TWI840527B - Resin composition, cured product of resin composition, resin sheet, printed wiring board and semiconductor device - Google Patents

Abstract

The subject of the present invention is to provide a resin composition that can obtain a cured product with a small dielectric tangent value, excellent adhesion to conductive materials after environmental resistance tests, and improved brittleness; a cured product of the resin composition; a resin sheet containing the resin composition; a printed wiring board containing an insulating layer formed by the cured product of the resin composition, and a semiconductor device. The solution of the present invention is a resin composition that includes (A) a maleimide compound, (B) an allyl-containing benzoxazine compound containing a substituted or unsubstituted allyl group, and (C) a high molecular weight component.

Description

Resin composition, cured product of resin composition, resin sheet, printed wiring board and semiconductor device

The present invention relates to a resin composition, and more particularly to a cured product of the resin composition, and a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

As a manufacturing technology for printed wiring boards, a manufacturing method using a stacking method in which insulating layers and conductive layers are alternately stacked is known.

As an insulating material for a printed wiring board used as such an insulating layer, for example, Patent Document 1 discloses a resin composition containing a maleimide compound. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2016-074871

[Problems to be solved by the invention]

In recent years, there has been a demand for a smaller value of the dielectric tangent of the insulating layer (eg, less than 0.0050) and for further improvement of the adhesion between the insulating layer and the conductive material (hereinafter, also simply referred to as "adhesion").

Generally speaking, the cured product of a resin composition containing a maleimide compound has a small dielectric tangent value. However, since maleimide compounds generally have a high softening point, the cured product of a resin composition containing a maleimide compound tends to be brittle. In addition, the inventors' research results show that the cured product of a resin composition containing a maleimide compound tends to have deteriorated adhesion after environmental resistance tests, especially after HAST (Highly Accelerated temperature and humidity Stress Test).

The subject of the present invention is to provide a resin composition that can obtain a small dielectric tangent value, excellent adhesion between conductive materials after environmental resistance tests, and improved brittleness of the cured product; a cured product of the resin composition; a resin sheet containing the resin composition; a printed wiring board containing an insulating layer formed by the cured product of the resin composition, and a semiconductor device. [Means for solving the subject]

As a result of intensive research, the inventors of the present invention have found that the above-mentioned problems can be solved by using a combination of (A) a maleimide compound, (B) an allyl-containing benzoxazine compound containing a substituted or unsubstituted allyl group, and (C) a high molecular weight component, thereby completing the present invention.

That is, the present invention includes the following contents. [1] A resin composition comprising (A) a maleimide compound, (B) an allyl group-containing benzoxazine compound, and (C) a high molecular weight component. [2] The resin composition as described in [1], wherein the content of component (A) is 10% by mass to 40% by mass, based on the non-volatile components in the resin composition being 100% by mass. [3] The resin composition as described in [1] or [2], wherein the content of component (B) is 0.01% by mass to 15% by mass, based on the non-volatile components in the resin composition being 100% by mass. [4] The resin composition as described in any one of [1] to [3], wherein the mass ratio of component (B) to component (A) [component (B)/component (A)] is 0.01 to 0.20. [5] The resin composition as described in any one of [1] to [4], wherein component (C) is a thermoplastic resin. [6] The resin composition as described in [5], wherein the thermoplastic resin is at least one selected from a polyimide resin, a polycarbonate resin and a phenoxy resin. [7] The resin composition as described in any one of [1] to [6], wherein the weight average molecular weight or number average molecular weight of component (C) is 5,000 to 100,000. [8] The resin composition as described in any one of [1] to [7], wherein the content of component (C) is 0.1% by mass to 10% by mass, based on 100% by mass of the non-volatile components in the resin composition. [9] The resin composition as described in any one of [1] to [8], further comprising (D) an inorganic filler. [10] The resin composition as described in [9], wherein component (D) is surface-treated with an amine coupling agent or a (meth)acrylic coupling agent. [11] The resin composition as described in [9] or [10], wherein the content of component (D) is 50% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. [12] A resin composition as described in any one of [1] to [11], wherein the cured product obtained by heat treatment at 200°C for 90 minutes has a dielectric tangent of 0.005 or less when measured by cavity resonance propagation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. [13] A resin composition as described in any one of [1] to [12], wherein the cured product obtained by heat treatment at 200°C for 90 minutes has an elongation at break of 0.7% or more when measured in accordance with Japanese Industrial Standard JIS K7127. [14] A resin composition as described in any one of [1] to [13], which is used for forming an insulating layer. [15] A resin composition as described in any one of [1] to [14], which is used to form an insulating layer for forming a conductive layer. [16] A cured product of the resin composition as described in any one of [1] to [15]. [17] A resin sheet comprising a support and a resin composition layer comprising the resin composition as described in any one of [1] to [15] disposed on the support. [18] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition as described in any one of [1] to [15] or a cured product as described in [16]. [19] A semiconductor device comprising the printed wiring board as described in [18]. [Invention Effect]

According to the present invention, there can be provided a resin composition which can obtain a cured product having a small dielectric tangent value, excellent adhesion to conductive materials after environmental resistance tests, and improved brittleness; a cured product of the resin composition; a resin sheet comprising the resin composition; a printed wiring board comprising an insulating layer formed by the cured product of the resin composition, and a semiconductor device.

The present invention is described in detail below with respect to its suitable embodiments. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications within the scope of the patent application of the present invention and its equivalents.

[Resin composition] The resin composition of the present invention comprises (A) a maleimide compound, (B) an allyl-containing benzoxazine compound, and (C) a high molecular weight component. The resin composition of the present invention, by comprising components (A) to (C), can provide a low dielectric tangent value, excellent adhesion between conductive materials after environmental resistance tests, and improved brittleness of the hardened material.

The resin composition is a combination of components (A) to (C) and may further include arbitrary components. Examples of the arbitrary components include (D) inorganic fillers, (E) polymerization initiators, (F) thermosetting resins (but excluding components (A), (B) and (C)) and (G) other additives. The following is a detailed description of each component included in the resin composition.

<(A) Maleimide compound> The resin composition contains a maleimide compound as the (A) component. By including the (A) component in the resin composition, it becomes possible to obtain a cured product having a smaller dielectric tangent value. The (A) component may be used alone or in combination of two or more.

The component (A) contains a maleimide compound represented by the following formula (1) in at least one molecule.

The number of maleimide groups per molecule of component (A) is 1 or more, preferably 2 or more, and more preferably 3 or more, from the viewpoint of obtaining a cured product having a small dielectric tangent value. The upper limit is not limited, but may be 10 or less, 6 or less, 4 or less, or 3 or less.

The first example of the component (A) is a maleimide compound having a biphenyl structure (hereinafter also referred to as "the first maleimide compound") from the viewpoint of obtaining a cured product with a small dielectric tangent value. The so-called biphenyl structure is a structure represented by the following formula (2). In formula (2), ^R1 and ^R2 each independently represent a substituent. a and b each independently represent an integer of 0 to 4. * represents a bonding moiety.

Examples of substituents represented by R ¹ and R ² include halogen atoms, -OH, -OC _1-10 alkyl, -N(C _1-10 alkyl) ₂ , C _1-10 alkyl, C _6-10 aryl, -NH ₂ , -CN, -C(O)OC _1-10 alkyl, -COOH, -C(O)H, -NO ₂ , etc. Here, the term "C _xy " (x and y are positive integers, and x < y) means that the number of carbon atoms in the organic group described immediately after the term is x to y. For example, the term "C _1-10 alkyl" means an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring or a condensed ring.

The above-mentioned substituents may further have a substituent (hereinafter, sometimes referred to as a "secondary substituent"). As the secondary substituent, the same ones as the above-mentioned substituents can be used unless otherwise specified.

a and b each independently represent an integer from 0 to 4, preferably represent an integer from 0 to 3, more preferably 0 or 1, and even more preferably 0.

The first maleimide compound preferably has maleimide groups at both ends in order to obtain a cured product having a small dielectric tangent value.

From the viewpoint of obtaining a cured product with a small dielectric tangent value, the first maleimide compound preferably further has either an aliphatic alkyl group or an aromatic alkyl group, and more preferably has both an aliphatic alkyl group and an aromatic alkyl group. The term "aromatic alkyl group" means a alkyl group containing an aromatic ring. However, the aromatic alkyl group does not need to be composed of only an aromatic ring, and may contain a chain structure or an alicyclic alkyl group in part, and the aromatic ring may be any of a monocyclic, polycyclic, and heterocyclic type.

The aliphatic alkyl group is preferably a divalent aliphatic alkyl group, more preferably a divalent saturated aliphatic alkyl group, and still more preferably an alkylene group. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, still more preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group.

As the aromatic alkyl group, a divalent aromatic alkyl group is preferred, an arylene group, an arylene group is more preferred, and an arylene group is still more preferred. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferred, an arylene group having 6 to 20 carbon atoms is more preferred, and an arylene group having 6 to 10 carbon atoms is still more preferred. Examples of such arylene groups include phenylene, naphthylene, anthracenylene, and biphenylene. As the arylene group, an arylene group having 7 to 30 carbon atoms is preferred, an arylene group having 7 to 20 carbon atoms is more preferred, and an arylene group having 7 to 15 carbon atoms is still more preferred. Examples of such arylene groups include benzylene and a group having a biphenylene-methylene structure. Among them, a phenylene group, a benzylene group, and a group having a biphenylene-methylene structure are preferred, and a phenylene group is more preferred.

The number of maleimide groups per molecule of the first maleimide compound is 1 or more, preferably 2 or more, and more preferably 3 or more, from the viewpoint of obtaining a cured product having a small dielectric tangent value. The upper limit is not limited, but may be 10 or less, 6 or less, 4 or less, or 3 or less.

In the first maleimide compound, the nitrogen atom of the maleimide group is preferably directly bonded to the aromatic hydrocarbon group from the viewpoint of significantly obtaining the expected effect of the present invention. Here, the term "directly" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

The first maleimide compound preferably has a structure represented by, for example, the following formula (A1-1). In formula (A1-1), ^R3 and ^R8 represent maleimide groups, ^R4 , ^R5 , ^R6 and ^R7 each independently represent a hydrogen atom, an alkyl group or an aryl group, ^R9 and ^R10 each independently represent a substituent, a1 and b1 each independently represent an integer of 0 to 4, m1 and m2 each independently represent an integer of 1 to 10, and n represents an integer of 1 to 100.

R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.

As the alkyl group in R ⁴ , R ⁵ , R ⁶ and R ⁷ , an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 3 carbon atoms is further preferred. The alkyl group may be linear, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl and the like.

The aryl group in R ⁴ , R ⁵ , R ⁶ and R ⁷ is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a monocyclic ring or a condensed ring. Examples of such aryl groups include phenyl, naphthyl, anthracenyl and the like.

The alkyl group and aryl group in R ⁴ , R ⁵ , R ⁶ and R ⁷ may have a substituent. The substituent is the same as that of R ¹ in formula (2).

^R9 and ^R10 each independently represent a substituent, and are the same as ^R1 and ^R2 in formula (2).

a1 and b1 represent integers from 0 to 4 independently, which are the same as a and b in formula (2).

m1 and m2 independently represent integers from 1 to 10, preferably from 1 to 6, more preferably from 1 to 3, even more preferably from 1 to 2, and even more preferably 1.

n represents an integer ranging from 1 to 100, preferably ranging from 1 to 50, more preferably ranging from 1 to 20, and even more preferably ranging from 1 to 5.

R ³ and R ⁸ represent maleimide groups, and the maleimide groups are directly bonded to the aromatic hydrocarbon group. The maleimide groups represented by R ³ and R ⁸ are preferably directly bonded to any _one of the ortho-position, meta-position and para-position, and more preferably directly bonded to the para-position, based on the bonding position of (CH ₂ ) m1 or (CH ₂ ) _m2 bonded to the aromatic hydrocarbon group.

The first maleimide compound preferably has a structure represented by formula (A1-1a). In formula (A1-1a), R ¹¹ and R ¹⁶ represent maleimide groups, R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group. m3 and m4 each independently represent an integer of 1 to 10, and n1 represents an integer of 1 to 100.

R ¹¹ and R ¹⁶ represent maleimide groups, which are the same as R ³ and R ⁸ in formula (A1-1).

R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group, and are the same as R ⁴ , R ⁵ , R ⁶ and R ⁷ in formula (A1-1).

m3 and m4 independently represent integers from 1 to 10, which are the same as m1 and m2 in formula (A1-1).

n1 represents an integer between 1 and 100, which is the same as n in formula (A1-1).

The first maleimide compound preferably has a structure represented by formula (A1-1b). In formula (A1-1b), R ¹⁷ and R ¹⁸ represent a maleimide group. n2 represents an integer of 1 to 100.

R ¹⁷ and R ¹⁸ represent maleimide groups, which are the same as R ³ and R ⁸ in formula (A1-1).

n2 represents an integer between 1 and 100, which is the same as n in formula (A1-1).

As the first maleimide compound, a commercially available product can be used. Examples of the commercially available product include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. (main component: a compound of the following formula (A1-1c)). (Wherein, S ¹ represents 1 or 2)

The second example of the component (A) is a maleimide compound containing at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms (hereinafter also referred to as the "second maleimide compound") from the viewpoint of obtaining a cured product with a small dielectric tangent value. However, the second maleimide compound does not have a biphenyl structure and is excluded from the first maleimide compound.

The carbon number of the alkyl group with 5 or more carbon atoms in the second maleimide compound is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. The alkyl group may be any of a straight chain, a branched chain, and a ring, and preferably a straight chain. Examples of such alkyl groups include pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group with 5 or more carbon atoms may be a substituent of an alkylene group with 5 or more carbon atoms.

