invention Association Publication Publication No. 2020-500211 or a method similar thereto.

(D) The compound having a radical reactive group is a suitable resin in the first embodiment, a suitable compound in the second embodiment, a suitable compound in the third embodiment, a suitable compound in the fourth embodiment, or a suitable compound in the fifth embodiment. Any one of the suitable compounds in may be included alone, but two or more of these may be included in combination at an arbitrary ratio.

(D) The radical reactive group equivalent of the compound having a radical reactive group is preferably 30 g/eq. to 2,500 g/eq., particularly preferably 75 g/eq. to 2,000 g/eq.

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

<(E) inorganic filler>

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.

(E) As a material of an inorganic filler, an inorganic compound is used. (E) Materials of the inorganic filler include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, hydroxide Aluminum, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, Zirconate barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, etc. are mentioned. Among these, silica is particularly suitable. As silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica etc. are mentioned, for example. Moreover, as a silica, spherical silica is preferable. (E) An inorganic filler may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

(E) As a commercial item of an inorganic filler, it is "SP60-05" by Nittetsu Chemical & Materials company, "SP507-05", for example; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex; "UFP-30" by Denka Corporation; "Silent NSS-3N", "Silent NSS-4N", and "Silent NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" by the Adomatex company; "DAW-03" by the Denka company, "FB-105FD", etc. are mentioned.

(E) The average particle diameter of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less. less than μm. (E) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. . (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 measured by creating the particle size distribution of the inorganic filler on a volume basis with a laser diffraction scattering type particle size distribution analyzer and taking the median diameter as the average particle size. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone were weighed into a vial bottle and dispersed by ultrasonic waves for 10 minutes can be used. The measurement sample was measured using a laser diffraction type particle size distribution device, using blue and red light source wavelengths, and measuring the volume-based particle size distribution of the inorganic filler by the flow cell method, and from the obtained particle size distribution, as the median diameter The average particle diameter was calculated. As a laser diffraction type particle size distribution measuring device, "LA-960" by Horiba Seisakusho Co., Ltd. etc. are mentioned, for example.

(E) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, even more preferably 1 m 2 /g or more, and particularly preferably 3 m 2 /g or more. m2/g or more. (E) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m2/g or less, more preferably 70 m2/g or less, still more preferably 50 m2/g or less, particularly preferably is 40 m 2 / g or less. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multi-point method. there is.

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

As a commercial item of a surface treatment agent, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane) Silane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by Kogyo Co., Ltd. "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane couple) manufactured by Shin-Etsu Chemical Co., Ltd. ring agent), Shin-Etsu Chemical Co., Ltd. "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc. are mentioned.

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

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

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

The content of the inorganic filler (E) in the resin composition is not particularly limited, but is preferably 90% by mass or less, more preferably 85% by mass or less, when the non-volatile component in the resin composition is 100% by mass. It may be preferably 80% by mass or less, particularly preferably 75% by mass or less. The lower limit of the content of the (E) inorganic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 1% by mass or more, or 10% by mass. % or more, preferably 20 mass% or more or 30 mass% or more, more preferably 40 mass% or more or 50 mass% or more, even more preferably 50 mass% or more or 55 mass% or more, even more preferably is 60 mass% or more or 65 mass% or more, particularly preferably 68 mass% or more or 70 mass% or more.

<(F) organic filler>

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

(F) The organic filler exists in a particulate form in the resin composition. (F) As the organic filler, it is preferable to use rubber particles from the viewpoint of remarkably obtaining the desired effects of the present invention. (F) An organic filler may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

Examples of the rubber component contained in the rubber particles include silicone-based elastomers such as polydimethylsiloxane; Polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutyl Olefin type thermoplastic elastomers, such as a rene copolymer, an isobutylene-butadiene copolymer, an ethylene-propylene-diene terpolymer, and an ethylene-propylene-butene terpolymer; and thermoplastic elastomers such as acrylic thermoplastic elastomers such as propyl poly(meth)acrylate, butyl poly(meth)acrylate, cyclohexyl poly(meth)acrylate, and octyl poly(meth)acrylate. Moreover, you may mix silicone type rubber, such as a polyorganosiloxane rubber, with a rubber component. The rubber component contained in the rubber particles has a glass transition temperature of, for example, 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and still more preferably -30°C or lower.

