CN114058236A

CN114058236A - Resin composition

Info

Publication number: CN114058236A
Application number: CN202110858634.0A
Authority: CN
Inventors: 川合贤司
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2020-07-29
Filing date: 2021-07-28
Publication date: 2022-02-18
Also published as: KR20220014836A; TW202208473A; JP2022025705A

Abstract

The present invention addresses the problem of providing a resin composition or the like that can provide a cured product that has low dielectric properties, excellent peel strength even when the surface roughness is small, and a high glass transition temperature. The solution of the present invention is a resin composition comprising (A) a polyether ether ketone compound having a maleimide group, (B) an epoxy resin, and (C) an active ester curing agent.

Description

Resin composition

Technical Field

The present invention relates to a resin composition. The present invention also relates to a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

Background

As a manufacturing technique of a printed wiring board, a manufacturing method based on a stacked-up (stacked-up) method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method by the stack method, the insulating layer is generally formed by curing a resin composition. As such a resin composition, for example, a resin composition disclosed in patent document 1 is known.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2019 and 066792.

Disclosure of Invention

Problems to be solved by the invention

A cured product formed by curing the resin composition can be used as an insulating layer of a printed wiring board of a semiconductor device. Therefore, it is required to lower the dielectric characteristics (dielectric constant and dielectric loss tangent) of the cured product. In addition, it is desired that the insulating layer formed from the cured product has a high glass transition temperature for excellent heat resistance, and is excellent in peel strength with the conductor layer even when the roughness of the surface of the insulating layer is small.

The present invention has been made in view of the above problems, and an object thereof is to provide: a resin composition which can give a cured product having low dielectric characteristics, excellent peel strength even when the surface roughness is small, and a high glass transition temperature; a resin sheet having a resin composition layer comprising the resin composition; a printed wiring board comprising an insulating layer formed from a cured product of the resin composition; and a semiconductor device including the printed wiring board.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, the present inventors have found that the above problems can be solved by using (a) a polyether ether ketone compound having a maleimide group, (B) an epoxy resin, and (C) an active ester-based curing agent, and have completed the present invention.

Namely, the present invention includes the following;

[1] a resin composition comprising:

(A) a polyether ether ketone compound having a maleimide group,

(B) an epoxy resin, and

(C) an active ester-based curing agent;

[2] the resin composition according to [1], wherein the number average molecular weight of the component (A) is 10000 or less;

[3] the resin composition according to [1] or [2], wherein the component (A) has a maleimide group at a terminal;

[4] the resin composition according to any one of [1] to [3], wherein the content of the component (A) is 5% by mass or more and 60% by mass or less, assuming that the resin component in the resin composition is 100% by mass;

[5] the resin composition according to any one of [1] to [4], wherein the component (B) comprises a naphthol type epoxy resin;

[6] the resin composition according to any one of [1] to [5], wherein the component (C) is at least 1 selected from a dicyclopentadiene type active ester-based curing agent and a naphthalene type active ester-based curing agent;

[7] the resin composition according to any one of [1] to [6], further comprising (D) a resin having a polymerizable unsaturated group;

[8] the resin composition according to [7], wherein the component (D) is a resin containing a maleimide group and an aromatic ring;

[9] the resin composition according to any one of [1] to [8], further comprising (E) an inorganic filler;

[10] the resin composition according to [9], wherein the content of the component (E) is 40 to 65 mass% inclusive, assuming that the nonvolatile content in the resin composition is 100 mass%;

[11] the resin composition according to any one of [1] to [10], which is used for forming an insulating layer;

[12] the resin composition according to any one of [1] to [11], which is used for forming an insulating layer for forming a conductor layer;

[13] a resin sheet comprising a support and, provided on the support, a resin composition layer comprising the resin composition according to any one of [1] to [12 ];

[14] a printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [12 ];

[15] a semiconductor device comprising the printed wiring board of [14 ].

ADVANTAGEOUS EFFECTS OF INVENTION

By the present invention, there can be provided: a resin composition which can give a cured product having low dielectric characteristics, excellent peel strength even when the surface roughness is small, and a high glass transition temperature; a resin sheet having a resin composition layer comprising the resin composition; a printed wiring board comprising an insulating layer formed from a cured product of the resin composition; and a semiconductor device including the printed wiring board.

Detailed Description

The present invention will be described below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be modified arbitrarily within the scope not departing from the claims and the equivalent scope of the present invention.

[ resin composition ]

The resin composition of the present invention comprises (A) a polyether ether ketone compound having a maleimide group, (B) an epoxy resin, and (C) an active ester curing agent. Such a resin composition can provide a cured product having low dielectric properties, excellent peel strength even with a small surface roughness, and a high glass transition temperature.

The resin composition may further comprise, as required: (D) a resin containing a radical polymerizable unsaturated group, (E) an inorganic filler, (F) a curing agent, (G) a curing accelerator, and (H) other additives.