The number of carbon atoms in the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. The alkylene group may be any of a linear chain, a branched chain, and a cyclic shape, and a linear chain shape is preferred. Here, the so-called cyclic alkylene group also includes the concept of only cyclic alkylene groups and both linear chain alkylene groups and cyclic alkylene groups. Examples of such an alkylene group include an pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecylene group, a dodecyl group, a tridecenyl group, a heptadecenyl group, a hexatriacontylene group, a group having an octyl-cyclohexyl group structure, a group having an octyl-cyclohexyl-octyl group structure, a group having a propyl-cyclohexyl-octyl group structure, and the like.

From the viewpoint of significantly obtaining the effect of the present invention, the second maleimide compound preferably contains both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms.

An alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms may bond to each other to form a ring, and the ring structure may include a spiro ring or a condensed ring. Examples of the ring formed by bonding to each other include a cyclohexane ring.

The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms may or may not have a substituent. The substituent is the same as the substituent represented by ^R1 in the above formula (2). Here, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms.

In the second maleimide compound, it is preferred that an alkyl group having 5 or more carbon atoms or an alkylene group having 5 or more carbon atoms is directly bonded to the nitrogen atom of the maleimide group.

The number of maleimide groups per molecule of the second maleimide compound may be 1, but is preferably 2 or more, more preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. The second maleimide compound can significantly achieve the effect of the present invention by having 2 or more maleimide groups per molecule.

The second maleimide compound is preferably a maleimide compound represented by the following general formula (A2-1). In the general formula (A2-1), M represents an alkylene group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

M represents an alkylene group having 5 or more carbon atoms which may have a substituent. The alkylene group of M is the same as the alkylene group having 5 or more carbon atoms described above. The substituent of M is the same as the substituent represented by ^R1 in the general formula (2), and the substituent is preferably an alkylene group having 5 or more carbon atoms. Here, the carbon number of the substituent is not included in the carbon number of the alkylene group having 5 or more carbon atoms.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C(=O)-, -C(=O)-O-, -NR ⁰ - (R ⁰ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), an oxygen atom, a sulfur atom, C(=O)NR ⁰ -, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and a group consisting of a combination of two or more of these divalent groups. The alkylene group, the alkenylene group, the alkynylene group, the arylene group, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and a group consisting of a combination of two or more of these divalent groups may have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide refers to a divalent group derived from phthalimide, specifically a group represented by the general formula (3). The divalent group derived from pyromellitic acid diimide refers to a divalent group derived from pyromellitic acid diimide, specifically a group represented by the general formula (4). In the formula, "*" represents a bonding part.

The alkylene group as the divalent linking group of L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and particularly preferably an alkylene group having 1 to 40 carbon atoms. The alkylene group may be any of a straight chain, a branched chain, and a ring. Examples of such alkylene groups include methyl ethylene, cyclohexylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecenyl, hexatriacontylene, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

The alkenylene group as the divalent linking group of L is preferably an alkenylene group having 2 to 20 carbon atoms, more preferably an alkenylene group having 2 to 15 carbon atoms, and particularly preferably an alkenylene group having 2 to 10 carbon atoms. The alkenylene group may be in any of a straight chain, a branched chain, or a ring shape. Examples of such alkenylene groups include ethylenylene, hexenylene, pentenylene, hexenylene, heptenylene, and octenylene.

The alkynylene group as the divalent linking group of L is preferably an alkynylene group having 2 to 20 carbon atoms, more preferably an alkynylene group having 2 to 15 carbon atoms, and particularly preferably an alkynylene group having 2 to 10 carbon atoms. The alkynylene group may be in any of a straight chain, a branched chain, or a ring shape. Examples of such alkynylene groups include methylethynylene, cyclohexynylene, pentynylene, hexynylene, heptynylene, and octynylene.

The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, still more preferably an arylene group having 6 to 14 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include phenylene, naphthylene, anthracenylene, and the like.

The divalent linking group of L, i.e., the alkylene group, alkenylene group, alkynylene group, and arylene group, may have a substituent. The substituent is the same as the substituent represented by ^R1 in the general formula (A-2), and is preferably an alkyl group having 5 or more carbon atoms.

Examples of the group consisting of a combination of two or more divalent groups included in L include a divalent group consisting of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group consisting of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a divalent group consisting of an alkylene group and a divalent group derived from pyromellitic acid diimide; and the like. The group consisting of a combination of two or more divalent groups can form a ring such as a condensed ring by combining the individual groups. Furthermore, the group consisting of a combination of two or more divalent groups can be a repeating unit having a repeating unit number of 1 to 10.

Among them, L in the general formula (A2-1) is preferably an oxygen atom, an aryl group having 6 to 24 carbon atoms which may have a substituent, an alkylene group having 1 to 50 carbon atoms which may have a substituent, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, or a divalent group consisting of a combination of two or more of these groups. Among them, L is more preferably an alkylene group; a divalent group having a structure of alkylene group-divalent group derived from phthalimide-oxygen atom-divalent group derived from phthalimide; a divalent group having a structure of alkylene group-divalent group derived from phthalimide-oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-divalent group derived from phthalimide; a divalent group having a structure of alkylene group-divalent group derived from phthalimide.

The second maleimide compound is preferably a maleimide compound represented by the following general formula (A2-2). In general formula (A2-2), ^M1 each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent, A each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group having an aromatic ring which may have a substituent. t represents an integer of 1 to 10.

^M1 each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent. ^M1 is the same as M in the general formula (A2-1).

A each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group having an aromatic ring which may have a substituent. The alkylene group in A may be any of a chain, a branched chain, and a ring, and preferably a ring, that is, a ring, having 5 or more carbon atoms which may have a substituent. The number of carbon atoms in the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. Examples of such alkylene groups include groups having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

Examples of the aromatic ring in the divalent group having the aromatic ring represented by A include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, and an aromatic heterocyclic ring, and a benzene ring, a phthalimide ring, and a pyromellitic acid diimide ring are preferred. That is, as the divalent group having an aromatic ring, a divalent group having a benzene ring which may have a substituent, a divalent group having a phthalimide ring which may have a substituent, and a divalent group having a pyromellitic acid diimide ring which may have a substituent are preferred. Examples of the divalent group having an aromatic ring include a group comprising a combination of a divalent group derived from phthalimide and an oxygen atom; a group comprising a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group comprising an alkylene group and a divalent group derived from pyromellitic acid diimide; a divalent group derived from pyromellitic acid diimide; a group comprising a combination of a divalent group derived from phthalimide and an alkylene group; etc. The above-mentioned arylene group and alkylene group are the same as the arylene group and alkylene group of the divalent linking group represented by L in the general formula (A2-1).

The divalent group having an alkylene group and an aromatic ring represented by A may have a substituent. The substituent is the same as the substituent represented by ^R1 in the above formula (2).

As specific examples of the group represented by A, the following groups can be cited. In the formula, "*" represents a bonding part.

The maleimide compound represented by the general formula (A2-2) is preferably any one of the maleimide compound represented by the following general formula (A2-2a) and the maleimide compound represented by the following general formula (A2-2b). In general formula (A2-2a), ^M2 and ^M3 each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent, ^R30 each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group consisting of two or more of these groups. t1 represents an integer of 1 to 10. In general formula (A2-2b), ^M4 , ^M6 and ^M7 each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent, and ^M5 each independently represents a divalent group having an aromatic ring which may have a substituent. ^R31 and ^R32 each independently represent an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

^M2 and ^M3 each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent. ^M2 and ^M3 are the same as the alkylene group having 5 or more carbon atoms represented by M in the general formula (A2-1), and preferably hexatriacontylene.

R ³⁰ each independently represents an oxygen atom, an arylene group, an alkylene group, or a group consisting of a combination of two or more divalent groups. The arylene group and the alkylene group are the same as the arylene group and the alkylene group of the divalent linking group represented by L in the general formula (A2-1). R ³⁰ is preferably a group consisting of a combination of two or more divalent groups or an oxygen atom.

As the group consisting of a combination of two or more divalent groups included in R ³⁰ , there can be mentioned a combination of an oxygen atom, an arylene group, and an alkylene group. As specific examples of the group consisting of a combination of two or more divalent groups, there can be mentioned the following groups. In the formula, "*" represents a bonding part.

^M4 , ^M6 and ^M7 each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent. ^M4 , ^M6 and ^M7 are the same as the alkylene group having 5 or more carbon atoms which may have a substituent represented by M in the general formula (A2-1), preferably hexylene, heptylene, octylene, nonylene, decylene, more preferably octylene.

M ⁵ each independently represents a divalent group having an aromatic ring which may have a substituent. M ⁵ is the same as the divalent group having an aromatic ring which may have a substituent represented by A in the general formula (A2-2), preferably a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group, and more preferably a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide. The above-mentioned arylene group and alkylene group are the same as the arylene group and alkylene group of the divalent linking group represented by L in the general formula (A2-1).

As specific examples of the group represented by M ⁵ , the following groups can be cited. In the formula, "*" represents a bonding part.

R ³¹ and R ³² each independently represent an alkyl group having at least 5 carbon atoms. R ³¹ and R ³² are the same as the above-mentioned alkyl group having at least 5 carbon atoms, preferably hexyl, heptyl, octyl, nonyl, decyl, more preferably hexyl or octyl.

u1 and u2 represent integers from 1 to 15, preferably from 1 to 10, respectively.

As specific examples of the second maleimide compound, the following compounds (A2-2c), (A2-2d), and (A2-2e) can be cited. However, the second maleimide compound is not limited to these specific examples. In the formula, v represents an integer of 1 to 10.

Specific examples of the second maleimide compound include "BMI-1500" (compound of formula (A2-2c)), "BMI-1700" (compound of formula (A2-2d)), and "BMI-689" (compound of formula (A2-2e)) manufactured by Designer Molecules. From the viewpoint of more significantly achieving the effect of the present invention, it is preferred to use a compound of formula (A2-2c) as the second maleimide compound.

The third example of the component (A) is a maleimide compound that does not belong to the first maleimide compound and the second maleimide compound (hereinafter, also referred to as the "third maleimide compound"). That is, the third maleimide compound does not have a biphenyl structure and does not contain any of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms. As the third maleimide compound, for example, there can be listed maleimide compounds having a substituted or unsubstituted aromatic hydrocarbon group (for example, N-phenylmaleimide compounds, maleimide compounds represented by the following formula (A3-1)), and maleimide compounds containing any of an alkyl group having 4 or less carbon atoms and an alkylene group having 4 or less carbon atoms (for example, N-methylmaleimide).

(Wherein, S ² represents 1 or 2)

The maleimide group equivalent of the component (A) is preferably 50 g/eq. to 2000 g/eq., more preferably 100 g/eq. to 1000 g/eq., and even more preferably 150 g/eq. to 500 g/eq., from the viewpoint of significantly obtaining the expected effect of the present invention. The maleimide group equivalent is the mass of the maleimide compound containing 1 equivalent of maleimide groups.

From the viewpoint of obtaining a cured product with a small dielectric tangent value, the content of component (A) is preferably 10% by mass or more, more preferably 20% by mass or more, preferably 40% by mass or less, and more preferably 35% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. In the present invention, the content of each component in the resin composition is a value when the non-volatile components in the resin composition are taken as 100% by mass, unless otherwise specified.

As component (A), at least one selected from the first maleimide compound, the second maleimide compound, and the third maleimide compound can be used, and at least one selected from the first maleimide compound and the second maleimide compound is preferably used. From the viewpoint of achieving better adhesion with the conductive material after the environmental resistance test and/or further improving brittleness, at least the first maleimide compound is preferably used as component (A).

<(B) Allyl-containing benzoxazine compound> The resin composition contains an allyl-containing benzoxazine compound as component (B). The so-called allyl-containing benzoxazine compound refers to a benzoxazine compound containing a substituted or unsubstituted allyl group. The so-called benzoxazine compound refers to a compound having a benzoxazine ring described below. The allyl-containing benzoxazine compound can be used as a hardener for thermally hardening the resin composition due to the reactivity of the allyl group and the reactivity of the benzoxazine ring. By including component (B) in the resin composition, a hardened material having excellent adhesion to a conductive material after an environmental resistance test can be obtained. Furthermore, by including the component (B) together with the component (C) described later in the resin composition, a hardened material having improved brittleness and excellent adhesion to the conductive material after environmental resistance testing can be obtained. The component (B) may be used alone or in combination of two or more.

The component (B) contains a benzoxazine ring in at least one molecule. The benzoxazine ring may be substituted with any substituent as long as the ring-opening reaction of the benzoxazine ring is not excessively hindered. In addition, a part of the double bond contained in the benzoxazine ring may be hydrogenated. Among the benzoxazine rings, there are, for example, 1,2-benzoxazine rings and 1,3-benzoxazine rings. Among them, from the perspective of obtaining the expected effect of the present invention, 3,4-dihydro-2H-1,3-benzoxazine ring (structure shown in the following formula (5)) is preferred. In the structure shown in the following formula (5), among the three bonding parts of the nitrogen atom, one bonding part that is not bonded to other atoms means a single bond.

The number of benzoxazine rings per molecule of component (B) is 1 or more, preferably 2 or more, from the viewpoint of obtaining excellent adhesion and/or improved brittleness. The upper limit is not limited, but may be 10 or less, 6 or less, 4 or less, or 3 or less.