(F) The organic filler preferably contains core-shell type rubber particles from the viewpoint of significantly obtaining the desired effects of the present invention. The core-shell rubber particle is a particulate organic filler composed of a core particle containing the rubber component as mentioned above and one or more layers of shell parts covering the core particle. In addition, the core-shell type rubber particle is a core-shell type graft copolymer composed of a core particle containing the rubber component as described above and a shell portion obtained by graft copolymerization of a monomer component copolymerizable with the rubber component included in the core particle. It is preferably a rubber particle. The core-shell type as used herein does not necessarily indicate only clearly distinguishable core particles and shell portions, but also includes those in which the boundary between the core particles and the shell portion is unclear, and the core particles do not have to be completely covered with the shell portion. .

The rubber component is preferably contained in a core-shell type rubber particle at 40% by mass or more, more preferably at least 50% by mass, and even more preferably at least 60% by mass. The upper limit of the content of the rubber component in the core-shell type rubber particles is not particularly limited, but from the viewpoint of sufficiently covering the core particles with the shell portion, for example, 95% by mass or less, preferably 90% by mass.

The monomer component forming the shell portion of the core-shell type rubber particle is, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, ( (meth)acrylic acid esters such as glycidyl meth)acrylate; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; Aromatic vinyl compounds, such as styrene, 4-vinyltoluene, and (alpha)-methylstyrene; (meth)acrylonitrile etc. are included, Among them, what contains (meth)acrylic acid ester is preferable, and what contains methyl (meth)acrylate is more preferable.

As a commercial item of a core-shell type rubber particle, it is "CHT" by the Cheil Industries company, for example; "B602" by UMGABS; "Pararoid EXL-2602", "Pararoid EXL-2603", "Pararoid EXL-2655", "Pararoid EXL-2311", "Pararoid EXL-2313", "Pararoid EXL" made by Dow Chemical Nippon -2315", "Pararoid KM-330", "Pararoid KM-336P", "Pararoid KCZ-201", Mitsubishi Rayon's "Metablen C-223A", "Metablen E-901", " "Metablen S-2001", "Metablen W-450A", "Metablen SRK-200", "Kaneka Ace M-511", "Kaneace M-600", "Kaneace M-400" manufactured by Kaneka Co., Ltd. , "Kane Ace M-580", "Kane Ace MR-01" and the like.

(F) The average particle diameter (average primary particle diameter) of the organic filler is not particularly limited, but is preferably 20 nm or more, more preferably 30 nm or more, still more preferably 50 nm 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 5,000 nm or less, more preferably 2,000 nm or less, still more preferably 1,000 nm 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 analyzer or the like.

The content of the organic filler (F) in the resin composition is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, when the non-volatile component in the resin composition is 100% by mass. Preferably it is 2 mass % or less. The lower limit of the content of the (F) organic filler in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it may be, for example, 0% by mass or more and 0.01% by mass or more, It may be preferably 0.1% by mass or more, more preferably 0.5% by mass or more.

<(G) Curing Accelerator>

The resin composition of the present invention may contain (G) a curing accelerator as an optional component. The (G) hardening accelerator described here is a component that does not correspond to the (A) component. (G) The curing accelerator has a function as a curing catalyst that promotes curing of the (B) epoxy resin.

Examples of the curing accelerator include phosphorus curing accelerators, urea curing accelerators, guanidine curing accelerators, imidazole curing accelerators, metal curing accelerators, and amine curing accelerators. Especially, an amine type hardening accelerator is preferable. (G) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus-based curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, and bis(tetrabutylphosphonium)pyro Mellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium aliphatic phosphonium salts such as tetraphenyl borate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra- p-Tolyl borate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrap-tolyl borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methylphenylborate) Aromatic phosphonium salts, such as oxyphenyl) ethylphosphonium tetraphenylborate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyl triphenylphosphonium thiocyanate; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; aromatic phosphine/quinone addition reactants such as triphenylphosphine/p-benzoquinone addition reactants; Tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, aliphatic phosphines such as tricyclohexylphosphine; Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolyl Phosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-isopropylphenyl) phosphine, Tris (4-butylphenyl) phosphine, tris (4-tert-butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris (2,5-dimethylphenyl) phosphine, tris (2, 6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine , tris (2-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphine, tris (4-tert-butoxyphenyl) phosphine, diphenyl- 2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2- and aromatic phosphines such as bis(diphenylphosphino)acetylene and 2,2'-bis(diphenylphosphino)diphenyl ether.