< (A) A polyether ether ketone compound having a maleimide group

The resin composition contains a polyether ether ketone compound having a maleimide group as the component (a). The maleimide group is represented by the following formula (A-1). By containing the component (A) in the resin composition, a cured product having a high glass transition temperature can be obtained;

[ chemical formula 1]

As the component (a), a compound having a maleimide group and a polyether ether ketone (PEEK) structure can be used. (A) Component (c) preferably has 1 or more maleimide groups, more preferably 2 or more maleimide groups, preferably 10 or less maleimide groups, more preferably 5 or less maleimide groups, and still more preferably 3 or less maleimide groups per 1 molecule. The maleimide group is preferably a maleimide group at a terminal of the component (a), and more preferably a maleimide group at both terminals, from the viewpoint of obtaining a cured product having excellent dielectric properties.

(A) The component has a polyetheretherketone structure. The polyether ether ketone structure preferably has a structure represented by the following formula (A-2):

[ chemical formula 2]

In the formula (A-2), Ar¹、Ar²、Ar³、Ar⁴And Ar⁵Each independently represents a divalent aromatic hydrocarbon group. n represents an integer of 2 to 50. Denotes a bond.

The aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring. However, the aromatic hydrocarbon group does not necessarily have to be composed of only an aromatic ring, and may include a chain structure or an alicyclic hydrocarbon group in a part thereof, and the aromatic ring may be any of a monocyclic ring, a polycyclic ring, and a heterocyclic ring.

Examples of the divalent aromatic hydrocarbon group include an arylene group, an aralkylene group, and a group having an arylene-alkylene-arylene structure.

The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include phenylene, naphthylene, anthrylene, and biphenylene.

The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and still more preferably an aralkylene group having 7 to 15 carbon atoms. Examples of such an aralkylene group include a benzylidene group and a group having a biphenylene-methylene structure.

The arylene group in the group having an arylene-alkylene-arylene structure is the same as the above-mentioned arylene 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, and still more preferably an alkylene group having 1 to 3 carbon atoms. Examples of such alkylene groups include methylene, ethylene, and propylene. In addition, the alkylene group optionally has a substituent. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; and a halogenated alkyl group, preferably an alkyl group or a halogenated alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or a trifluoromethyl group, and still more preferably a methyl group. Specific examples of such a group having an arylene-alkylene-arylene structure include structures represented by the following formulas (1) to (2). Among them, the group represented by the formula (1) is preferable;

[ chemical formula 3]

In the formula, "", indicates a bond.

Among these, as Ar¹、Ar²、Ar⁴And Ar⁵Preferably, an arylene group or a group having an arylene-alkylene-arylene structure is used, more preferably an arylene group, and still more preferably a phenylene group. As Ar³Preferably, the group is an arylene group or a group having an arylene-alkylene-arylene structure, more preferably a group having an arylene-alkylene-arylene structure, and still more preferably a group having a phenylene-dimethylmethylene-phenylene structure (the group represented by formula (1)).

n represents an integer of 2 to 50, preferably an integer of 3 to 40, more preferably an integer of 4 to 30, and further preferably an integer of 5 to 20.

Specific examples of the structure represented by formula (a-2) include, for example, structures represented by the following formulae (a1) to (a2), but are not limited thereto (in the formulae, a represents a bond),

[ chemical formula 4]

n1 and n2 are the same as n in the formula (A-2).

The component (A) is preferably a compound represented by the following formula (A-3):

[ chemical formula 5]

In the formula, D¹And D²Each independently represents a single bond or a divalent linking group. Ar (Ar)¹¹、Ar¹²、Ar¹⁴And Ar¹⁵Each independently of Ar in formula (A-2)¹、Ar²、Ar⁴And Ar⁵The same is true. Ar (Ar)¹³Each independently of Ar in formula (A-2)³The same is true. m is the same as n in the formula (A-2).

D¹And D²Each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, an imide bond, and a group in which a plurality of these are linked. The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group.

Examples of the divalent aliphatic hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, and a linear or branched alkenylene group having 2 to 18 carbon atoms. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene and the like. Examples of the linear or branched alkenylene group having 2 to 18 carbon atoms include an ethenylene group, a 1-methylethenylene group, an propenylene group, a 1-butenylene group, and a 2-butenylene group.

Examples of the divalent alicyclic hydrocarbon group include divalent alicyclic hydrocarbon groups having 3 to 18 carbon atoms, and examples thereof include cycloalkylene groups (including cycloalkylidene groups) such as 1, 2-cyclopentylidene group, 1, 3-cyclopentylidene group, cyclopentylidene group (cyclopentylidene), 1, 2-cyclohexylidene group, 1, 3-cyclohexylidene group, 1, 4-cyclohexylidene group, cyclohexylidene group (cyclohexylidene) and the like.

Examples of the divalent aromatic hydrocarbon group include arylene groups having 6 to 14 carbon atoms, and examples thereof include 1, 2-phenylene, 1, 4-phenylene, 1, 3-phenylene, 4 '-biphenylene, 3' -biphenylene, 2, 6-naphthylene, 2, 7-naphthylene, 1, 8-naphthylene, and anthracenylene.