Furthermore, component (B) contains a substituted or unsubstituted allyl group in at least one molecule. The unsubstituted allyl group is 2-propenyl. The allyl group may have any substituent as long as its reactivity is not excessively hindered. An example of a substituted allyl group is 2-methylallyl. The number of allyl groups per molecule of component (B) is preferably the same as or greater than the number of benzoxazine rings per molecule of component (B) from the viewpoint of obtaining excellent adhesion and/or improved brittleness, preferably more than 2, more preferably more than 4, and although the upper limit is not limited, it may be 20 or less, 12 or less, 8 or less, or 6 or less.

In the component (B), the allyl group is preferably bonded to any one of a nitrogen atom constituting the benzoxazine ring and a carbon atom constituting the benzoxazine ring, and more preferably bonded to a carbon atom constituting the benzoxazine ring, from the viewpoint of significantly obtaining the expected effect of the present invention.

The first example of the component (B) is a first allyl group-containing benzoxazine compound represented by the following formula (B1-1). In formula (B1-1), R ²⁰ and R ²¹ each independently represent a substituted or unsubstituted allyl group, R ²² represents a q-valent group, q represents an integer of 1 to 10, p1 each independently represents an integer of 0 to 4, and p2 each independently represents an integer of 0 to 2.

The q-valent group represented by R ²² is preferably a q-valent group selected from the group consisting of a substituted or unsubstituted allyl group, a q-valent aromatic hydrocarbon group, a q-valent aliphatic hydrocarbon group, an oxygen atom, and a combination thereof. At least one of the hydrogen atoms possessed by the q-valent aromatic hydrocarbon group and the q-valent aliphatic hydrocarbon group may be substituted by a halogen atom. When R ²² is a substituted or unsubstituted allyl group, q=1, in which case both p1 and p2 may be 0. When R ²² is a substituted or unsubstituted allyl group, the allyl group may be a substituent of any of the q-valent aromatic hydrocarbon group and the q-valent aliphatic hydrocarbon group. For example, when q is 2, ^R22 is preferably a group comprising an arylene group, an alkylene group, an oxygen atom or a combination of two or more of these divalent groups, more preferably a group comprising an arylene group or a combination of two or more divalent groups, and even more preferably a group comprising a combination of two or more divalent groups.

The arylene group in R ²² is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and still more preferably an arylene group having 6 to 12 carbon atoms. Specific examples of the arylene group include phenylene, naphthylene, anthracenyl, biphenylene, etc., and phenylene is preferred.

The alkylene group in R ²² is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples of the alkylene group include methylene, ethylene, and propylene, and methylene is preferred.

Examples of the group consisting of a combination of two or more divalent groups included in ^R22 include a group bonding to one or more arylene groups and one or more oxygen atoms; a group bonding to one or more arylene groups and one or more alkylene groups, such as a group having an arylene-alkylene-arylene structure; a group bonding to one or more alkylene groups and one or more oxygen atoms; a group bonding to one or more arylene groups, one or more alkylene groups, and one or more oxygen atoms; and the like, preferably a group bonding to one or more arylene groups and one or more oxygen atoms, and a group bonding to one or more arylene groups and one or more alkylene groups.

q represents an integer from 1 to 10, preferably represents an integer from 1 to 4, more preferably represents an integer from 1 to 3, and even more preferably represents 1 or 2.

p1 represents an integer of 0 to 4 independently, preferably represents an integer of 0 to 2, more preferably represents 0 or 1, and even more preferably represents 1. p2 represents an integer of 0 to 2 independently, represents 0 or 1, and is preferably 0.

From the viewpoint of obtaining the expected effects of the present invention, the benzoxazine compound represented by the general formula (B1-1) is preferably an allyl group-containing benzoxazine compound represented by the following general formula (B1-1a).

In formula (B1-1a), R ²⁰ , R ²¹ and R ²³ each independently represent a substituted or unsubstituted allyl group, p1' each independently represents an integer of 0 to 4, p2' each independently represents an integer of 0 to 2, and p3' each independently represents an integer of 0 to 4. However, at least one of the plurality of p1', p2', and p3' represents an integer greater than 1.

The allyl group-containing benzoxazine compound represented by general formula (B1-1a) is preferably a benzoxazine compound represented by formula (B1-1b).

In formula (B1-1b), R ²⁰ , R ²¹ , p1′ and p2′ are the same as R ²⁰ , R ²¹ , p1′ and p2′ in formula (B1-1a), respectively.

The first allyl group-containing benzoxazine compound can be a commercial product. Examples of commercial products include "ALP-d" manufactured by Shikoku Chemical Industries, Ltd. (an allyl group-containing P-d type benzoxazine compound having the structure of the above formula (B1-1a)). In addition, the first allyl group-containing benzoxazine compound can be a benzoxazine compound disclosed in Japanese Patent Application Publication No. 2016-074871 or a derivative thereof. In addition, the first allyl group-containing benzoxazine compound can be produced according to the method described in Japanese Patent Application Publication No. 2016-074871.

The second example of the component (B) is a second allyl group-containing benzoxazine compound represented by the following formula (B2-1). In formula (B2-1), R ^20a , R ^21a and R ^22a each independently represent a substituted or unsubstituted allyl group, R ^22′ represents a q′-valent group bonded to a carbon atom possessed by the benzoxazine ring. q′ represents an integer of 1 to 10, p1a each independently represents an integer of 0 to 4, and p2a each independently represents an integer of 0 to 2. For each benzoxazine ring bonded to R ^22′ , the maximum value of the sum of p1a and p2a is 5.

It is preferred that at least one of R ^20a , R ^21a and R ^22a is a substituted or unsubstituted allyl group. When all of R ^20a , R ^21a and R ^22a are not substituted or unsubstituted allyl groups, R ^22′ has at least one substituted or unsubstituted allyl group.

The q'-valent group represented by R ^22' is preferably a q'-valent aromatic hydrocarbon group, a q'-valent aliphatic hydrocarbon group, a q'-valent group selected from the group consisting of an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, and a combination thereof. At least one of the hydrogen atoms possessed by the q'-valent aromatic hydrocarbon group and the q'-valent aliphatic hydrocarbon group may be substituted by a halogen atom or a substituted or unsubstituted allyl group. For example, when q' is 2, R ^22' is preferably a group selected from the group consisting of an aryl group, an alkylene group, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, and a combination of two or more of these divalent groups.

The arylene group in R ^22' is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and still more preferably an arylene group having 6 to 12 carbon atoms. Specific examples of the arylene group include phenylene, naphthylene, anthracenylene, biphenylene, and the like, and phenylene is preferred.

The alkylene group in R ^22′ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples of the alkylene group include methylene, ethyl, and propyl groups, and methylene is preferred.

Examples of the group consisting of a combination of two or more divalent groups included in R ^22' include a group bonding to one or more arylene groups and one or more oxygen atoms; a group bonding to one or more arylene groups and one or more alkylene groups, such as a group having an arylene-alkylene-arylene structure; a group bonding to one or more alkylene groups and one or more oxygen atoms; a group bonding to one or more arylene groups, one or more alkylene groups, and one or more oxygen atoms; and the like, preferably a group bonding to one or more arylene groups and one or more oxygen atoms, and a group bonding to one or more arylene groups and one or more alkylene groups.

q' represents an integer of 1 to 10, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1 or 2. When q' is an integer of 2 or more, the q' benzoxazine rings and the substituents thereof bonded to R ^22' may be the same as or different from each other.

p1a each independently represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 1. p2a each independently represents an integer of 0 to 2, 0 or 1, and more preferably 0. However, for each benzoxazine ring bonded to R ^22' , the maximum value of the sum of p1a and p2a is 5.

The second allyl group-containing benzoxazine compound may be, for example, a benzoxazine compound disclosed in Japanese Unexamined Patent Publication No. 2016-074871 or a derivative thereof. The second allyl group-containing benzoxazine compound may be produced according to the method described in Japanese Unexamined Patent Publication No. 2016-074871.

The third example of the component (B) is a third allyl-containing benzoxazine compound that does not belong to the first allyl-containing benzoxazine compound and the second allyl-containing benzoxazine compound. Examples of the third allyl-containing benzoxazine compound include allyl-containing benzoxazine compounds that contain a 1,2-benzoxazine ring or a 1,4-benzoxazine ring and are capable of a ring-opening reaction.

The molecular weight of the component (B) is preferably 200 or more, more preferably 300 or more, and further preferably 400 or more, and is preferably 1000 or less, more preferably 800 or less, and further preferably 500 or less, from the viewpoint of improving adhesion.

The equivalent weight of the benzoxazine ring of the component (B) (hereinafter also referred to as "ring-opening reaction participating group equivalent weight") is preferably 100 g/eq. to 1000 g/eq., more preferably 150 g/eq. to 500 g/eq., and even more preferably 200 g/eq. to 300 g/eq., from the viewpoint of significantly obtaining the expected effect of the present invention. The ring-opening reaction participating group equivalent weight is the mass of the allylmaleimide compound including 1 equivalent of the ring-opening reaction participating group (benzoxazine ring).

From the viewpoint of significantly obtaining the expected effect of the present invention, the allyl equivalent of the component (B) is preferably 100 g/eq. to 1000 g/eq., more preferably 150 g/eq. to 500 g/eq., and even more preferably 200 g/eq. to 300 g/eq. The allyl equivalent is the mass of the allylmaleimide compound containing 1 equivalent of allyl groups.

When the non-volatile components in the resin composition are set to 100 mass%, the content of component (B) is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, and even more preferably 0.03 mass% or more. The upper limit is preferably 15 mass% or less, more preferably 10 mass% or less, and even more preferably 7 mass% or less or 5 mass% or less. By setting the content of component (B) within this range, the performance of the cured product, especially the adhesion between the cured product and the conductive layer, can be improved. In addition, the content of component (B) is preferably set in accordance with the maleimide group equivalent of component (A), the ring-opening reaction participating group equivalent and the allyl group equivalent of component (B).

In the resin composition, the mass ratio of the component (B) to the component (A) [component (B)/component (A)] is preferably 0.01 or more, more preferably 0.02 or more, from the viewpoint of exerting the expected effect of the present invention, and is preferably 0.20 or less, more preferably 0.19 or less, from the viewpoint of suppressing excessive crosslinking reaction and improving adhesion. In addition, the mass ratio of the component (B) to the component (A) [component (B)/component (A)] is preferably set according to the maleimide group equivalent of the component (A), the ring-opening reaction participating group equivalent and the allyl group equivalent of the component (B).

<(C) High molecular weight component> The resin composition contains a high molecular weight component as the (C) component. By including the (C) component in the resin composition, the stress of the resin composition is relieved, and as a result, a hardened material having improved brittleness while maintaining a smaller value of the dielectric tangent of the hardened material obtained by the (A) component can be obtained. In addition, by including the (C) component together with the (B) component in the resin composition, a hardened material having improved brittleness and better adhesion to the conductive material after the environmental resistance test can be obtained. The (C) component can be used alone or in combination of two or more.

As the component (C), a component having a high weight average molecular weight or a high number average molecular weight can be used. Examples of such components include thermoplastic resins such as polyimide resins, polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyamide imide resins, polyether imide resins, polysulfide resins, polyethersulfide resins, polyphenylene ether resins, polyetheretherketone resins, polystyrene resins, and polyester resins. Among them, as the component (C), from the viewpoint of obtaining a cured product that more significantly exhibits the expected effect of the present invention, it is preferably at least one selected from polyimide resins, polycarbonate resins, and phenoxy resins.

The polyimide resin may be a resin having an imide structure. Generally, the polyimide resin includes a resin obtained by an imidization reaction of a diamine compound and an acid anhydride.

The diamine compound used for preparing the polyimide resin is not particularly limited, but examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

Examples of the aliphatic diamine compound include linear aliphatic diamine compounds such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1,5-diaminopentane, and 1,10-diaminodecane; 1,2-diamino-2-methylpropane, 2,3-diamino-2 ,3-butane, and 2-methyl-1,5-diaminopentane; aliphatic cyclic diamine compounds such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine); dimer acid type diamine (hereinafter also referred to as "dimer diamine"), etc. The so-called dimer acid type diamine refers to a diamine compound obtained by replacing the two terminal carboxylic acid groups (-COOH) of the dimer acid with aminomethyl (-CH ₂ -NH ₂ ) or amino (-NH ₂ ). Dimer acid is a compound obtained by dimerizing unsaturated fatty acids (preferably those with 11 to 22 carbon atoms, particularly preferably those with 18 carbon atoms), and its industrial production process is also well known.

Examples of the aromatic diamine compound include phenylenediamine compounds, naphthalenediamine compounds, and diphenylamine compounds.

The so-called phenylenediamine compound refers to a compound comprising a benzene ring having two amino groups, and the benzene ring may have 1 to 3 substituents. The substituents are not particularly limited. Specifically, phenylenediamine compounds include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobiphenyl, and 2,4,5,6-tetrafluoro-1,3-phenylenediamine.

The so-called naphthalene diamine compound refers to a compound comprising a naphthalene ring having two amino groups, and the naphthalene ring may have 1 to 3 substituents. The substituents are not particularly limited. Specific examples of the naphthalene diamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene.

The so-called diphenylamine compound refers to a compound containing two aniline structures in the molecule, and further, the two benzene rings in the two aniline structures may further have 1 to 3 substituents. The substituents herein are not particularly limited. The two aniline structures in the diphenylamine compound may be bonded by direct bonding and/or by 1 or 2 linking structures having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. The diphenylamine compound also includes two aniline structures bonded by two bonds.