Examples of the urea-based curing accelerator include 1,1-dimethylurea; Aliphatic dimethyl urea, such as 1,1,3-trimethyl urea, 3-ethyl-1,1-dimethyl urea, 3-cyclohexyl-1,1-dimethyl urea, and 3-cyclooctyl-1,1-dimethyl urea; 3-phenyl-1,1-dimethyl urea, 3-(4-chlorophenyl)-1,1-dimethyl urea, 3-(3,4-dichlorophenyl)-1,1-dimethyl urea, 3-(3- Chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4 -Dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4 -Nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]- 1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea ), and aromatic dimethylurea such as N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea].

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid addition Water, 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-benzimidazolium chloride, 2-methylimidazoline, imidazole compounds such as 2-phenylimidazolin, imidazole compounds and epoxy resin An adduct body can be mentioned.

As the imidazole-based curing accelerator, a commercially available product may be used, for example, "1B2PZ" manufactured by Shikoku Chemical Co., Ltd., "2MZA-PW", "2PHZ-PW", "C11Z-A" manufactured by Mitsubishi Chemical Co., Ltd. "P200-H50" etc. are mentioned.

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

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

As an amine-type hardening accelerator, you may use a commercial item, For example, "MY-25" by Ajinomoto Fine Techno Co., Ltd. etc. are mentioned.

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, when the non-volatile component in the resin composition is 100% by mass. It is preferably 5% by mass or less, particularly preferably 2% by mass or less. The lower limit of the content of the (G) curing accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0.001% by mass or more, or 0.01% by mass. % or more, 0.1 mass % or more, and the like.

<(H) other additives>

The resin composition of this invention may further contain arbitrary additives as a non-volatile component. As such an additive, for example, 4-vinylphenyl, acryloyl group, methacryloyl group, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group), etc. a radically polymerizable compound having; 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, urethane resins, cyanate 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; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; antifoaming agents such as silicone antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenolic antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (eg, phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red), nitrogen-based flame retardants (eg, melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (eg, antimony trioxide); dispersants such as phosphoric acid ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; Stabilizers, such as a borate type stabilizer, a titanate type stabilizer, an aluminate type stabilizer, a zirconate type stabilizer, an isocyanate type stabilizer, a carboxylic acid type stabilizer, and a carboxylic acid anhydride type stabilizer, etc. are mentioned. (H) Other additives may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios. (H) The content of other additives can be appropriately set by those skilled in the art.

<(I) organic solvent>

The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the above non-volatile component. (I) As the organic solvent, a known one can be appropriately used, and the kind is not particularly limited. (I) Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester 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, ethyl diglycol acetate, γ-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,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide-based solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (I) The organic solvent may be used individually by 1 type, or may be used in combination of 2 or more types in an arbitrary ratio.

The content of the organic solvent (I) in the varnish-like resin composition before drying is not particularly limited, but when all components in the resin composition are 100% by mass, for example, 40% by mass or less, 30% by mass or less, preferably It is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, and particularly preferably 6% by mass or less. 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, but is preferably 5% by mass or less when all components in the resin composition are 100% by mass, More preferably, it is 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

<Method for producing resin composition>

The resin composition of the present invention, for example, (A) an aromatic nitrogen compound containing a phenolic hydroxyl group, (B) an epoxy resin, (C) an active ester compound, (C') other curing agents as necessary, (D) a compound having a radical reactive group as needed, (E) an inorganic filler as needed, (F) an organic filler as needed, (G) a curing accelerator as needed, (H) other additives as needed, and as needed Therefore, (I) can be prepared by adding and mixing the organic solvent in any order and/or partially or all simultaneously. In addition, in the process of adding and mixing each component, the temperature can be set appropriately, and you may heat and/or cool temporarily or continuously. In addition, in the process of adding and mixing, or after that, the resin composition may be uniformly dispersed by stirring or shaking using a stirring device or shaking device such as a mixer, for example. Moreover, you may perform defoaming under low-pressure conditions, such as under vacuum, simultaneously with stirring or shaking.

<Characteristics of Resin Composition>

The resin composition of the present invention contains (A) 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 low dielectric loss tangent (Df) can be obtained. Further, in one embodiment, the resin composition of the present invention may have a low melt viscosity.

A cured product of the resin composition of the present invention may be characterized by excellent coating adhesion. Therefore, in one embodiment, for example, as in Test Example 2 below, the copper plating peel strength calculated from the load when the copper plating conductor layer is formed on the cured product and the copper plating conductor layer is removed in the vertical direction is , preferably 0.2 kgf / cm or more, more preferably 0.25 kgf / cm or more, still more preferably 0.3 kgf / cm or more, 0.35 kgf / cm or more, particularly preferably 0.4 kgf / cm or more, 0.45 kgf / cm may be ideal The upper limit is not particularly limited, but may be, for example, 10 kgf/cm or less.