The heterocyclic ring constituting the divalent heterocyclic group includes aromatic heterocyclic rings and non-aromatic heterocyclic rings. Examples of the heterocyclic ring include three-to ten-membered rings having carbon atoms and at least 1 kind of hetero atoms among atoms constituting the ring, condensed rings thereof, and the like. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. The heterocycle is preferably a three-to ten-membered ring, more preferably a four-to six-membered ring. Examples of the heterocyclic ring constituting the divalent heterocyclic group include: a three-membered ring such as an oxirane ring; a four-membered ring such as an oxetane ring; five-membered rings such as furan ring, tetrahydrofuran ring, oxazole ring, isoxazole ring, γ -butyrolactone ring, thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, pyrrole ring, pyrrolidine ring, pyrazole ring, imidazole ring, and triazole ring; a six-membered ring such as a 4-oxo-4H-pyran ring, a tetrahydropyran ring, a morpholine ring, a 4-oxo-4H-thiopyran ring, an isocyanuric acid ring (isocyanuric ring), a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, and a piperazine ring; 3-oxatricyclo [4.3.1.1^4,8]Undecane-2-one ring, 3-oxatricyclo [4.2.1.0^4,8]A bridged ring such as nonane-2-one ring; fused rings such as a benzofuran ring, an isobenzofuran ring, a 4-oxo-4H-benzopyran ring, a chroman ring, an isochroman ring, a benzothiophene ring, an indole ring, an indoline ring, a quinoline ring, an acridine ring, a naphthyridine ring, a quinazoline ring, and a purine ring. The divalent heterocyclic group is a group obtained by removing 2 hydrogen atoms from the structural formula of the above heterocyclic ring.

Wherein as D¹And D²From the viewpoint of remarkably obtaining the effect of the present invention, the aromatic hydrocarbon group preferably represents a divalent aromatic hydrocarbon group, more preferably represents an arylene group having 6 to 16 carbon atoms, and further preferably represents 1, 2-phenylene, 1, 4-phenylene, 1, 3-phenylene, 4 '-biphenylene, 3' -biphenylene, 2, 6-naphthylene, 2, 7-naphthylene, 1, 8-naphthylene, orAnthracenylene, particularly preferably 1, 2-phenylene, 1, 4-phenylene or 1, 3-phenylene.

Specific examples of the component (A) include the following examples, but the present invention is not limited thereto. In the formula, na and nb independently represent an integer of 2 to 50;

[ chemical formula 6]

As the component (A), commercially available ones can be used, and those synthesized by a known method can also be used. The component (A) can be synthesized, for example, by the synthesis method described in Polymer 1989, p.978. (A) The components can be used singly or in combination of 2 or more.

The weight average molecular weight of the component (a) is preferably 1000 or more, more preferably 1200 or more, further preferably 1400 or more, preferably 10000 or less, more preferably 7500 or less, and further preferably 5000 or less, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to a copper foil. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by Gel Permeation Chromatography (GPC).

The number average molecular weight of the component (a) is preferably 1000 or more, more preferably 1200 or more, further preferably 1400 or more, preferably 10000 or less, more preferably 7500 or less, and further preferably 5000 or less, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to a copper foil. The number average molecular weight of the resin can be measured as a value in terms of polystyrene by Gel Permeation Chromatography (GPC).

The content of the component (a) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to the copper foil. In the present invention, unless otherwise specified, the content of each component in the resin composition is a value when the nonvolatile content in the resin composition is 100 mass%.

The content of the component (a) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, preferably 60% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less, based on 100% by mass of the resin component in the resin composition, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to the copper foil. The resin component means a component other than (E) the inorganic filler among nonvolatile components in the resin composition.

(B) epoxy resin

The resin composition contains an epoxy resin as the component (B). By containing (B) an epoxy resin in the resin composition, a cured product having low dielectric characteristics and excellent peel strength can be obtained.

Examples of the component (B) include: a biscresol (bixylenol) type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolac (naphthol novolac) type epoxy resin, a phenol novolac (phenol novolac) type epoxy resin, a tert-butyl-catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac (cresol novolac) type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, an epoxy resin having a spiro ring, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a dicyclopentadiene type epoxy resin, a naphthol novolac type epoxy resin, a naphthol type epoxy resin, a phenol type epoxy resin, a styrene type epoxy, Naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, and the like. Among these, the naphthol type epoxy resin is preferable as the component (B) from the viewpoint of remarkably obtaining the effect of the present invention.

The resin composition preferably contains, as the component (B), an epoxy resin having 2 or more epoxy groups in 1 molecule. From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more, relative to 100% by mass of the nonvolatile component of the component (B).

The epoxy resin includes an epoxy resin which is liquid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "liquid epoxy resin") and an epoxy resin which is solid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "solid epoxy resin"). The resin composition may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin as the component (B), and preferably contains only a solid epoxy resin from the viewpoint of remarkably obtaining the desired effect of the present invention.