Specifically, the "linked structure" of the diphenylamine compound includes -NHCO-, -CONH-, -OCO-, -COO-, -CH ₂ -, -CH 2 CH 2 _- , -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH _{2 CH 2 CH 2} -, -CH ₂ CH ₂ CH _{2 CH 2} -, -CH(CH ₃ )-, -C( _{CH 3 ) 2} -, -C(CF ₃ ) ₂ -, -CH=CH-, -O-, -S-, -CO-, -SO ₂ -, -NH-, -Ph-, -Ph-Ph-, -C(CH ₃ ) ₂ -Ph-C(CH ₃ ) ₂ -, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO ₂ -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O-, -C(CH ₃ ) ₂ -Ph-C(CH ₃ ) ₂ -, and the like.

In the present specification, "Ph" represents 1,4-phenylene, 1,3-phenylene or 1,2-phenylene.

In one embodiment, the diphenylamine compound includes, specifically, 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate. , 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropyne (Propylidene))diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) phenyl] hexafluoropropane, α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluorene)diphenylamine, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl -4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane, etc.

As the diamine compound, a commercially available one may be used, or one synthesized by a known method may be used. The diamine compound may be used alone or in combination of two or more.

The acid anhydride used to prepare the polyimide resin is not particularly limited, but in a suitable embodiment, it is an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride include benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, anthracene tetracarboxylic dianhydride, and diphthalic dianhydride, and diphthalic dianhydride is preferred.

The so-called benzene tetracarboxylic dianhydride refers to a benzene dianhydride having four carboxyl groups, and the benzene ring may have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ³³ -R ³³ (same as defined in the following formula (6)). Specific examples of benzene tetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

Naphthalenetetracarboxylic dianhydride refers to naphthalene dianhydride having four carboxyl groups, and the naphthalene ring may have 1 to 3 substituents. The substituents are preferably selected from a halogen atom, a cyano group, and -X ³³ -R ³³ (same as defined in the following formula (6)). Specific examples of naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride.

The so-called anthracenetetracarboxylic dianhydride refers to an anthracene dianhydride having four carboxyl groups, and the anthracene ring may have 1 to 3 substituents. Here, the substituent is preferably selected from a halogen atom, a cyano group, and -X ³³ -R ³³ (same as defined in the following formula (6)). Specific examples of anthracenetetracarboxylic dianhydride include 2,3,6,7-anthracenetetracarboxylic dianhydride.

The so-called diphthalic anhydride refers to a compound containing two phthalic anhydrides in the molecule, and the two benzene rings in the two phthalic anhydrides may each have 1 to 3 substituents. Here, the substituents are preferably selected from halogen atoms, cyano groups and -X ³³ -R ³³ (same as the definition in the following formula (6)). The two phthalic anhydrides in the diphthalic anhydride may be bonded by a direct bond or by a linking structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.

As diphthalic dianhydride, for example, there can be mentioned a compound represented by formula (6),

[In formula (6), R ³¹ and R ³² each independently represent a halogen atom, a cyano group, a nitro group or -X ³³ -R ³³ , X ³³ each independently represents a single bond, -NR ^33' -, -O-, -S-, -CO-, -SO ₂ -, -NR ^33' CO-, -CONR ^33' -, -OCO- or -COO-, R ³³ each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R ^33' each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, Y represents a single bond or a link structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms, and n10 and m10 each independently represent an integer of 0 to 3].

Y is preferably a chain structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. n and m are preferably 0.

The "linked structure" of Y has 1 to 100 backbone atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. The "linked structure" is preferably a divalent group represented by -[A1-Ph] _a10 -A1-[Ph-A1] _b10 -[wherein A1 independently represents a single bond, -(substituted or unsubstituted alkylene)-, -O-, -S-, -CO-, -SO ₂ -, -CONH-, -NHCO-, -COO- or -OCO-, and a10 and b10 independently represent an integer of 0 to 2 (preferably 0 or 1)].

Specifically, the "linked structure" of Y includes _{-CH2- ,} -CH2CH2- _{, -CH2CH2CH2- ,} -CH2CH2CH2CH2- _, -CH2CH2CH2CH2- _, -CH2CH2CH2CH2CH2-, -CH( _CH3 ) _- , -C(CH3) _{2- ,} -O-, _{-CO-, -SO2-, -Ph-, -O-Ph-O-, -O- Ph - SO2 - Ph -} O-, -O-Ph-C( _CH3 ) ₂ -Ph-O-, and the like. In the present specification, "Ph" represents 1,4-phenylene, _1,3 -phenylene or _1,2 -phenylene.

Specific examples of diphthalic acid dianhydride include 4,4'-oxydiphthalic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, Acid dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfonate tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfonate dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethynylene (ethenylidene)-4,4'-diphthalic acid dianhydride, 2,2 -Propylidene-4,4'-diphthalic anhydride, 1,2-ethyl-4,4'-diphthalic anhydride, 1,3-trimethylene-4,4'-diphthalic anhydride, 1,4-tetramethylene-4,4'-diphthalic anhydride, 1,5-pentamethylene-4,4'-diphthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1, 4-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropyne (propylidene) diphenoxy) bis(diphthalic acid) dianhydride, etc.

Acid anhydrides may be commercially available or may be synthesized by a known method or a method in accordance therewith. Acid anhydrides may be used alone or in combination of two or more.

The polyimide resin may be a commercially available product. Examples of the commercially available products include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Chemical Co., Ltd.

Polycarbonate resin is a resin having a carbonate structure. Examples of such resins include carbonate resins without reactive groups, carbonate resins containing hydroxyl groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing acid anhydride groups, carbonate resins containing isocyanate groups, carbonate resins containing urethane groups, and carbonate resins containing epoxy groups. The reactive group here refers to a functional group that can react with other components such as hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, acid anhydride groups, isocyanate groups, urethane groups, and epoxy groups.

Commercially available carbonate resins may be used. Examples of commercially available products include "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemicals, and "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals.

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

Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by the company; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical Corporation; etc.

The polyamide imide resin is a resin having an amide imide structure. From the viewpoint of compatibility with other components in the resin composition, the polyamide imide resin preferably uses a polyamide imide resin having an alicyclic structure in the molecular structure, a polyamide imide resin having a siloxane structure as described in Japanese Patent Application Laid-Open No. 05-112760, a polyamide imide resin having a high-volume branched chain structure, a polyamide imide resin using an asymmetric monomer as a raw material, a polyamide imide resin having a multi-branched structure, and the like.

Among them, from the viewpoint of improving the compatibility and dispersibility of the resin varnish by having an isocyanuric acid ring structure in the polyamide imide resin, more preferred are (i) a polyamide imide resin having an isocyanuric acid ring structure in its molecular structure (i.e., a polyamide imide resin having an isocyanuric acid ring structure and an imide skeleton or an amide skeleton), (ii) a polyamide imide resin having an isocyanuric acid ring structure and an alicyclic structure in its molecular structure. (i) a polyamide-imide resin having a repeating unit comprising an isocyanuric acid ring structure and an alicyclic structure (i.e., a polyamide-imide resin having a repeating unit comprising an isocyanuric acid ring structure and an alicyclic structure and an imide skeleton or an amide skeleton); and (ii) a polyamide-imide resin having a repeating unit comprising an isocyanuric acid ring structure and an alicyclic structure (i.e., a polyamide-imide resin having a repeating unit comprising an isocyanuric acid ring structure and an alicyclic structure and an imide skeleton or an amide skeleton).

As a suitable embodiment of the polyamideimide resin of (i) to (iii), there can be cited (1) a compound obtained by reacting a polyisocyanate compound containing an isocyanuric acid ring derived from an alicyclic diisocyanate with an acid anhydride derived from a polycarboxylic acid having three or more carboxyl groups (e.g., a carboxylic dianhydride having one or more carboxyl groups), namely, a branched polyamideimide containing a carboxylic acid group (hereinafter, the compound may be referred to as "(compound)"); (C-1)")), (2) a compound obtained by reacting a compound having one epoxy group and one or more free radical polymerizable unsaturated groups with compound (C-1), i.e., a branched polymerizable polyamide imide containing a carboxylic acid group (hereinafter, sometimes referred to as "compound (C-2)"), or (3) a compound obtained by reacting a compound having one hydroxyl group and one or more free radical polymerizable unsaturated groups with a residual isocyanate group, i.e., a branched polymerizable polyamide imide containing a carboxylic acid group (hereinafter, sometimes referred to as "compound (C-3)"), etc.

Specific examples of the compound (C-1) include compounds represented by the following general formula (I): In general formula (I), the structural unit enclosed by parentheses is defined as a repeating unit (I-1). (In formula (I), w represents 0 to 15)

As compound (C-2), there can be cited compound (II) having a structure represented by the following formula (I-2) by adding GMA (glycidyl methacrylate) to the carboxyl group and/or the terminal carboxyl group of any part of the repeating unit (I-1) in the general formula (I). That is, compound (II) is a compound in which the carboxyl group of the compound represented by the general formula (I) is modified with GMA. Here, the so-called terminal carboxyl group means that in the general formula (I), there is a carboxyl group at a position not included in the repeating unit (I-1).

In formula (I-2), * represents a bonding part.

The structure represented by the above formula (I-2) is a group bonded to a structure in which a hydrogen atom is removed from any part of the carboxyl groups and/or the terminal carboxyl groups in the repeating units (I-1) of the general formula (I).

The ratio of GMA modification of carboxyl groups, i.e., the ratio of GMA addition relative to the molar number of carboxyl groups of compound (C-1), is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, further preferably 0.7 mol% or more or 0.9 mol% or more. The upper limit is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less or 20 mol% or less.

As compound (C-3), there can be cited compounds in the above formula (I) in which any part of the repeating unit (I-1) and/or the terminal imide group is an isocyanate group, and compounds (III) having a structure represented by the following formula (I-3) in which a hydroxyl group of pentaerythritol triacrylate is added to the isocyanate group. Here, the so-called terminal imide group means that in the general formula (I), there is an imide group at a position not included in the repeating unit (I-1). The compound in which any part and/or the terminal imide group is an isocyanate group is obtained by leaving an isocyanate group when obtaining a branched polyamide imide containing a carboxylic acid group of the general formula (1).

In formula (I-3), * represents a bonding part.

The structure represented by the above formula (I-3) forms a urethane bond by bonding with an isocyanate group.

The amount of pentaerythritol triacrylate added is preferably 40 mol% or less, more preferably 38 mol% or less, and even more preferably 35 mol% or less, relative to the number of mols of isocyanate groups of the polyisocyanate when inserted. On the other hand, the amount of pentaerythritol triacrylate added is preferably 0.3 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more relative to the number of mols of isocyanate groups of the polyisocyanate when inserted, from the viewpoint of fully obtaining the effect of addition.

The polyamide imide resin can be synthesized by various known methods. For the synthesis method of the polyamide imide resin, for example, reference can be made to paragraphs 0020 to 0030 of International Publication No. 2010/074197, and the contents are incorporated into this specification.

The polyamide imide resin may be a commercially available product. Examples of commercially available products include EPICLON (registered trademark) "V-8000" and "V-8001" manufactured by DIC Corporation, "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd., and "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd. (polyamide imide containing a polysiloxane skeleton) and other modified polyamide imides.

As the polystyrene resin, any resin containing a repeating unit (styrene unit) having a structure obtained by polymerizing styrene can be used. The polystyrene resin is preferably an elastomer. In addition, the polystyrene resin may be a copolymer containing any repeating unit different from the aforementioned styrene unit combined with the styrene unit, or may be a hydrogenated polystyrene resin.

As the arbitrary repeating unit, for example, there can be listed a repeating unit having a structure obtained by polymerizing a conjugated diene (conjugated diene unit), a repeating unit having a structure obtained by hydrogenating the same (hydrogenated conjugated diene unit), etc. As the conjugated diene, for example, there can be listed aliphatic conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, etc.; halogenated aliphatic conjugated dienes such as chloroprene, etc. As the conjugated diene, from the viewpoint of significantly obtaining the effect of the present invention, an aliphatic conjugated diene is preferred, and butadiene is more preferred. The conjugated diene may be used alone or in combination of two or more. Furthermore, the polystyrene resin may be a random copolymer or a block copolymer.

Examples of the polystyrene resin include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer, styrene-maleic anhydride copolymer, etc. Among them, styrene-maleic anhydride copolymer is preferred as the polystyrene resin.

Specific examples of polystyrene resins include "EF-40" manufactured by Cray Valley Corporation and "H1043" manufactured by Asahi Kasei Corporation.

From the viewpoint of compatibility with other components in the resin composition, the polyester resin preferably has a fluorene structure in its molecular structure, and preferably has a structural unit derived from a diol and a structural unit derived from a dicarboxylic acid in addition to the fluorene structure.

Specific examples of polyester resins include "OKP4HT" manufactured by Osaka Gas Chemicals Co., Ltd.

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

Examples of the polyvinyl acetal resin include polyvinyl formaldehyde resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include S-Lec BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Industries, Ltd.

Specific examples of polyether sulfide resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

The weight average molecular weight (Mw) of the component (C) is preferably 5000 or more, more preferably 8000 or more, particularly preferably 10000 or more, preferably 100000 or less, more preferably 80000 or less, and particularly preferably 50000 or less, from the viewpoint of obtaining a cured product that more significantly exhibits the intended effect of the present invention. The weight average molecular weight of the component (C) is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

From the viewpoint of reducing the melt viscosity of the resin composition, the number average molecular weight (Mn) of the component (C) is preferably 5,000 or more, more preferably 8,000 or more, particularly preferably 10,000 or more, preferably 100,000 or less, more preferably 80,000 or less, and particularly preferably 50,000 or less. The number average molecular weight can be measured according to the following <Determination of number average molecular weight>. In addition, the component (C) can be used as long as one of the weight average molecular weight and the number average molecular weight is within the above range. For example, when the molecular weight of the component (C) is generally operated as the weight average molecular weight, the number average molecular weight does not need to be within the above range. Similarly, when the molecular weight of the component (C) is generally operated as the number average molecular weight, the weight average molecular weight does not need to be within the above range.