A cured product of the resin composition of the present invention may have a low dielectric loss tangent (Df). Therefore, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below is preferably 0.0200 or less, 0.0100 or less, more preferably 0.0070 or less, 0.0050 or less, more preferably 0.0040 or less, 0.0030 or less, particularly preferably 0.0028 or less, 0.0026 or less.

In one embodiment, the resin composition of the present invention may have a low melt viscosity. Therefore, the resin composition is excellent in circuit embedding during lamination. In one embodiment, the minimum melt viscosity of the resin composition at 60 ° C to 200 ° C when measured as in Test Example 3 is preferably 5,000 poise or less, more preferably 3,000 poise or less, still more preferably 2,000 poise or less, more preferably 1,600 poise or less, particularly preferably 1,400 poise or less. The lower limit thereof is not particularly limited, but 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, it may be 400 poise or more.

<Use of resin composition>

The resin composition of the present invention can be suitably used as a resin composition for insulating purposes, particularly as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition (resin composition for forming an insulating layer for forming a conductor layer) for forming the insulating layer for forming a conductor layer (including a redistribution layer) formed on the insulating layer. there is. Moreover, in the printed wiring board mentioned later, it can use suitably as a resin composition (resin composition for forming the insulating layer of a printed wiring board) for forming the insulating layer of a printed wiring board. The resin composition of the present invention can also be used in a wide range of applications requiring a resin composition, such as resin sheets, sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, and parts embedding resins. can

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is a resin composition for a redistribution layer as an insulating layer for forming a redistribution layer (cultivation It can also be suitably used also as a resin composition for forming a linear forming layer) and a resin composition for sealing semiconductor chips (resin composition for semiconductor chip sealing). When a semiconductor chip package is manufactured, a redistribution layer may be further formed on the sealing layer.

(1) a step of laminating a temporarily fixed film on a base material;

(2) a step of temporarily fixing a semiconductor chip on a temporarily fixing film;

(3) forming a sealing layer on the semiconductor chip;

(4) a step of peeling the substrate and temporarily fixed film from the semiconductor chip;

(5) a step of forming a redistribution forming layer as an insulating layer on the substrate of the semiconductor chip and the surface from which the temporarily fixed film was peeled off; and

(6) Step of forming a redistribution layer as a conductor layer on the rewiring formation layer

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

<Sheet-like laminated material>

The resin composition of the present invention may be used after being applied in a varnish state, but industrially it is generally suitable to use it in the form of a sheet-like laminated material containing the resin composition.

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

In one embodiment, a resin sheet comprises a support and a resin composition layer provided on the support, and the resin composition layer is formed of the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product with excellent insulating properties even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, but is usually 5 μm or more, 10 μm or more, and the like.

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

When using a film made of a plastic material as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter abbreviated as "PEN") ), polyesters such as polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide ( PES), polyether ketone, and polyimide. Especially, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using metal foil as a support body, as a metal foil, copper foil, aluminum foil, etc. are mentioned, for example, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) good night.

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

Moreover, as a support body, you may use the support body with a release layer which has a release layer on the surface to which it joins with a resin composition layer. As a release agent used for the release layer of the support body with a release layer, 1 or more types of release agents selected from the group which consists of alkyd resins, polyolefin resins, urethane resins, and silicone resins are mentioned, for example. The support with the release layer may use a commercial item, for example, "SK-1", "AL-5", "AL-5", "AL- 7", "Lumiror T60" manufactured by Tore, Inc., "Purex" manufactured by Teijin, and "Uni-Peel" manufactured by Unitica, etc. are exemplified.

The thickness of the support is not particularly limited, but is preferably in the range of 5 µm to 75 µm, and more preferably in the range of 10 µm to 60 µm. Moreover, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

In one embodiment, the resin sheet may further contain an arbitrary layer as needed. As such an optional layer, for example, a protective film or the like provided on the surface of the resin composition layer that is not bonded to the support (ie, the surface on the opposite side to the support) according to the support is exemplified. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

The resin sheet is, for example, prepared by preparing a liquid (varnish) resin composition as it is or by dissolving the resin composition in an organic solvent, and applying this to a support using a die coater or the like It can be manufactured by further drying to form a resin composition layer.