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

As the solid epoxy resin, a biphenol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol AF-type epoxy resin, a tetraphenylethane-type epoxy resin are preferable, and a naphthol-type epoxy resin is more preferable.

Specific examples of the solid epoxy resin include: HP4032H (naphthalene epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200", "HP-7200 HH" and "HP-7200H" (dicyclopentadiene type epoxy resins) manufactured by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" and "HP 6000" (naphthylene ether type epoxy resins) manufactured by DIC corporation; EPPN-502H (trisphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemicals); "NC 3000H", "NC 3000L" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemical company; "ESN 475V" (naphthol type epoxy resin) manufactured by NIPPON STEEL Chemical & Material co., Ltd.); ESN485 (naphthol novolac type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "YX 4000H", "YX 4000", "YL 6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical company; "YX 4000 HK" (bisphenol type epoxy resin) manufactured by Mitsubishi chemical corporation; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; PG-100 and CG-500 manufactured by Osaka gas chemical company; "YL 7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 1010" (solid bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER 1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation, and the like. These can be used alone in 1 kind, also can be combined with more than 2 kinds.

As the liquid epoxy resin, a liquid epoxy resin having 2 or more epoxy groups in 1 molecule is preferable.

The liquid epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidyl amine type epoxy resin, and an epoxy resin having a butadiene structure, and more preferably a naphthalene type epoxy resin.

Specific examples of the liquid epoxy resin include: "HP 4032", "HP 4032D" and "HP 4032 SS" (naphthalene epoxy resins) manufactured by DIC; "828 US", "jER 828 EL", "825", "EPIKOTE 828 EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi chemical company; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical corporation; "630" and "630 LSD" (glycidyl amine type epoxy resins) manufactured by mitsubishi chemical corporation; "ZX 1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon iron chemical Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Dailuo corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Dailuo corporation; "ZX 1658" and "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resins) manufactured by Nippon iron chemical Co., Ltd. These can be used alone in 1 kind, also can be combined with more than 2 kinds.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (B), the amount ratio thereof (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 in terms of mass ratio. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within the above range, the desired effects of the present invention can be remarkably obtained. In addition, when used in the form of a resin sheet, the sheet generally has appropriate adhesiveness. In addition, when used in the form of a resin sheet, sufficient flexibility is obtained, and handling properties are improved. In addition, a cured product having sufficient breaking strength can be usually obtained.

(B) The epoxy equivalent of the component is preferably 50g/eq to 5000g/eq, more preferably 50g/eq to 3000g/eq, even more preferably 80g/eq to 2000g/eq, and even more preferably 110g/eq to 1000g/eq. By setting the content to the above range, the crosslinking density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be formed. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the component (B) is preferably 100 to 5000, more preferably 200 to 3000, and still more preferably 250 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention.

From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and good insulation reliability, the content of the component (B) is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 15 mass% or more, assuming that the nonvolatile component in the resin composition is 100 mass%. The upper limit of the content of the epoxy resin is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

The content of the component (B) is preferably 20 mass% or more, more preferably 25 mass% or more, further preferably 30 mass% or more, preferably 50 mass% or less, more preferably 45 mass% or less, and further preferably 40 mass% or less, when the resin component in the resin composition is 100 mass%, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and good insulation reliability.

Active ester curing agent (C)

The resin composition contains (C) an active ester curing agent. By using the active ester-based curing agent, the dielectric characteristics can be improved and the peel strength can be improved. (C) The components can be used singly or in combination of 2 or more.

As the active ester curing agent (C), a compound having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, can be preferably used. 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-based curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac (phenol novolac), and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensation of 1 molecule of dicyclopentadiene and 2 molecules of phenol.

Specifically, examples of the component (C) include a dicyclopentadiene type active ester-based curing agent, a naphthalene type active ester-based curing agent, an active ester-based curing agent containing an acetylate of a novolac resin, an active ester-based curing agent containing a benzoyl of a novolac resin, and the like. The naphthalene type active ester curing agent contains a naphthalene structure. Among these, the component (C) is more preferably 1 or more selected from the group consisting of a dicyclopentadiene type active ester-based curing agent and a naphthalene type active ester-based curing agent, and further preferably a naphthalene type active ester-based curing agent. As the dicyclopentadiene type active ester-based curing agent, an active ester-based curing agent containing a dicyclopentadiene type diphenol structure is preferable. The "dicyclopentadiene type diphenol structure" refers to a divalent structural unit formed from phenylene-dicyclopentylene (ジシクロペンチレン) -phenylene.