<Determination of number average molecular weight> 100 mg of component (C) and 5 g of dispersant ("N-methylpyrrolidone" manufactured by Kanto Chemical Co., Ltd.) were weighed in a small bottle and dispersed by ultrasonic for 20 minutes. Then, the mixture was filtered using a membrane filter ("ADVANTEC" manufactured by Toyo Filter Paper Co., Ltd., cutoff 0.5 μm), and the number average molecular weight (Mn) was calculated using a gel permeation chromatography measuring apparatus ("Shodex GPC-101" manufactured by Shoko Scientific Co., Ltd.).

From the viewpoint of obtaining a cured product that exhibits the intended effect of the present invention, the content of the component (C) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more, and is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

When the content of the nonvolatile components in the resin composition of the component (C) is taken as 100 mass %, and the content of the nonvolatile components in the resin composition of the component (A) is taken as a1, a1/c1 is preferably 2 or more, more preferably 5 or more, and further preferably 10 or more, and preferably 50 or less, more preferably 40 or less, and further preferably 30 or less. By setting a1/c1 within this range, the effect of the present invention can be significantly obtained.

<(D) Inorganic filler> In addition to the above-mentioned components, the resin composition may further contain an inorganic filler as the (D) component as an optional component.

As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silicon dioxide is particularly suitable. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. In addition, spherical silicon dioxide is preferred as silicon dioxide. (D) The inorganic filler may be used alone or in combination of two or more.

Examples of commercially available products of the component (D) include "UFP-30" manufactured by Electrochemical Corporation; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs; "SYLFIL NSS-3N", "SYLFIL NSS-4N", and "SYLFIL NSS-5N" manufactured by Tokuyama Corporation; and "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs.

From the viewpoint of improving moisture resistance and dispersibility, component (D) is preferably treated with a surface treatment agent. Examples of surface treatment agents include amine coupling agents, (meth) acrylic coupling agents, and vinyl coupling agents. Among them, the use of amine coupling agents and (meth) acrylic coupling agents is preferred from the viewpoint of obtaining a cured product having excellent environmental test resistance (HAST resistance). Here, the amine coupling agent refers to a coupling agent having an amino group. The (meth) acrylic coupling agent refers to a coupling agent having a methacryloyloxy group or an acryloxy group. The vinyl coupling agent refers to a coupling agent having a vinyl group, and is not a (meth) acrylic coupling agent. Each of the above-mentioned amine coupling agents, (meth) acrylic coupling agents and vinyl coupling agents may include silane coupling agents, alkoxysilanes, organic silazane compounds, titanium ester coupling agents, etc., and may also belong to any type of silane coupling agents. As silane coupling agents, for example, fluorine-containing silane coupling agents, epoxysilane coupling agents, and butylsilane coupling agents may be listed. Among them, from the viewpoint of significantly obtaining the effect of the present invention, silane coupling agents are preferred, and amine coupling agents belonging to silane coupling agents and (meth) acrylic coupling agents belonging to silane coupling agents are more preferred. Furthermore, the surface treatment agent may be used alone or in combination of two or more.

Examples of commercially available surface treatment agents include "KBM1003" (vinyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM503" (3-methacryloyloxypropyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidyloxypropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-butyl propyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBE903" (3-amine "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc. Among them, it is preferred to use at least one selected from "KBM503" belonging to the (meth)acryloxy-based coupling agent and "KBM573" and "KBE903" belonging to the amine-based coupling agent, and it is more preferred to use at least one of "KBM503" and "KBM573".

The degree of surface treatment by the surface treatment agent is preferably within a specified range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by weight of the inorganic filler is preferably surface treated with 0.2 to 5 parts by weight of the surface treatment agent, preferably 0.2 to 3 parts by weight, and preferably 0.3 to 2 parts by weight.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/ ^m2 or more, more preferably 0.1 mg/ ^m2 or more, and even more preferably 0.2 mg/ ^m2 or more. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity of the sheet form, it is preferably 1 mg/ ^m2 or less, more preferably 0.8 mg/ ^m2 or less, and even more preferably 0.5 mg/ ^m2 or less.

The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, as a solvent, a sufficient amount of MEK is added to the inorganic filler treated with a surface treatment agent, and then ultrasonically washed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, the "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The specific surface area of the component (D) is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly preferably 3 m ² /g or more. The upper limit is not particularly limited, but is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method and calculating the specific surface area using the BET multipoint method.

From the viewpoint of remarkably obtaining the expected effect of the present invention, the average particle size of the component (D) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

The average particle size of component (D) can be measured by laser diffraction and scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by using a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be set as the average particle size for measurement. The measurement sample can be 100 mg of inorganic filler and 10 g of methyl ethyl ketone weighed in a small bottle, and dispersed by ultrasound for 10 minutes. The measurement sample is used in a laser diffraction type particle size distribution measuring device, and the wavelength of the light source used is set to blue and red. The volume-based particle size distribution of component (D) is measured by the flow cell method, and the average particle size can be calculated from the obtained particle size distribution as the median diameter. As a laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba, Ltd. can be cited.

From the viewpoint of reducing the value of dielectric tangent, when the non-volatile components in the resin composition are defined as 100 mass %, the content of the component (D) is preferably 50 mass % or more, more preferably 55 mass % or more, and even more preferably 60 mass % or more. The upper limit is not limited as long as dispersibility can be ensured, but for example, it can be 95 mass % or less, 90 mass % or less, 85 mass % or less, or 80 mass % or less.

<(E) Polymerization initiator> In addition to the above-mentioned components, the resin composition may further contain a polymerization initiator as the (E) component as an optional component. The (E) component may be used alone or in combination of two or more.

Examples of the component (E) include peroxides such as t-butyl cumyl peroxide, t-butyl peroxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butyl peroxylaurate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, and di-t-hexylperoxide.

Examples of commercially available products of the component (E) include "PERBUTYL (registered trademark) C", "PERBUTYL (registered trademark) A", "PERBUTYL (registered trademark) P", "PERBUTYL (registered trademark) L", "PERBUTYL (registered trademark) O", "PERBUTYL (registered trademark) ND", "PERBUTYL (registered trademark) Z", "PERBUTYL (registered trademark) I", "PERCUMYL P", "PERCUMYL D", "PERHEXYL (registered trademark) D", "PERHEXYL (registered trademark) A", "PERHEXYL (registered trademark) I", "PERHEXYL (registered trademark) Z", "PERHEXYL (registered trademark) ND", "PERHEXYL (registered trademark) O", "PERHEXYL (registered trademark) PV", "PERHEXYL (registered trademark) O", etc.

From the viewpoint of significantly obtaining the expected effects of the present invention, when the non-volatile components in the resin composition are taken as 100 mass %, the content of the component (E) is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, further preferably 0.1 mass % or more, and preferably 1 mass % or less, more preferably 0.5 mass % or less, and further preferably 0.3 mass % or less.

<(F) Thermosetting resin> In addition to the above-mentioned components, the resin composition may further contain a thermosetting resin as the (F) component as an arbitrary component. However, the (F) component excludes any component equivalent to the (A) component, the (B) component, and the (C) component. The so-called thermosetting resin refers to a resin that can be cured by heat. Here, the thermosetting compound includes a compound that can be polymerized by heat curing, a compound that is reactive with a component contained in the resin composition of the present invention, and a compound that can react with a component contained in the resin composition of the present invention due to the reactivity of the component.

The first example of the component (F) is an epoxy resin. Examples of the epoxy resin include bixylenol epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, phenol epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-ophthalic acid epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, etc. Resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, oxalic acid type epoxy resin, oxalic acid dimethanol type epoxy resin, naphthyl ether type epoxy resin, trihydroxymethyl type epoxy resin, tetraphenylethane type epoxy resin, etc. The epoxy resin may be used alone or in combination of two or more types.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as an epoxy resin. From the viewpoint of significantly obtaining the intended effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more relative to 100% by mass of the nonvolatile component of the component (F).

Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin as the (F) component, or only a solid epoxy resin. Although it may contain a combination of a liquid epoxy resin and a solid epoxy resin, it is preferred to contain only a liquid epoxy resin from the viewpoint of significantly obtaining the intended effect of the present invention.

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

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure are preferred, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-based epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "EPIKOTE" manufactured by Mitsubishi Chemical Corporation; "828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation; Nagase "EX-721" (glycidyl ester type epoxy resin) manufactured by ChemteX; "Celloxide2021P" (lipidic epoxy resin with ester skeleton) manufactured by Daicel; "PB-3600" (epoxy resin with butadiene structure) manufactured by Daicel; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemicals Co., Ltd. These can be used alone or in combination of two or more types.

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

As the solid epoxy resin, preferred are bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin, and more preferred is naphthalene type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-based epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-based tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac-based epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac-based epoxy resin) manufactured by DIC Corporation; and "HP-4710" (naphthalene-based tetrafunctional epoxy resin) manufactured by DIC Corporation. "HP-7200HH", "HP-7200H", "HP-7200" (dicyclopentadiene epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether epoxy resin) manufactured by Nippon Kayaku Co., Ltd. N-502H" (phenol type epoxy resin); "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; "ESN485" (naphthol novolac type epoxy resin) manufactured by Osaka Gas; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical; "PG-100" and "CG-500" manufactured by Chemicals; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical, etc. These can be used alone or in combination of two or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as epoxy resin, the mass ratio of the liquid epoxy resin: solid epoxy resin is preferably 1:1 to 1:20, more preferably 1:1.5 to 1:15, and particularly preferably 1:2 to 1:10. By setting the mass ratio of the liquid epoxy resin to the solid epoxy resin within this range, the expected effect of the present invention can be significantly obtained. Furthermore, when it is usually used in the form of a resin sheet, it can bring about moderate adhesion. In addition, when it is usually used in the form of a resin sheet, it can obtain sufficient flexibility and improve operability. Furthermore, a cured product with sufficient breaking strength can usually be obtained.

The epoxy equivalent of the epoxy resin is preferably 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., still more preferably 80 g/eq. to 2000 g/eq., and still more preferably 110 g/eq. to 1000 g/eq.. By being within this range, the crosslinking density of the cured product of the resin composition becomes sufficient, and an insulating layer with a small surface roughness can be provided. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin is preferably 100 or more and less than 5000, more preferably 250 or more and less than 3000, and even more preferably 400 or more and less than 1500, from the viewpoint of significantly obtaining the expected effect of the present invention. The weight average molecular weight of the component (F) can be measured by the same method as that of the component (C).

From the viewpoint of significantly obtaining the expected effects of the present invention, when the non-volatile components in the resin composition are taken as 100 mass %, the content of the epoxy resin is preferably 0.1 mass % or more, more preferably 0.3 mass % or more, further preferably 0.5 mass % or more, preferably 5 mass % or less, more preferably 4 mass % or less, and further preferably 3 mass % or less.

The second example of the component (F) is a resin other than an epoxy resin. As an example of a resin other than an epoxy resin, there can be cited a resin having a weight average molecular weight or a number average molecular weight smaller than the resin that can be used as the high molecular weight component listed as the component (C) (also referred to as a "low molecular weight resin" for convenience). As an example of a low molecular weight resin, there can be cited a polyphenylene ether resin. As a specific example of a polyphenylene ether resin, there can be cited an oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd.

The third example of component (F) is a hardener other than component (B), that is, a second hardener that can be used together with component (B).

Examples of the second hardener include active ester hardeners, phenol hardeners, naphthol hardeners, allyl-free benzoxazine hardeners, cyanate hardeners, carbodiimide hardeners, amine hardeners, and acid anhydride hardeners. The second hardener may be used alone or in combination of two or more.

As the active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester curing agent, a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds, is preferred. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, diphthalic 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, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, o-cresol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phenoxytriol, benzenetriol, dicyclopentadiene-type diphenolic compounds, and phenol novolac. Here, the so-called "dicyclopentadiene-type diphenolic compound" refers to a diphenolic compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Preferred specific examples of active ester hardeners include active ester hardeners containing a dicyclopentadiene diphenol structure, active ester hardeners containing a naphthalene structure, active ester hardeners containing acetylated phenol novolacs, and active ester hardeners containing benzoylated phenol novolacs. Among them, active ester hardeners containing a naphthalene structure and active ester hardeners containing a dicyclopentadiene diphenol structure are more preferred. The so-called "dicyclopentadiene diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

As commercially available active ester hardeners, as active ester hardeners containing a dicyclopentadiene-type diphenol structure, there are "EXB9451", "EXB9460", "EXB9460S", "HPC8000-65T", "HPC8000H-65TM", "EXB8000L-65TM", "EXB8150-65T" (manufactured by DIC Corporation); as active ester hardeners containing a naphthalene structure, there is "EXB9416-70BK" (manufactured by DIC Corporation); as active ester hardeners containing acetylated phenol novolacs ... Examples of active ester hardeners include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester hardeners including benzoyl compounds of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); examples of active ester hardeners for acetylated phenol novolacs include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester hardeners for benzoyl compounds of phenol novolacs include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

As phenolic hardeners and naphthol hardeners, those having a phenolic structure are preferred from the viewpoint of heat resistance and water resistance. Furthermore, from the viewpoint of adhesion to the conductive layer, nitrogen-containing phenolic hardeners are preferred, and phenolic hardeners containing a triazine skeleton are more preferred.

Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Wa Kasei Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", and "SN375" manufactured by Nippon Steel & Sumitomo Chemicals Co., Ltd.; and "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", and "EXB-9500" manufactured by DIC Corporation.

Specific examples of the benzoxazine-based curing agent not containing an allyl group (i.e., a benzoxazine compound other than the component (B)) include "ODA-BOZ" manufactured by JFE Chemicals, and "P-d" and "F-a" manufactured by Shikoku Chemicals.

Examples of cyanate curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, 4,4'-methylenebis(2,6-dimethylphenylcyanate), hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, and bis(4-cyanatephenyl)sulfide; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; prepolymers of these cyanate resins partially triazine-treated; and the like.

Specific examples of cyanate-based curing agents include "PT60" (phenol novolac type multifunctional cyanate resin), "ULL-950S" (multifunctional cyanate resin), "BA230", and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is converted into a trimer through triazine) manufactured by Lonza Japan.

Specific examples of carbodiimide-based hardeners include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

As the amine-based hardener, there can be cited those having one or more amine groups in one molecule, for example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred from the viewpoint of exerting the intended effect of the present invention. The amine-based hardener is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-diaminodiphenylmethane, diphenyldiaminosulfonate, 4,4'-diaminodiphenylsulfonate, 3,3'-diaminodiphenylsulfonate, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3-dimethyl-5,5-diethyl-4,4 -diphenylmethanediamine, 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)sulfonate, bis(4-(3-aminophenoxy)phenyl)sulfonate, etc. Amine-based hardeners can be commercially available products, for example, "KAYABOND C-100" manufactured by Nippon Kayaku Co., Ltd., etc.

Examples of the acid anhydride curing agent include those having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadicarboxylic anhydride, hydrogenated methylnadicarboxylic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenylmethanedicarboxylic anhydride, and the like. Ketonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonatetetracarboxylic 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(dehydrated trimellitate), copolymerized styrene and maleic acid, styrene-maleic acid resin, and other polymer-type acid anhydrides.

From the viewpoint of remarkably obtaining the expected effect of the present invention, the content of the second hardener is preferably 0.1 mass % or more, more preferably 0.3 mass % or more, further preferably 0.5 mass % or more, and preferably 5 mass % or less, more preferably 4 mass % or less, and further preferably 3 mass % or less, based on 100 mass % of the non-volatile components in the resin composition.

From the viewpoint of significantly obtaining the expected effects of the present invention, when the non-volatile components in the resin composition are taken as 100 mass %, the content of the component (F) is preferably 0.1 mass % or more, more preferably 0.3 mass % or more, further preferably 0.5 mass % or more, preferably 15 mass % or less, more preferably 13 mass % or less, and particularly preferably 10 mass % or less.

＜(G) Other additives＞ In addition to the above-mentioned components, the resin composition may further contain other additives as arbitrary components. Examples of such additives include thickeners, defoamers, leveling agents, adhesion-imparting agents, and resin additives, hardening accelerators, etc. These additives may be used alone or in combination of two or more. The individual contents may be appropriately set by those with common knowledge in the field of the present invention.

Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Component (F) may be used alone or in combination of two or more.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, among which triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

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

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

As the imidazole-based hardening accelerator, a commercially available product can be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation can be mentioned.

Examples of the guanidine-based hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triaza[4.4.0]dec-5-ene, 7-methyl-1,5,7-triaza[4.4.0] Dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, etc., preferably dicyanamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Examples of metal hardening accelerators include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organic metal complexes include organic cobalt complexes such as cobalt (II) acetylacetate and cobalt (III) acetylacetate, organic copper complexes such as copper (II) acetylacetate, organic zinc complexes such as zinc (II) acetylacetate, organic iron complexes such as iron (III) acetylacetate, organic nickel complexes such as nickel (II) acetylacetate, and organic manganese complexes such as manganese (II) acetylacetate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc cycloalkanoate, cobalt cycloalkanoate, tin stearate, zinc stearate, and the like.

<Preparation method of resin composition> The preparation method of the resin composition of the present invention is not particularly limited, and examples thereof include a method of adding a solvent to the blending components as necessary, and mixing and dispersing the components using a rotary mixer. The resin composition can be obtained as a resin varnish, for example, by including a solvent.

<Physical properties and uses of resin composition> The resin composition comprises (A) a maleimide compound, (B) an allyl group-containing benzoxazine compound and (C) a high molecular weight component. By using these components in combination, a hardened material having a small dielectric tangent value, excellent adhesion to conductive materials after environmental resistance tests and improved brittleness can be obtained. Although all of the above has been mentioned above, in general, the hardened material of the resin composition containing the maleimide compound has a small dielectric tangent value. However, since the maleimide compound generally has a high softening point, the hardened material of the resin composition containing the maleimide compound tends to be brittle. In addition, the cured product of the resin composition containing the maleimide compound tends to have poor adhesion after environmental resistance tests, especially after HAST (Highly Accelerated Temperature and Humidity Stress Test). However, by containing (B) an allyl group-containing benzoxazine compound and (C) a high molecular weight component relative to the resin composition containing (A), as demonstrated in the examples, by containing (A) component, the dielectric tangent obtained is kept at a smaller value, and excellent adhesion to the conductive material after the environmental resistance test and improved brittleness of the cured product can be obtained. This is speculated to be due to the presence of component (B) in the resin composition, which contains an allyl group and a benzoxazine ring that can react with component (A) in the same molecule, and a cross-linked structure can be formed in a state where component (C) is embedded. As a result, the cross-linked structure has a structure that passes environmental resistance tests (such as HAST tests), and the expected effect of the present invention can be exerted. In this regard, the presence of high molecular weight component (C) is also a reason for the improvement of brittleness, which can alleviate the stress in the hardened material (cross-linked structure), and it is believed that this also contributes to the improvement of adhesion and the improvement of environmental test resistance (HAST resistance).

The resin composition of the present embodiment is heat cured at 200°C for 90 minutes, and the cured product shows a small dielectric tangent value. Specifically, the dielectric tangent (Df) value is preferably 0.005 or less, more preferably 0.0049 or less, and even more preferably 0.0048 or less. The dielectric tangent (Df) value can be measured by the method described in the embodiment described below.

The resin composition of the present embodiment is heat cured at 200°C for 90 minutes, and the cured product shows improved brittleness. Specifically, one example of the evaluation item of brittleness is the value of the elongation at break (%), which is preferably more than 0.6%, more preferably more than 0.7%, more preferably more than 1.0%, and particularly preferably more than 1.2%. The value of the elongation at break can be measured by the method described in the embodiment described below.

The resin composition of the present embodiment is heat-cured at 200°C for 90 minutes. Even before being subjected to an environmental resistance test, the cured product shows good adhesion to conductive materials, especially excellent adhesion to thin film conductive materials (such as copper foil). Therefore, the cured product provides an insulating layer with excellent peel strength of conductive materials, which is one example of an evaluation item for adhesion. The peel strength before the environmental resistance test is preferably greater than 0.49kgf/cm, more preferably greater than 0.50kgf/cm, and even more preferably greater than 0.51kgf/cm. The upper limit of the peel strength before the environmental resistance test may be less than 10kgf/cm. The peel strength before the environmental resistance test can be measured according to the method described in the examples described below. The unit of the peel strength can be replaced with N/cm of the SI unit system.

The resin composition of the present embodiment is heat-cured at 200°C for 90 minutes. Even after being subjected to an environmental resistance test, the cured product shows good adhesion to the conductive material, especially excellent adhesion to the thin film conductive material (such as copper foil). Therefore, the cured product provides an insulating layer with excellent peeling strength of the conductive material even after being subjected to an environmental resistance test. The peeling strength after the environmental resistance test is preferably greater than 0.38kgf/cm, more preferably greater than 0.39kgf/cm, and even more preferably greater than 0.40kgf/cm. The upper limit of the peeling strength after the environmental resistance test may be less than 10kgf/cm, etc. The peel strength after the environmental resistance test can be measured according to the method described in the embodiments described below.

The cured product of the resin composition of the present embodiment, which was heat cured at 200°C for 90 minutes, showed adhesion to the conductive material before the environmental resistance test even after the environmental resistance test, and in particular showed the property of being able to maintain adhesion to the thin film conductive material (such as copper foil). Therefore, the cured product provided an insulating layer that could maintain the peeling strength of the conductive material even after the environmental resistance test. The ratio (percentage) of the peel strength value before the environmental resistance test to the peel strength value after the environmental resistance test is preferably 30% or less, more preferably 28% or less, further preferably less than 17%, and particularly preferably 15% or less, even in a harsh test environment of the environmental resistance test (for example, 100 hours under high temperature and high humidity conditions of 130°C and 85%RH).

The resin composition of the present invention can provide an insulating layer with a small dielectric tangent value, excellent adhesion to conductive materials after environmental resistance tests, and improved brittleness. Accordingly, the resin composition of the present invention can be used as a resin composition for insulating purposes. Specifically, it can be used as a resin composition for forming the insulating layer (resin composition for forming an insulating layer for forming a conductive layer), and the insulating layer is used to form a conductive layer (including a redistribution layer) formed on the insulating layer. The resin composition of the present invention can provide a hardened material with improved brittleness. Accordingly, the resin composition of the present invention can also be used as a resin composition for purposes other than insulation.

Furthermore, in the multilayer printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board) and a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board).

Furthermore, for example, when manufacturing a semiconductor chip package through the following steps (1) to (6), the resin composition of the present invention can also be used as a resin composition for forming a redistribution layer (resin composition for forming a redistribution layer) for forming an insulating layer of a redistribution layer, and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When manufacturing a semiconductor chip package, a redistribution layer can be further formed on the sealing layer. (1) a step of laminating a temporarily fixed film on a substrate, (2) a step of temporarily fixing a semiconductor chip on the temporarily fixed film, (3) a step of forming a sealing layer on the semiconductor chip, (4) a step of peeling the substrate and the temporarily fixed film from the semiconductor chip, (5) a step of forming a redistribution layer as an insulating layer on the surface of the substrate and the temporarily fixed film from which the semiconductor chip is peeled, and (6) a step of forming a redistribution layer as a conductive layer on the redistribution layer.

[Resin sheet] The resin sheet of the present invention comprises a support and a resin composition layer comprising the resin composition of the present invention disposed on the support.

The resin composition layer may contain any material other than the resin composition of the present invention, without significantly impairing the effect of the present invention, for example, a sheet-like reinforcing member such as glass cloth. However, when the resin composition layer contains a sheet-like reinforcing member, the thickness of the resin composition layer tends to increase. Therefore, from the viewpoint of reducing the thickness, the resin composition layer preferably does not contain a sheet-like reinforcing member, for example, the resin composition layer is composed only of the resin composition. In addition, the properties of the cured product described above are the properties of the cured product obtained by curing a resin composition layer of a resin composition that does not contain a sheet-like reinforcing member.

The thickness of the resin composition layer is preferably 70 μm or less, more preferably 50 μm or less, more preferably 45 μm or less, and even more preferably 40 μm or less, from the viewpoint of providing a cured product having excellent insulation properties even when the printed wiring board is thinned and 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 generally 1 μm or more, 1.5 μm or more, 2 μm or more, or 5 μm or more.

Examples of the support include films made of plastic materials, metal foils, and release papers, and films made of plastic materials and metal foils are preferred.

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

When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a foil made of a single metal including copper can be used, and a foil made of an alloy including copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used. As a specific example of a polyethylene terephthalate film, "Lumirror R80" manufactured by Toray Industries, Inc. can be cited.

The support may be subjected to matte treatment, corona treatment, and anti-static treatment on the surface that is bonded to the resin composition layer.

In addition, as the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent for the release layer used in the support with a release layer, for example, at least one release agent selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins can be listed. As an alkyd resin-based release agent, "AL-5" manufactured by Lintec Corporation can be listed. The support with a release layer can be a commercially available product, for example, a PET film having a release layer with an alkyd resin release agent as a main component, namely "SK-1", "AL-5", "AL-7" manufactured by Lintec, "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, "Unipiel" manufactured by Unitika, etc.

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

In one embodiment, the resin sheet may further include other layers if necessary. Examples of such other layers include a protective film provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support) and the like. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion or scratching of dirt and the like on the surface of the resin composition layer.

The resin sheet can be produced, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and then drying the varnish to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetates such as ethyl acetate, butyl acetate, solvent acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as solvent and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone, etc. The organic solvent may be used alone or in combination of two or more.

Drying can be carried out by known methods such as heating and hot air blowing. Although the drying conditions are not particularly limited, drying is performed in such a manner that the content of the organic solvent in the resin composition layer becomes 10 mass % or less, preferably 5 mass % or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30 mass % to 60 mass % of an organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

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

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

For example, a printed wiring board can be manufactured by using the above-mentioned resin sheet, and a method comprising the following steps (I) and (II). (I) A step of laminating the resin composition layer of the resin sheet on the inner substrate in such a manner as to bond the resin composition layer to the inner substrate (II) A step of thermally curing the resin composition layer to form an insulating layer

The so-called "inner substrate" used in step (I) is a component that becomes the substrate of the printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. In addition, the substrate may have a conductive layer on one or both sides thereof, and the conductive layer may be patterned. An inner substrate having a conductive layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner circuit substrate." In addition, when manufacturing a printed wiring board, an intermediate product that further forms an insulating layer and/or a conductive layer is also included in the so-called "inner substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner substrate with built-in components can be used.