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

You may perform drying by a well-known method, such as heating and hot air spray. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin composition, for example, when using a resin composition containing 30% by mass to 60% by mass of the organic solvent, the resin composition layer is dried at 50°C to 150°C for 3 minutes to 10 minutes. can form

The resin sheet can be wound up in a roll shape and stored. When a resin sheet has a protective film, it becomes usable by peeling off a protective film.

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

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

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

The thickness of the prepreg can be set within the same range as that of the resin composition layer in the resin sheet.

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

<Printed Wiring Board>

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

A printed wiring board can be manufactured by the method including the process of following (I) and (II) using the said resin sheet, for example.

(I) Step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate

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

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

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the support body side. Examples of the member for heat-pressing the resin sheet to the inner-layer substrate (hereinafter also referred to as "heat-compression member") include a heated metal plate (such as a SUS head plate) or a metal roll (SUS roll). In addition, it is preferable to press the hot-compression member not directly onto the resin sheet, but through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the irregularities on the surface of the inner layer substrate.

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

Lamination can be performed with a commercially available vacuum laminator. As a commercially available vacuum laminator, a vacuum pressure type laminator made by Meiki Sesakusho, a vacuum applicator made by Nikko Materials, a batch type vacuum pressure laminator, etc. are mentioned, for example.

After lamination, the laminated resin sheets may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing the hot-compression bonding member from the support body side. The press conditions for the smoothing treatment can be the same conditions as the thermal compression conditions for the above laminate. The smoothing process can be performed with a commercially available laminator. In addition, you may perform lamination and smoothing processing continuously using the said commercially available vacuum laminator.

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

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

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

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

When manufacturing a printed wiring board, you may further perform (III) the process of making a hole in an insulating layer, the process of roughening (IV) an insulating layer, and the process of forming a (V) conductor layer. These steps (III) to (V) may be performed according to various methods known to those skilled in the art used in the manufacture of printed wiring boards. In the case where the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). You can do it in between. Moreover, if necessary, you may form a multilayer wiring board by repeating the formation of the insulating layer and the conductor layer of process (II) - process (V).

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

Step (III) is a step of perforating the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma or the like depending on the composition of the resin composition used for forming the insulating layer. You may determine the size and shape of a hole suitably according to the design of a printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, smear is also removed in this step (IV). The order and conditions of the roughening treatment are not particularly limited, and known procedures and conditions normally used when forming the insulating layer of a printed wiring board can be employed. For example, the insulation layer can be roughened by performing the swelling treatment with a swelling liquid, the roughening treatment with an oxidizing agent, and the neutralization treatment with a neutralization liquid in this order.

Although it does not specifically limit as a swelling liquid used for a roughening process, An alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. As a swelling liquid marketed, "Swelling Deep Securiganth P" by Atotech Japan, "Swelling Deep Securiganth SBU", etc. are mentioned, for example. The swelling treatment by the swelling solution is not particularly limited, but can be performed by, for example, immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 minute 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°C to 80°C for 5 minutes to 15 minutes.

Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline performance manganic acid solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. 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°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As an oxidizing agent marketed, alkaline permanganic acid solutions, such as "Concentrate Compact CP" by the Atotech Japan company and "Dosing Solution Securiganth P", are mentioned, for example.

Moreover, as a neutralization liquid used for a roughening process, acidic aqueous solution is preferable, and as a commercial item, "Reduction Solution Securigant P" by Atotech Japan Co., Ltd. is mentioned, for example.

The treatment with the neutralization liquid can be performed by immersing the treated surface subjected to the roughening treatment by the oxidizing agent in the neutralization liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the standpoint of workability and the like, a method of immersing the object subjected to the roughening treatment with an oxidizing agent in a neutralization solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

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

Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In suitable embodiments, the conductor layer comprises 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. do. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more types of metals selected from the above groups (eg, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). ) may be mentioned. Among them, from the viewpoint of versatility of formation of a conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, a nickel-chromium alloy, a copper-nickel alloy, An alloy layer of copper/titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or an alloy layer of nickel/chromium alloy is more preferred, and a single metal layer of copper is further desirable.

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

The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 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. It is preferable to form by an additive method. Hereinafter, an example in which the conductor layer is formed by a semi-additive method is shown.

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

In another embodiment, you may form a conductor layer using metal foil. When forming a conductor layer using metal foil, it is suitable to carry out a process (V) between process (I) and process (II). For example, after step (I), the support is removed and metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. Lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method using the metal foil on the insulating layer.

Metal foil can be manufactured by well-known methods, such as an electrolysis method and a rolling method, for example. As a commercial item of metal foil, HLP foil by the JX Nikko Nisseki Kinzoku company, JXUT-III foil, 3EC-III foil by the Mitsui Kinzokukozan company, TP-III foil, etc. are mentioned, for example.