Commercially available products of (C) the active ester-based curing agent include: "EXB 9451", "EXB 9460S", "HPC-8000-65T", "HPC-8000H-65 TM" and "EXB-8000L-65 TM" (manufactured by DIC corporation) as active ester-based curing agents containing dicyclopentadiene type diphenol structure; "EXB 9416-70 BK", "EXB-8100L-65T", "EXB-8150-65T", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC Co., Ltd.), and "PC 1300-02-65T" (manufactured by Air Water Co., Ltd.) as naphthalene type active ester curing agents; "DC 808" (manufactured by mitsubishi chemical corporation) as an active ester-based curing agent containing an acetylated novolac resin; "YLH 1026" (manufactured by mitsubishi chemical corporation) which is an active ester-based curing agent containing a benzoyl compound of a novolac resin; "DC 808" (manufactured by mitsubishi chemical corporation) as an active ester-based curing agent which is an acetylated product of a novolac resin; "YLH 1026" (manufactured by mitsubishi chemical corporation), "YLH 1030" (manufactured by mitsubishi chemical corporation), and "YLH 1048" (manufactured by mitsubishi chemical corporation), which are active ester-based curing agents for benzoylates of novolac resins; "EXB-8500-65T" (manufactured by DIC corporation); and so on.

The active ester group equivalent of the (C) active ester-based curing agent is preferably 50g/eq to 500g/eq, more preferably 50g/eq to 400g/eq, and even more preferably 100g/eq to 300g/eq, from the viewpoint of obtaining a cured product which not only can reduce the dielectric loss tangent but also has excellent adhesion. The active ester group equivalent is the mass of an active ester-based curing agent containing 1 equivalent of active ester groups.

(B) The amount ratio of the epoxy resin to the active ester-based curing agent (C) is preferably 0.01 or more, more preferably 0.3 or more, further preferably 0.5 or more, preferably 5 or less, more preferably 3 or less, and further preferably 2 or less in terms of the ratio of [ total number of active groups of active ester-based curing agent ]/[ total number of epoxy groups of epoxy resin ]. The "number of epoxy groups of the epoxy resin" herein is a value obtained by adding all the values obtained by dividing the mass of the nonvolatile components of the epoxy resin present in the resin composition by the epoxy equivalent weight. The "number of active groups of the active ester-based curing agent" is a value obtained by adding all the values obtained by dividing the mass of nonvolatile components of the active ester-based curing agent present in the resin composition by the active ester group equivalent. When the amount ratio of the epoxy resin to the active ester-based curing agent is within the above range, the effects of the present invention can be remarkably obtained.

The content of the (C) active ester-based curing agent is preferably 1 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more, when the nonvolatile component in the resin composition is 100 mass%, from the viewpoint of obtaining a cured product which not only can reduce the dielectric characteristics but also has excellent peel strength. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less.

The content of the active ester-based curing agent (C) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less, based on 100% by mass of the resin component in the resin composition, from the viewpoint of obtaining a cured product having excellent peel strength while reducing dielectric properties.

< (D) resin containing radically polymerizable unsaturated group

The resin composition may contain, as an optional component, a resin containing a radical polymerizable unsaturated group (D) in addition to the above-mentioned components. By incorporating (D) a resin containing a radical polymerizable unsaturated group in the resin composition, a cured product having low dielectric characteristics and excellent peel strength can be obtained. (D) The components (A) to (C) are not included in the component (A).

(D) The radical polymerizable unsaturated group contained in the component means a group containing an unsaturated bond exhibiting radical polymerizability. Examples of the radical polymerizable unsaturated group include groups containing an ethylenic double bond. The component (D) containing such a radically polymerizable unsaturated group can be radically polymerized by heat or active energy rays to cure the resin composition.

Examples of the radical polymerizable unsaturated group include: maleimido, vinyl, vinylphenyl, acryloyl, methacryloyl, fumaryl, maleoyl, benzocyclobutene, allyl, and the like. Among them, as the component (D), a maleimide group is preferable from the viewpoint of remarkably obtaining the effect of the present invention. (D) The number of radical polymerizable unsaturated groups contained in the component (a) is usually 1 or more, preferably 2 or more. (D) When component (b) contains 2 or more radically polymerizable unsaturated groups, the 2 or more radically polymerizable unsaturated groups may be the same or different.

As the component (D), a resin containing an aromatic ring in the molecule is preferably used. Therefore, component (D) is preferably a resin containing an aromatic ring and a radical polymerizable unsaturated group. (D) The aromatic ring contained in the component (A) may be an aromatic carbocyclic ring or an aromatic heterocyclic ring. The aromatic ring may be a monocyclic aromatic ring, a fused aromatic ring in which 2 or more monocyclic aromatic rings are fused, or a fused aromatic ring in which 1 or more monocyclic aromatic rings are fused with 1 or more monocyclic non-aromatic rings. Examples of the aromatic ring include: monocyclic aromatic rings such as benzene rings and pyridine rings; a fused aromatic ring such as an indane ring, a fluorene ring, a naphthalene ring, etc. Among them, the aromatic ring is preferably an aromatic carbocyclic ring. The number of carbon atoms of the aromatic carbon ring is preferably 6 or more and 10 or less.