The inner substrate and the resin sheet can be laminated, for example, by heating and pressing the resin sheet onto the inner substrate from the support body side. As a member for heating and pressing the resin sheet onto the inner substrate (hereinafter, also referred to as a "heating and pressing member"), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller) can be cited. However, it is preferred that the heating and pressing member is not directly pressed onto the resin sheet, but is pressed through an elastic material such as heat-resistant rubber in a manner that the resin sheet fully follows the surface irregularities of the inner substrate.

The lamination of the inner substrate and the resin sheet can be performed by vacuum lamination. In the vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably performed under reduced pressure conditions with a pressure of less than 26.7hPa.

Lamination can be performed by a commercially available vacuum laminating press. Examples of commercially available vacuum laminating presses include a vacuum press made by Nobuki Seisakusho Co., Ltd., a vacuum applicator made by Nikko Materials Co., Ltd., and a batch vacuum press.

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

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

In step (II), the resin composition layer is heat-cured to form an insulating layer. The heat-curing conditions of the resin composition layer are not particularly limited, and the conditions generally used when forming an insulating layer of a printed wiring board can be used.

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

Before heat-hardening the resin composition layer, the resin composition layer may be pre-heated at a temperature lower than the hardening temperature. For example, before heat-hardening the resin composition layer, the resin composition layer may be pre-heated at a temperature of 50°C to 120°C (preferably 60°C to 115°C, more preferably 70°C to 110°C) for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, the step (III) of drilling holes in the insulating layer, the step (IV) of roughening the insulating layer, and the step (V) of forming a conductive layer may be further performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art for the manufacture of printed wiring boards. Furthermore, when the support is removed after step (II), the removal of the support may be performed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Furthermore, if necessary, the steps (II) to (V) of forming the insulating layer and the conductive layer can be repeated to form a multi-layer wiring board.

Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as through holes and through-holes in the insulating layer. Step (III) can be performed using, for example, a drilling machine, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size or shape of the hole can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), the slurry is also removed. The order and conditions of the roughening treatment are not particularly limited, and the known order and conditions usually used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid. Although the swelling liquid used for the roughening treatment is not particularly limited, alkaline solutions, surfactant solutions, etc. can be listed. Alkaline solutions are preferred, and sodium hydroxide solutions and potassium hydroxide solutions are more preferred as the alkaline solution. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P", "Swelling Dip Securiganth SBU", and "Swelling Dip Securigant P" manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes. The oxidizing agent used for the roughening treatment is not particularly limited, but for example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be cited. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in the 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 commercially available oxidizing agents, for example, alkaline permanganic acid solutions such as "Concentrate ･Compact CP" and "Dosing solution ･Securiganth P" manufactured by Atotech Japan can be cited. In addition, the neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution. As a commercial product, for example, "Reduction solution･Securigant P" manufactured by Atotech Japan Co., Ltd. can be listed. The treatment with the neutralizing solution can be performed by immersing the surface treated by the roughening treatment with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 1 minute to 30 minutes. From the perspective of workability, etc., it is preferable to immerse the object treated by the roughening treatment with the oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes.

In one embodiment, the arithmetic average roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. Although the lower limit is not particularly limited, it is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductive layer, and the conductive layer is formed on the insulating layer. The conductive material used for the conductive layer is not particularly limited. In a suitable embodiment, the conductive layer includes one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductive layer can be a single metal layer or an alloy layer. As an alloy layer, for example, a layer formed by an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be listed. Among them, from the viewpoint of versatility of formation of the conductive layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or 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 even more preferred.

The conductive layer may be a single layer structure or a composite structure, wherein the composite structure is a single metal layer or an alloy layer formed by laminating two or more layers of different types of metals or alloys. When the conductive layer is a composite structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium or an alloy layer of nickel-chromium alloy.

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

In one embodiment, the conductive layer can be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. From the perspective of manufacturing simplicity, it is preferably formed by a semi-additive method. The following is an example of forming a conductive layer by a semi-additive method.

First, a seed layer is formed on the surface of the insulating layer by electroless plating. Then, a mask pattern is formed on the formed seed layer to expose a portion of the seed layer corresponding to the desired wiring pattern. After a metal layer is formed on the exposed seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary seed layer can be removed by etching, etc., to form a conductive layer with the desired wiring pattern.

[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.

As semiconductor devices, there can be listed various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and transportation vehicles (such as motorcycles, cars, trains, ships, and aircrafts).

The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) on the conductive part of a printed wiring board. The so-called "conductive part" is "the place where the electrical signal is transmitted on the printed circuit board", and the place can be the surface or the embedded place. In addition, the semiconductor chip is not particularly limited as long as it is an electrical circuit element using semiconductor as a material.

The semiconductor chip mounting method when manufacturing semiconductor devices is not particularly limited as long as the semiconductor chip functions effectively. Specifically, there are wire bonding mounting methods, flip chip mounting methods, mounting methods by bumpless laminate (BBUL), mounting methods by anisotropic conductive film (ACF), mounting methods by non-conductive film (NCF), etc. Here, the so-called "mounting method by bumpless laminate (BBUL)" is "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed circuit board and the semiconductor chip is connected to the wiring on the printed circuit board." [Example]

The present invention is described below in detail by showing an embodiment, but the present invention is not limited to the following embodiment. In the following description, "parts" and "%" mean "parts by mass" and "% by mass" respectively, unless otherwise specified. In addition, the operations described below are performed at room temperature and pressure unless otherwise specified.

[Synthesis Example 1: Synthesis of high molecular weight component] A varnish containing a polyimide resin as a high molecular weight component is prepared as follows. A 500 mL separation flask equipped with a water dosing receiver connected to a reflux cooler, a nitrogen inlet tube, and a stirrer is prepared. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane (Indane) are added to the flask, and the mixture is stirred at 45°C for 2 hours under a nitrogen flow to obtain a reaction solution.

Next, the reaction solution is heated up and maintained at about 160°C while condensed water is removed azeotropically together with toluene under a nitrogen flow. Confirm that a specified amount of water is retained in the water quantitative receiver and until the outflow of water is no longer observed. After confirmation, the reaction solution is further heated up and stirred at 200°C for 1 hour. Then, it is cooled to obtain a varnish containing 20 mass% of a polyimide resin having a 1,1,3-trimethylindane skeleton (hereinafter sometimes referred to as "the polyimide resin of Synthesis Example 1"). The polyimide resin of Synthesis Example 1 has a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). The weight average molecular weight of the polyimide resin of Synthesis Example 1 was 12,000 when measured by the same method as the weight average molecular weight of the component (C).

[Example 1] (Preparation of resin varnish A containing resin composition) 100 parts of biphenyl aralkyl maleimide resin "MIR-3000-70MT" (maleimide group equivalent: 275 g/eq., MEK/toluene mixed solution with a non-volatile content of 70%) (hereinafter, also referred to as "solution containing maleimide compound A") manufactured by Nippon Kayaku Co., Ltd. as a maleimide compound, 30 parts of a varnish containing 20% by mass of the polyimide resin as a high molecular weight component obtained in Synthesis Example 1 (hereinafter, also referred to as "varnish containing high molecular weight component A"), 15 parts of toluene, 15 parts of methyl ethyl ketone (MEK), "ALP-d" manufactured by Shikoku Chemical Industries, Ltd. as an allyl group-containing benzoxazine compound (an allyl group-containing benzoxazine compound containing a non-substituted allyl group; ring-opening reaction reagent) were mixed. 4 parts of a MEK solution containing 50% of a non-volatile component (with an allyl group equivalent weight: 257 g/eq., an allyl group equivalent weight: 257 g/eq.), 0.5 parts of "PERHEXYL (registered trademark) D" manufactured by NOF Corporation (hereinafter also referred to as "polymerization initiator A") as a polymerization initiator, and 135 parts of spherical silica "SO-C2" manufactured by Admatechs Corporation as an inorganic filler and surface-treated with phenylaminosilane coupling agent "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd. as an amine coupling agent (hereinafter also referred to as "inorganic filler A") as an inorganic filler were uniformly dispersed with a high-speed rotary stirrer to obtain a resin varnish A containing a resin composition. The average particle size of the inorganic filler A measured by the aforementioned measuring method is 0.5 μm, and the specific surface area measured by the aforementioned measuring method is 5.9 m ² /g.

(Preparation of resin sheet A) A support having a release layer was prepared by subjecting one side of a polyethylene terephthalate film ("Lumirror R80" manufactured by Toray Industries, Inc., thickness 38μm, softening point 130°C) to a release treatment using an alkyd resin-based release agent ("AL-5" manufactured by Lintec Corporation).

On the release layer of this support, the aforementioned resin varnish A is uniformly applied using a die coater in such a manner that the thickness of the resin composition layer after drying becomes 40 μm. Then, the resin varnish A is dried from 70°C to 105°C for 3 minutes. In this way, a resin sheet comprising a support and a resin composition layer is obtained, and the resin composition layer comprises a resin composition disposed on the support. Next, the rough surface of a polypropylene film ("ALPHAN MA-411" manufactured by Prince F-TEX Co., Ltd., with a thickness of 15 μm) is bonded as a protective film to the surface of the support that is not bonded to the resin composition layer. In this way, a resin sheet A having a support, a resin composition layer and a protective film in sequence is obtained.

(Evaluation of cured resin composition) The cured resin composition layer of the obtained resin sheet A was used to evaluate the value of dielectric tangent, brittleness and adhesion of the cured resin composition according to the evaluation method described below.

[Example 2] 70 parts of polyphenylmethane maleimide "BMI-2300" (maleimide group equivalent 186 g/eq.) (hereinafter, also referred to as "maleimide compound B") manufactured by Yamato Chemical Industry Co., Ltd. as a maleimide compound and 6 parts of polycarbonate resin "FPC2136" (weight average molecular weight 30,000, number average molecular weight 20,895) (hereinafter, also referred to as "high molecular weight component B") manufactured by Mitsubishi Gas Chemical Co., Ltd. as a high molecular weight component were stirred in 40 parts of toluene and 40 parts of MEK and heated to dissolve. After the obtained solution was cooled to room temperature, 4 parts of a solution containing an allyl group-containing benzoxazine compound A, 0.5 parts of a polymerization initiator A, and 135 parts of spherical silica "SO-C2" manufactured by Admatechs and surface-treated with a (meth)acrylic coupling agent "KBM503" manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter also referred to as "inorganic filler B") were uniformly dispersed in the solution using a high-speed rotary stirrer to obtain a resin varnish A containing a resin composition. The average particle size of the inorganic filler B measured by the aforementioned measurement method was 0.5 μm, and the specific surface area measured by the aforementioned measurement method was 5.9 m ² /g. Furthermore, using resin varnish A, the same procedures as in Example 1 were carried out to obtain resin sheet A, and the resin composition layer of resin sheet A was subjected to the same procedures as in Example 1 and evaluated.

[Example 3] 3 parts of high molecular weight component B was stirred in 20 parts of toluene and 20 parts of MEK while being heated and dissolved. After the obtained solution was cooled to room temperature, 100 parts of a solution containing maleimide compound A, 15 parts of liquid bismaleimide "BMI-689" (maleimide equivalent 345 g/eq.) manufactured by Designer Molecules as a maleimide compound (hereinafter also referred to as "maleimide compound C"), 4 parts of a solution containing an allyl group-containing benzoxazine compound A, 0.5 parts of a polymerization initiator A, and 235 parts of an inorganic filler material A were uniformly dispersed with a high-speed rotary mixer to obtain a resin varnish A containing a resin composition. Furthermore, using resin varnish A, the same procedures as in Example 1 were carried out to obtain resin sheet A, and the resin composition layer of resin sheet A was subjected to the same procedures as in Example 1 and evaluated.

[Example 4] 70 parts of maleimide compound B were stirred in 40 parts of toluene and 40 parts of MEK while being heated to dissolve. After the obtained solution was cooled to room temperature, 15 parts of liquid bismaleimide "BMI-1500" (maleimide equivalent 750 g/eq.) manufactured by Designer Molecules as maleimide compound (hereinafter also referred to as "maleimide compound D"), 15 parts of phenoxy resin "YX7553BH30" (weight average molecular weight 35000; 1:1 solution of MEK and cyclohexanone with 30% by mass of non-volatile components) manufactured by Mitsubishi Chemical Corporation as high molecular weight component were added. 10 parts of a solution containing a high molecular weight component C), 4 parts of a solution containing an allyl group-containing benzoxazine compound A, 0.5 parts of a polymerization initiator A, and 235 parts of an inorganic filler A were uniformly dispersed with a high-speed rotary stirrer to obtain a resin varnish A containing a resin composition. Furthermore, using the resin varnish A, the same method as in Example 1 was used to obtain a resin sheet A, and the resin composition layer of the resin sheet A was subjected to the same method as in Example 1 and evaluated.

[Example 5] 100 parts of a solution containing maleimide compound A, 20 parts of toluene, 20 parts of MEK, 15 parts of maleimide compound C, 15 parts of a varnish containing a high molecular weight component A, 20 parts of a solution containing an allyl group-containing benzoxazine compound A, 0.5 parts of a polymerization initiator A, and 235 parts of an inorganic filler B were uniformly dispersed with a high-speed rotary mixer to obtain a resin varnish A containing a resin composition. Furthermore, using the resin varnish A, the same process as in Example 1 was performed to obtain a resin sheet A, and the resin composition layer of the resin sheet A was subjected to the same process as in Example 1 and evaluated.