<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 provided for electric appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, electric cars, ships, aircraft, etc.). there is.

[Example]

Hereinafter, the present invention will be specifically described by examples. The present invention is not limited to these examples. In addition, in the following, "part" and "%" indicating quantity mean "part by mass" and "% by mass", respectively, unless otherwise specified. In particular, the temperature condition in the case of no designation of temperature is room temperature (23 ° C.), and the pressure condition in the case of particularly no designation of pressure is atmospheric pressure (1 atm).

<Example 1>

A mixture of bisphenol A type epoxy and bisphenol F type epoxy ("ZX-1059" manufactured by Nittetsu Chemical & Materials Co., Ltd., epoxy equivalent 170 g/eq.) 3 parts, naphthalene backbone epoxy resin ("HP-4032-SS" manufactured by DIC Corporation) , Epoxy equivalent 144 g/eq.) 4 parts, biphenyl skeleton epoxy resin (Nippon Kayaku Co., Ltd. "NC-3000L", epoxy equivalent 272 g/eq.) 3 parts, active ester curing agent (DIC Corporation "HPC-8150-62T" ", Toluene solution of 62% by mass of non-volatile components, 234 g/eq. of active ester group equivalent) 22.6 parts, aminotriazine-containing cresol novolac ("LA-3018-50P" manufactured by DIC Corporation, 50% by mass of non-volatile components 1-methoxy-2-propanol solution) 4 parts, spherical silica (manufactured by Adomatex, “SO-C2”) surface-treated with an inorganic filler (amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) , Average particle diameter 0.5 μm, specific surface area 5.8 m / g)) 75 parts, organic filler (“EXL-2655” manufactured by DOW) 1 part, curing accelerator (4-dimethylaminopyridine manufactured by Wako Pure Chemical Industries Ltd.) 0.2 part 0.2 parts of a benzotriazole compound having a phenolic hydroxyl group ("JF-79" manufactured by Johoku Chemical Industry Co., Ltd.), 10 parts of MEK, and 10 parts of toluene were mixed, and uniformly dispersed using a high-speed rotary mixer to form a varnish phase. A resin composition was obtained.

<Example 2>

A benzotriazole compound having a phenolic hydroxyl group ("JF-79" manufactured by Johoku Chemical Industry Co., Ltd.) 0.2 part of a benzotriazole compound having a phenolic hydroxyl group (manufactured by Johoku Chemical Industry Co., Ltd. "JF-80") Except having used 0.2 part, it carried out similarly to Example 1, and obtained the varnish-like resin composition.

<Example 3>

A benzotriazole compound having a phenolic hydroxyl group ("JF-79" manufactured by Johoku Chemical Industry Co., Ltd.) 0.2 part of a benzotriazole compound having a phenolic hydroxyl group (manufactured by Johoku Chemical Industry Co., Ltd. "JF-83") Except having used 0.2 part, it carried out similarly to Example 1, and obtained the varnish-like resin composition.

<Example 4>

A benzotriazole compound having a phenolic hydroxyl group ("JF-79" manufactured by Johoku Chemical Industry Co., Ltd.) 0.2 part of a benzotriazole compound having a phenolic hydroxyl group (manufactured by Johoku Chemical Industry Co., Ltd. "JF-832") Except having used 0.2 part, it carried out similarly to Example 1, and obtained the varnish-like resin composition.

<Example 5>

Benzotriazole compound having a phenolic hydroxyl group ("JF-79" manufactured by Johoku Chemical Industry Co., Ltd.) 0.2 part benzotriazole compound having a phenolic hydroxyl group (manufactured by Johoku Chemical Industry Co., Ltd. "JAST-500") Except having used 0.2 part, it carried out similarly to Example 1, and obtained the varnish-like resin composition.

<Example 6>

Maleimide compound A (Mw/Mn = 1.81, m' = 1.47 (mainly 1, 2 or 3 ), MEK solution of 70% by mass of non-volatile components) was prepared.

[Formula (8')]

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%) was further added.

<Example 7>

Varnish in the same manner as in Example 6, except that 3.1 parts of styryl-modified polyphenylene ether resin (“OPE-2St-1200” manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution of 65% non-volatile content) was used instead of maleimide compound A. A resin composition of the phase was obtained.