(D) Substituents may be bonded to the aromatic ring included in the component. The number of substituents bonded to 1 aromatic ring may be 1, or 2 or more. When the number of the substituents is 2 or more, the 2 or more substituents may be the same or different.

Examples of the substituent include an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a halogen atom, a hydroxyl group, and a mercapto group.

The number of carbon atoms of the alkyl group is preferably 1 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group.

The number of carbon atoms of the alkyloxy group is preferably 1 to 10. Examples of the alkyloxy group include methoxy, ethoxy, propoxy, and butoxy.

The number of carbon atoms of the alkylthio group is preferably 1 to 10. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group.

The number of carbon atoms of the aryl group is preferably 6 to 10. Examples of the aryl group include a phenyl group and a naphthyl group.

The number of carbon atoms of the aryloxy group is preferably 6 to 10. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, and the like.

The number of carbon atoms of the arylthio group is preferably 6 to 10. Examples of the arylthio group include phenylthio group and naphthylthio group.

The number of carbon atoms of the cycloalkyl group is preferably 3 to 10. Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and cycloheptyl.

Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom and the like.

Among them, the aromatic ring contained in the component (D) is preferably not bonded with a substituent or bonded with an alkyl group.

(D) The number of aromatic rings contained in the component (a) is usually 1 or more, preferably 2 or more. (D) When component (A) contains 2 or more aromatic rings, the 2 or more aromatic rings may be the same or different.

(D) The components can be used singly or in combination of 2 or more.

(D) One preferred embodiment of component (b) is a resin containing a maleimide group. The maleimide group-containing resin preferably further contains an aromatic ring. The resin containing a maleimide group is a resin belonging to the component (D), and therefore does not include a resin belonging to the component (A). The maleimide group-containing resin may be used alone in 1 kind, or in combination with 2 or more kinds.

The maleimide group-containing resin is preferably 1 or more selected from the following (D-1) to (D-3):

(D-1) a maleimide compound comprising an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of the maleimide group,

(D-2) a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group, and (D-3) a maleimide compound comprising a trimethylindane skeleton.

The term "directly" as used herein means that no other group is present between the nitrogen atom of the maleimide group and the aliphatic group having 5 or more carbon atoms in the component (D-1); in the component (D-2), it means that no other group is present between the nitrogen atom of the maleimide and the aromatic ring.

The component (D-1) is a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of the maleimide compound. The component (D-1) can be obtained, for example, by subjecting a component containing an aliphatic amine compound (e.g., a diamine compound having a dimer acid skeleton), maleic anhydride, and, if necessary, a tetracarboxylic dianhydride to an imidization reaction.

Examples of the aliphatic group having 5 or more carbon atoms include an alkyl group, an alkylene group, and an alkenylene group.

The alkyl group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, preferably 50 or less carbon atoms, more preferably 45 or less carbon atoms, and still more preferably 40 or less carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear. Examples of such an alkyl group include pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. The alkyl group having 5 or more carbon atoms may have a substituent of an alkylene group having 5 or more carbon atoms. The alkyl group having 5 or more carbon atoms may be a part of an alkenyl group or a part of a polyene (alkapolyenyl) (the number of double bonds is preferably 2).

The alkylene group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, preferably 50 or less carbon atoms, more preferably 45 or less carbon atoms, and further preferably 40 or less carbon atoms. The alkylene group may be linear, branched or cyclic, and is preferably linear. Here, the cyclic alkylene group is a concept including "a case of being composed only of a cyclic alkylene group" and "a case of including both a linear alkylene group and a cyclic alkylene group". Examples of the alkylene group include a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, a hexadecylene group, 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 alkylene group having 5 or more carbon atoms may be a part of an alkenylene group or a part of an alkenylene (alkarylene) (the number of double bonds is preferably 2).

The number of carbon atoms of the alkenylene 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 further preferably 40 or less. The alkenylene group may be linear, branched or cyclic, and is preferably linear. Here, the cyclic alkenylene group is a concept including "a case where the cyclic alkenylene group is composed only of" and "a case where both of the linear alkenylene group and the cyclic alkenylene group are included". Examples of such alkenylene groups include pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, heptadecenylene, thirty-hexaenylene, a group having an octenylene-cyclohexenylene structure, a group having an octenylene-cyclohexenylene-octenylene structure, and a group having a propenylene-cyclohexenylene-octenylene structure.

As the component (D-1), preferred are compounds represented by the following formula (D-1-1):

[ chemical formula 7]

In the general formula (D-1-1), M represents an optionally substituted divalent aliphatic group having 5 or more carbon atoms, and L represents a single bond or a divalent linking group.

M represents a divalent aliphatic group having 5 or more carbon atoms and optionally having a substituent. The divalent aliphatic group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, preferably 50 or less carbon atoms, more preferably 45 or less carbon atoms, and further preferably 40 or less carbon atoms. The aliphatic group may be linear, branched or cyclic, and is preferably linear. Here, the cyclic aliphatic group is a concept including "a case where the cyclic aliphatic group is formed only" and "a case where both of the linear aliphatic group and the cyclic aliphatic group are included". Examples of the divalent aliphatic group include an alkylene group, an alkenylene group, and a polyalkenylene group (more preferably, the number of double bonds is 2). As regards alkylene and alkenylene, the same applies as above.