[Example 6] 100 parts of a solution containing maleimide compound A, 15 parts of maleimide compound D, 20 parts of toluene, 20 parts of MEK, 15 parts of a varnish containing a high molecular weight component A, 30 parts of a solution containing an allyl group-containing benzoxazine compound A, 0.5 parts of a polymerization initiator A, and 235 parts of an inorganic filler A were uniformly dispersed with a high-speed rotary mixer to obtain a resin varnish A containing a resin composition. Furthermore, using the resin varnish A, the same process as in Example 1 was performed to obtain a resin sheet A, and the resin composition layer of the resin sheet A was subjected to the same process as in Example 1 and evaluated.

[Example 7] 100 parts of a solution containing maleimide compound A, 15 parts of maleimide compound C, 20 parts of toluene, 20 parts of MEK, 10 parts of a solution containing high molecular weight component C, 4 parts of a solution containing allyl-containing benzoxazine compound A, 0.5 parts of a polymerization initiator A, 235 parts of an inorganic filler material A, and a naphthalene-type epoxy resin "HP4032SS" (epoxy equivalent weight of about 144 g/eq.) manufactured by DIC Corporation as a thermosetting resin were mixed. ) 8 parts, DIC Corporation active ester curing agent "HPC-8000-65T" as a thermosetting resin (active group equivalent of about 223 g/eq., non-volatile components 65 mass % toluene solution) 18.5 parts, and 1-benzyl-2-phenylimidazole (1B2PZ) as a thermosetting resin (non-volatile components 20 mass % MEK solution) 1 part, were uniformly dispersed with a high-speed rotary stirrer to obtain a resin varnish A containing a resin composition. Then, using the resin varnish A, the same method as in Example 1 was performed to obtain a resin sheet A, and the resin composition layer of the resin sheet A was subjected to the same method as in Example 1 and evaluated.

[Example 8] 100 parts of a solution containing maleimide compound A, 15 parts of maleimide compound C, 20 parts of toluene, 20 parts of MEK, 15 parts of a varnish containing a high molecular weight component A, 4 parts of a solution containing an allyl group-containing benzoxazine compound A, 0.5 parts of a polymerization initiator A, 235 parts of an inorganic filler B, and 50 parts of a toluene solution containing 65% by mass of a radical polymerizable compound "OPE-2St" (number average molecular weight 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd. as a thermosetting resin) were uniformly dispersed in a high-speed rotary mixer to obtain a resin varnish A containing a resin composition. Furthermore, using resin varnish A, the same procedures as in Example 1 were carried out to obtain resin sheet A, and the resin composition layer of resin sheet A was subjected to the same procedures as in Example 1 and evaluated.

[Comparative Example 1] In Example 1, 4 parts of the solution containing the allyl-containing benzoxazine compound A were replaced with 4 parts of a 50% MEK solution of "P-d" (benzoxazine compound having no functional group reactive with maleimide group; ring-opening reaction participating group equivalent: 217 g/eq., allyl group equivalent: 0 g/eq.) manufactured by Shikoku Chemical Industries, Ltd. as component (B'). Except for the above matters, the same procedures as in Example 1 were followed to obtain a resin varnish A containing a comparative resin composition. Furthermore, using the resin varnish A, the same procedures as in Example 1 were followed to obtain a resin sheet A, and the resin composition layer of the resin sheet A was subjected to the same evaluation as in Example 1.

[Comparative Example 2] In Example 1, 4 parts of the solution containing the allyl-containing benzoxazine compound A were replaced with 2 parts of diallyl phthalate "DAISO DAP (registered trademark) monomer" (molecular weight 246; allyl equivalent: 123 g/eq.) manufactured by Osaka Soda Co., Ltd. as the (B") component. Except for the above matters, the same procedures as in Example 1 were followed to obtain a resin varnish A containing a comparative resin composition. Furthermore, using the resin varnish A, the same procedures as in Example 1 were followed to obtain a resin sheet A, and the resin composition layer of the resin sheet A was subjected to the same evaluation as in Example 1.

[Comparative Example 3] In Example 1, 4 parts of the solution containing the allyl-containing benzoxazine compound A were replaced with 2 parts of a 50% non-volatile component MEK solution of "P-d" manufactured by Shikoku Chemical Industries, Ltd. and 1 part of diallyl phthalate "DAISO DAP (registered trademark) monomer" (molecular weight 246) manufactured by Osaka Soda Co., Ltd. as the (B') component. Except for the above matters, the same procedures as in Example 1 were followed to obtain a resin varnish A containing a comparative resin composition. Furthermore, using the resin varnish A, the same procedures as in Example 1 were followed to obtain a resin sheet A, and the resin composition layer of the resin sheet A was subjected to the same evaluation as in Example 1.

[Comparative Example 4] 20 parts of the varnish containing the high molecular weight component A in Example 1 were not used. Except for the above matters, the same procedures as in Example 1 were followed to obtain a resin varnish A containing a comparative resin composition. Furthermore, using the resin varnish A, the same procedures as in Example 1 were followed to obtain a resin sheet A, and the resin composition layer of the resin sheet A was subjected to the same evaluation as in Example 1. However, for Comparative Example 4, the dielectric tangent value and brittleness could not be evaluated.

[Evaluation method] The resin composition layer of the resin sheet A obtained in the above-mentioned embodiment and comparative example was used, and the cured product of the resin composition layer was evaluated from the viewpoints of dielectric tangent value, brittleness and adhesion by the following method.

<Evaluation of Adhesion> The evaluation of adhesion was performed by measuring the peel strength of the copper foil in the following order. <<Production of Evaluation Substrate>> (1) Base treatment of copper foil The glossy surface of "3EC-III" (electric copper foil, 35μm) manufactured by Mitsui Metal Mining Co., Ltd. was etched 1μm on "CZ8101" manufactured by Mec Co., Ltd. to roughen the copper surface, and then anti-rust treatment (CL8300) was performed. This copper foil is called CZ copper foil. It was then heated in an oven at 130°C for 30 minutes. In this way, the inner layer substrate was obtained.

(2) Preparation of the inner layer substrate: The glass cloth substrate epoxy resin copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.4mm, "R1515A" manufactured by Panasonic) that forms the inner layer circuit is etched 1μm on both sides using "CZ8101" manufactured by Mec to roughen the copper surface. In this way, a CZ copper foil with a treated surface is obtained.

(3) Lamination of resin composition layer The protective film was peeled off from the resin sheet A prepared in the embodiment and the comparative example to expose the resin composition layer. The resin composition layer was laminated on both sides of the inner substrate in such a manner that the resin composition layer was bonded to the inner substrate using a batch vacuum pressure laminating press (manufactured by Nikko Materials Co., Ltd., two-stage stacking laminating press, CVP700). Lamination was performed by reducing the pressure for 30 seconds to adjust the air pressure to less than 13 hPa, and then pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Then, hot pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds. The support is then peeled off to expose the resin composition layer.

(4) Copper foil lamination and resin composition layer hardening The treated surface of the CZ copper foil was laminated on the exposed resin composition layer under the same conditions as above. Furthermore, the resin composition layer was hardened at 200°C for 90 minutes to form a hardened product (insulating layer). Thus, an evaluation substrate A with CZ copper foil laminated on both sides was obtained.

<<Measurement of the peel strength of copper foil before HAST>> The prepared evaluation substrate A was cut into small pieces of 150mm×30mm. A cutter was used to insert a section of 10mm wide and 100mm long into the copper foil portion of the small piece, and this end was peeled off and clamped with the clamp of the tensile tester described later. At room temperature (normal temperature), the load [kgf/cm] when peeling 35mm in the vertical direction was measured at a speed of 50mm/min. The load value obtained from this measurement result was defined as the "peel strength of copper foil before HAST". A tensile tester (Autocom universal testing machine "AC-50C-SL" manufactured by TSE Corporation) was used for the measurement. The measurement was carried out in accordance with Japanese industrial standard JIS C6481. The results are shown in Table 1.

<<Measurement of the peeling strength of copper foil after HAST>> The prepared evaluation substrate A was subjected to an accelerated environmental test at 130°C and 85%RH for 100 hours using a highly accelerated life tester ("PM422" manufactured by Kusumoto Chemicals Co., Ltd.). Then, the evaluation substrate A after HAST was sliced as above, and one end of the peeled slice was clamped with the clamp of the above tensile tester as in the above measurement. The load [kgf/cm] when peeled 35mm in the vertical direction was measured at a speed of 50mm/min at room temperature (normal temperature). The load value obtained from this measurement result was defined as the "peeling strength of copper foil after HAST". The measurement was performed in accordance with Japanese industrial standard JIS C6481. The results are shown in Table 1.

<Evaluation of dielectric tangent> The dielectric tangent was evaluated by measuring its value according to the following procedure. <<Preparation of evaluation hardened material>> By peeling off the protective film from the resin sheet A prepared in the embodiment and the comparative example, heating at 200°C for 90 minutes to thermally cure the resin composition layer, and then peeling off the support, a hardened material film formed of the hardened material of the resin composition was obtained. For comparative example 4, no hardened material film was obtained. The hardened material film was cut into a width of 2 mm and a length of 80 mm to obtain the evaluation hardened material A.

<<Measurement>> For each evaluation hardener A, the dielectric tangent value (Df value) was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C using the cavity resonance method using the "HP8362B" manufactured by Agilent Technologies. The measurement was performed on three test pieces, and the average value was calculated. The results are shown in Table 1.

<Evaluation of brittleness> Evaluation of brittleness was performed by measuring the elongation at the fracture point in the following procedure. For the evaluation hardened material A, a tensile test was performed in accordance with Japanese industrial standard JIS K7127 using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientech Co., Ltd.) to measure the elongation at the fracture point [%]. The results are shown in Table 1.

[Results] The results of the above-mentioned Examples and Comparative Examples are shown in Table 1 below. In Table 1 below, the amount of each component represents the amount of non-volatile components. The content of component (C) and the content of component (D) in Table 1 represent the percentage [mass %] when the non-volatile components in the resin composition are set to 100 mass %.

<Conclusion> It is clear from Table 1 that, from the comparison between the embodiment and the comparative example, in the embodiment, a resin composition can be provided that can obtain a small dielectric tangent value, excellent adhesion between conductive materials after environmental resistance test, and improved brittleness of the cured product. In addition, it is also understood that it is possible to provide a resin composition related to the embodiment when the cured product of the resin composition; a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device containing an insulating layer formed by the cured product of the resin composition.

In Examples 1 to 8, even when the components (D) to (F) are not contained, it is confirmed that the same results as those of the above examples are obtained, although the extent is different. In Examples 1 to 8, even when one or both of the components (B') and (B") are contained in an amount that does not hinder the expected effect of the present invention, it is confirmed that the same results as those of the above examples are obtained, although the extent is different.

Claims (19)

A resin composition comprising (A) a maleimide compound, (B) an allyl-containing benzoxazine compound and (C) a high molecular weight component, wherein the weight average molecular weight or number average molecular weight of the component (C) is 5000 to 100000, the content of the component (B) is 0.01 to 15% by mass when the non-volatile components in the resin composition are taken as 100% by mass, the mass ratio of the component (B) to the component (A) [component (B)/component (A)] is 0.01 to 0.20, and the content of the component (C) is 0.1 to 10% by mass when the non-volatile components in the resin composition are taken as 100% by mass. The resin composition described in claim 1, wherein the content of component (A) is 10% by mass or more and 40% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. The resin composition described in claim 1, wherein the content of component (B) is 0.02% by mass or more and 10% by mass or less when the non-volatile components in the resin composition are taken as 100% by mass. The resin composition described in claim 1, wherein the mass ratio of component (B) to component (A) [component (B)/component (A)] is 0.02 or more and 0.19 or less. The resin composition described in claim 1, wherein component (C) is a thermoplastic resin. The resin composition described in claim 5, wherein the thermoplastic resin is at least one selected from polyimide resin, polycarbonate resin and phenoxy resin. The resin composition described in claim 1, wherein the weight average molecular weight or number average molecular weight of component (C) is greater than 8,000 and less than 80,000. The resin composition described in claim 1, wherein the content of component (C) is 0.2% by mass or more and 8% by mass or less when the non-volatile components in the resin composition are taken as 100% by mass. The resin composition described in claim 1 further comprises (D) an inorganic filler material. The resin composition described in claim 9, wherein component (D) is surface treated with an amine coupling agent or a (meth)acrylic coupling agent. The resin composition described in claim 9, wherein the content of component (D) is 50% by mass or more when the non-volatile components in the resin composition are taken as 100% by mass. The resin composition described in claim 1, wherein the cured product obtained by heat treatment at 200°C for 90 minutes has a dielectric tangent of less than 0.005 when measured by cavity resonance propagation method at a measuring frequency of 5.8 GHz and a measuring temperature of 23°C. For the resin composition described in claim 1, the hardened product obtained by heat treatment at 200°C for 90 minutes has an elongation at break of 0.7% or more when measured in accordance with Japanese industrial standard JIS K7127. The resin composition described in claim 1 is used to form an insulating layer. The resin composition described in claim 1 is used to form an insulating layer of a conductive layer. A cured product of a resin composition as described in any one of claim items 1 to 15. A resin sheet comprising a support and a resin composition layer comprising a resin composition as described in any one of claims 1 to 15 disposed on the support. A printed wiring board comprising an insulating layer formed by a cured product of a resin composition as described in any one of claims 1 to 15 or a cured product as described in claim 16. A semiconductor device comprising a printed wiring board as described in claim 18.