<Example 8>

A varnish-like resin composition was obtained in the same manner as in Example 6, except that 2 parts of the dimer acid skeleton-containing maleimide compound ("BMI-689" manufactured by Designer Molecules) was used instead 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 glycol diacrylate (“A-DOG” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) was used instead 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 ("JF-79" manufactured by Johoku Chemical Co., Ltd.) was not used.

<Comparative Example 2>

A cresol furnace containing aminotriazine without using a benzotriazole compound having a phenolic hydroxyl group ("JF-79" manufactured by Johoku Chemical Co., Ltd.) and an active ester compound ("HPC-8150-62T" manufactured by DIC Corporation). The amount of rockfish ("LA-3018-50P" manufactured by DIC Corporation) was changed from 4 parts to 16 parts, and a mixture of bisphenol A-type epoxy and bisphenol F-type epoxy ("ZX-1059" manufactured by Nittetsu Chemical & Materials Co., Ltd., epoxy Eq. 170 g/eq.) is changed from 3 parts to 5 parts, and the amount of naphthalene backbone epoxy resin (“HP-4032-SS” manufactured by DIC, epoxy equivalent 144 g/eq.) is changed from 4 parts to 8 parts, , The amount of biphenyl backbone epoxy resin (“NC-3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 272 g/eq.) was changed from 3 parts to 5 parts, and the curing accelerator (4-dimethylaminopyridine manufactured by Wako Pure Chemical Industries Ltd.) A varnish-like resin composition was obtained in the same manner as in Example 1 except that the amount of was changed from 0.2 part to 0.3 part.

<Test Example 1: Measurement of dielectric loss tangent (Df)>

As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec, 38 μm in thickness) provided with a release layer was prepared. On the release layer of the support body, the varnish-like resin composition obtained in Examples and Comparative Examples was uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition layer was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet including a support and a resin composition layer.

The obtained resin sheet was heated at 190°C 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 a test piece having a width of 2 mm and a length of 80 mm. About the said test piece, the dielectric loss tangent (Df) was measured by the cavity resonance perturbation method using "HP8362B" by Agilent Technologies at a measurement frequency of 5.8 GHz and a measurement temperature of 23 degreeC. Measurements were made on three test pieces.

<Test Example 2: Copper Plating Peel Strength>

(1) Underlay treatment of the inner layer circuit board

As an inner-layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness of 18 μm, substrate thickness of 0.4 mm, “R1515A” manufactured by Panasonic Corporation) having inner-layer circuits (copper foil) on both sides was prepared. Both sides of the inner layer circuit board were 1 μm etched with "CZ8101" manufactured by Mack Corporation, and a copper surface roughening treatment was performed.

(2) Laminate of resin sheets

A resin sheet obtained in the same manner as in Test Example 1 was laminated on both sides of the inner-layer circuit board using a batch-type vacuum pressure laminator (two-stage build-up laminator, CVP700 manufactured by Nikko Materials). The lamination was carried out so that the resin composition layer of the resin sheet was in contact with the inner circuit board. In addition, the said lamination was carried out by reducing the pressure for 30 seconds, setting the air pressure to 13 hPa or less, and compressing the laminate at 130°C and a pressure of 0.74 MPa for 45 seconds. Then, hot pressing was performed at 120°C and a pressure of 0.5 MPa for 75 seconds.

(3) curing of resin composition

The laminated resin sheet and the inner-layer circuit board were heated at 130°C for 30 minutes and subsequently heated at 170°C for 30 minutes to cure the resin composition, thereby forming an insulating layer. After that, the support was peeled off to obtain a laminated board having an insulating layer, an inner-layer circuit board, and an insulating layer in this order.

(4) Harmonization treatment

The laminated substrate was immersed in a swelling liquid (Diethylene glycol monobutyl ether-containing Swelling Deep Securigant P (glycol ether, aqueous solution of sodium hydroxide) manufactured by Atotech Japan) at 60°C for 10 minutes. Next, the laminated substrate was immersed in a roughening solution (Concentrate Compact P (KMnO ₄ : 60g/L, NaOH: 40g/L aqueous solution) manufactured by Atotech Japan) at 80°C for 20 minutes. Thereafter, the laminated substrate was immersed in a neutralization solution (reduction solucin securigant P (sulfuric acid aqueous solution) manufactured by Atotech Japan) at 40° C. After that, the laminated substrate was dried at 80° C. for 30 minutes, and “evaluation Substrate A” was obtained.