Examples of the substituent for M include: halogen atom, -OH, -O-C_1-10Alkyl, -N (C)_1-10Alkyl radical)₂、C_1-10Alkyl radical, C_2-30Alkenyl radical, C_2-30Alkynyl, C_6-10Aryl, -NH₂、-CN、-C(O)O-C_1-10Alkyl, -COOH, -C (O) H, -NO₂And the like. Here, the term "C_x-y"(x and y are positive integers, and x < y is satisfied) means that the number of carbon atoms of the organic group described immediately after the term is x to y. For example, "C_1-10The expression "alkyl" denotes 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 includes a spiro ring and a condensed ring. The substituent is preferably an alkyl group having 5 or more carbon atoms.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include alkylene, alkenylene, alkynylene, arylene, -C (═ O) -O-, -NR⁰-(R⁰Hydrogen atom, alkyl group having 1 to 3 carbon atoms), oxygen atom, sulfur atom, C (═ O) NR⁰A divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, a combination of 2 or more divalent groups of these, and the like. The alkylene group, the alkenylene group, the alkynylene group, the arylene group, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, and a group formed by combining 2 or more divalent groups may have an alkyl group having 5 or more carbon atoms as a substituent. The term "divalent group derived from phthalimide" refers to a divalent group derived from phthalimide, specifically, a group represented by the general formula (D-1-2). The divalent group derived from pyromellitic diimide means a divalent group derived from pyromellitic diimide, specifically, a group represented by the general formula (D-1-3). Wherein "+" represents a bond;

[ chemical formula 8]

The alkylene group as the divalent linking group in 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 linear, branched or cyclic. Examples of such alkylene groups include methylethylene, cyclohexylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, hexadecylene, 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 in L is preferably an alkenylene group having 2 to 50 carbon atoms, more preferably an alkenylene group having 2 to 45 carbon atoms, and particularly preferably an alkenylene group having 2 to 40 carbon atoms. The alkenylene group may be linear, branched or cyclic. Examples of such alkenylene groups include methylvinylene, cyclohexenylene, pentenylene, hexenylene, heptenylene, and octenylene.

The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 50 carbon atoms, more preferably an alkynylene group having 2 to 45 carbon atoms, and particularly preferably an alkynylene group having 2 to 40 carbon atoms. The alkynylene group may be linear, branched or cyclic. Examples of such an alkynylene group include methylacetylene, cyclohexylene, pentylene, hexylene, heptylene, octylene, and the like.

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 yet more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

The alkylene group, alkenylene group, alkynylene group, and arylene group as the divalent linking group in L may have a substituent. As the substituent, an alkyl group having 5 or more carbon atoms is preferable, as in the substituent of M in the general formula (B2-1-1).

Examples of the group consisting of a combination of 2 or more divalent groups in L include: a divalent group composed of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group composed of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a divalent group composed of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; and so on. Groups composed of a combination of 2 or more divalent groups can form a ring such as a condensed ring by the combination of the groups. In addition, the group formed by combining more than 2 divalent groups can be a repeating unit with the number of repeating units being 1-10.

In the general formula (D-1-1), L is preferably an oxygen atom, an arylene group having 6 to 24 carbon atoms which may be substituted, an alkylene group having 1 to 50 carbon atoms which may be substituted, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, or a divalent group formed by combining 2 or more of these groups. Among them, as L, more preferred are: an alkylene group; a divalent group having a structure of alkylene-divalent group derived from phthalimide-oxygen atom-divalent group derived from phthalimide; a divalent group having a structure of alkylene-a divalent group derived from phthalimide-oxygen atom-arylene-alkylene-arylene-oxygen atom-a divalent group derived from phthalimide; a divalent group having a structure of alkylene-a divalent group derived from pyromellitic diimide; a divalent group having a structure of alkynylene-a divalent group derived from phthalimide-an oxygen atom-a divalent group derived from phthalimide; a divalent group having the structure alkynylene-a divalent group derived from phthalimide-oxygen atom-arylene-alkynylene-arylene-oxygen atom-a divalent group derived from phthalimide; divalent radicals having the structure alkynylene-a divalent radical derived from pyromellitic diimide.

The maleimide resin represented by the general formula (D-1-1) is preferably a maleimide resin represented by the general formula (D-1-4);

[ chemical formula 9]

In the general formula (D-1-4), M¹Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and each Z independently represents a divalent aliphatic 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.

M¹Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M¹The same as M in the general formula (D-1-1).

Each Z independently represents a divalent aliphatic 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. Examples of the divalent aliphatic group in Z include an alkylene group, an alkenylene group, and a polyalkenylene group (more preferably, the number of double bonds is 2). The divalent aliphatic group may be any of a chain, a branched chain and a cyclic group, and among them, a cyclic divalent aliphatic group having 5 or more carbon atoms, which is optionally substituted, is preferable.