(5) Plating by semi-additive method

The evaluation substrate A was immersed in an electroless plating solution containing Pdcl ₂ at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. Thereafter, an annealing treatment was performed by heating at 150°C for 30 minutes. After that, an etching resist was formed and pattern formation was performed by etching. Thereafter, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20 µm. Next, an annealing treatment was performed at 190°C for 60 minutes to obtain "evaluation substrate B".

(6) Measurement of copper plating peel strength

An incision was formed in the conductor layer of the evaluation substrate B to enclose a rectangular portion with a width of 10 mm and a length of 100 mm. One end of the rectangular portion was peeled off and pinched with a clamping tool (Autocomb type tester "AC-50C-SL" manufactured by TSE Co., Ltd.). The rectangular portion was peeled in the vertical direction at a rate of 50 mm/min at room temperature with a clamping tool, and the load (kgf/cm) when peeling 35 mm was measured as 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 device (“Rheosol-G3000” manufactured by UBM Corporation). The above measurement was performed using a parallel plate having a diameter of 18 mm with respect to a 1 g sample collected from the resin composition layer. The measurement conditions were a starting temperature of 60°C to 200°C, a heating rate of 5°C/min, a measurement temperature interval of 2.5°C, and a vibration of 1 Hz/deg. The lowest melt viscosity (poise) was obtained from the obtained measured melt viscosity.

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

As shown in Table 1, in Comparative Examples 1 and 2 in which no aromatic nitrogen compound containing a phenolic hydroxyl group was used, the copper plating peel strength was low and the dielectric loss tangent was high. On the other hand, it can be seen that these problems can be overcome when a resin composition containing (A) a phenolic hydroxyl group-containing aromatic nitrogen compound, (B) an epoxy resin, and (C) an active ester compound is used. Moreover, it turns out that such a resin composition has a low melt viscosity. Further, (D) In Examples 6 to 9 containing a compound having a radical reactive group, it is found that the dielectric loss tangent is suppressed to a lower level than in other Examples and Comparative Examples.

Claims (24)

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

[Formula (1b)]

[during expression,
R is
(1) an aryl group that is substituted with at least one hydroxyl group and may further have a substituent; or
(2) represents an aralkyl group which is substituted with a hydroxyl group on at least one aromatic carbon atom and may further have a substituent;
X and Y each independently represent CH or N;
Ring Z represents an aromatic ring which may have a substituent]
A resin composition comprising a compound represented by, (B) an epoxy resin and (C) an active ester compound. 3. The method of claim 2, wherein R is
(1) an aryl group substituted with at least one hydroxyl group, further substituted with at least one alkyl group having 3 or more carbon atoms, and which may further have a substituent; or
(2) A resin composition that is substituted with a hydroxyl group on at least one aromatic carbon atom, further substituted with an alkyl group having 3 or more carbon atoms on at least one aromatic carbon atom, and an aralkyl group which may further have a substituent. The method of claim 1 or 2, wherein component (A) is of formula (2a) or (2b):
[Formula (2a)]

[Formula (2b)]

[during expression,
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 represent a substituent;
a and b each independently represent an integer of 0 to 4]
A resin composition comprising a compound represented by The resin composition according to claim 4, wherein at least one of R ² 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. The resin composition according to claim 1 or 2, wherein the component (A) contains a compound having a molecular weight of 300 or more. The resin composition according to claim 1 or 2, wherein the content of the component (A) is 0.001% by mass to 5% by mass when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1 or 2, further comprising (D) a compound having a radical reactive group. The resin composition according to claim 1 or 2, wherein the content of the component (B) is 0.1% by mass to 30% by mass, when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1 or 2, wherein the content of the component (C) is 10% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1 or 2, further comprising (E) an inorganic filler. The resin composition according to claim 11, wherein the component (E) is silica. The resin composition according to claim 11, wherein the content of the component (E) is 40% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1 or 2, further comprising (F) an organic filler. The resin composition according to claim 1 or 2, further comprising a phenolic curing agent. The resin composition according to claim 1 or 2, wherein the lowest melt viscosity at 60°C to 200°C is 1,400 poise or less. The resin composition according to claim 1 or 2, wherein the cured product of the resin composition has a dielectric loss tangent (Df) of 0.0026 or less when measured at 5.8 GHz and 23°C. The resin composition according to claim 1 or 2, which is for forming an insulating layer for forming a conductor layer. The resin composition according to claim 1 or 2, which is for forming an insulating layer of a printed wiring board. A cured product of the resin composition according to claim 1 or 2. A sheet-like laminated material containing the resin composition according to claim 1 or 2. 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. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to claim 1 or 2. A semiconductor device comprising the printed wiring board according to claim 23 .