The number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. Examples of such alkylene groups include: a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.

The number of carbon atoms of the alkenylene 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 further preferably 40 or less. The alkenylene group may be linear, branched or cyclic, and is preferably linear. Here, the cyclic alkenylene group is a concept including "a case where the cyclic alkenylene group is composed only of" and "a case where both of the linear alkenylene group and the cyclic alkenylene group are included". Examples of such alkenylene groups include: pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, heptadecenylene, thirty-hexaenylene, a group having an octenylene-cyclohexenylene structure, a group having an octenylene-cyclohexenylene-octenylene structure, a group having a propenylene-cyclohexenylene-octenylene structure, and the like.

Examples of the aromatic ring in the divalent group having an aromatic ring represented by Z include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic diimide ring, an aromatic heterocycle, and the like, and a benzene ring, a phthalimide ring, and a pyromellitic diimide ring are preferable. That is, as the divalent group having an aromatic ring, a divalent group having a benzene ring which may be substituted, a divalent group having a phthalimide ring which may be substituted, and a divalent group having a pyromellitic diimide ring which may be substituted are preferable. Examples of the divalent group having an aromatic ring include a group composed of a combination of a divalent group derived from phthalimide and an oxygen atom; a group composed of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group composed of an alkylene group and a divalent group derived from pyromellitic diimide; a divalent group derived from pyromellitic diimide; a group composed of a divalent group derived from phthalimide and an alkylene group; and the like. The arylene group is the same as the arylene group in the divalent linking group represented by L in the general formula (D-1-1).

The alkylene group represented by Z and the divalent group having an aromatic ring may have a substituent. The substituent is the same as the substituent which M in the general formula (D-1-1) may have.

Specific examples of the group represented by Z include the following groups. In the formula, "+" represents a bond (chemical bond);

[ chemical formula 10]

[ chemical formula 11]

The compound represented by the general formula (D-1-1) is preferably any of the compounds represented by the general formula (D-1-5) and the compounds represented by the general formula (D-1-6);

[ chemical formula 12]

In the general formula (D-1-5), M²And M³Each independently represents a divalent aliphatic group having 5 or more carbon atoms and optionally having a substituent, R⁴⁰Each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group formed by combining 2 or more of these groups. t1 represents an integer of 1 to 10;

in the general formula (D-1-6), M⁴、M⁶And M⁷Each independently represents an optionally substituted aliphatic group having 5 or more carbon atoms, M⁵Each independently represents a divalent group having an aromatic ring optionally having a substituent, R⁴¹And R⁴²Each independently represents 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.

M²And M³Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M²And M³As with the divalent aliphatic group having 5 or more carbon atoms represented by M in the general formula (D-1-1), triacontahenylene (ヘキサトリアコンチニレン group) and triacontahlylene (ヘキサトリアコンチレン group) are preferable.

R⁴⁰Each independently represents an oxygen atom, an arylene group, an alkylene group, or a compound of2 or more divalent groups of these groups. The arylene group and the alkylene group are the same as those in the divalent linking group represented by L in the general formula (D-1-1). As R⁴⁰Preferably, the group is a combination of 2 or more divalent groups or an oxygen atom.

As R⁴⁰The group composed of a combination of 2 or more kinds of divalent groups in (1) includes a combination of an oxygen atom, an arylene group, and an alkylene group. Specific examples of the group consisting of a combination of 2 or more kinds of divalent groups include the following groups. Wherein "+" represents a bond;

[ chemical formula 13]

M⁴、M⁶And M⁷Each independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent. M⁴、M⁶And M⁷As with the aliphatic group having 5 or more carbon atoms optionally having a substituent represented by M in the general formula (D-1-1), a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group are preferable, and an octyl group is more preferable.

M⁵Each independently represents a divalent group having an aromatic ring optionally having a substituent. M⁵As with the optionally substituted divalent group having an aromatic ring represented by Z in the general formula (D-1-4), a combination of an alkylene group and a divalent group derived from pyromellitic diimide is preferable; the group comprising a combination of a divalent group derived from phthalimide and an alkylene group, and more preferably a combination of an alkylene group and a divalent group derived from pyromellitic diimide. The arylene group and the alkylene group are the same as those in the divalent linking group represented by L in the general formula (D-1-1).

As M⁵Specific examples of the group include the following groups. Wherein "+" represents a bond; [ chemical formula 14]

R⁴¹And R⁴²Each independently represents an alkyl group having 5 or more carbon atoms. R⁴¹And R⁴²As with the alkyl group having 5 or more carbon atoms, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group are preferable, and a hexyl group and an octyl group are more preferable.

u1 and u2 each independently represent an integer of 1 to 15, preferably an integer of 1 to 10.

Specific examples of the component (D-1) include the following compounds (D-i) to (D-iii), and are not limited to these specific examples. Wherein v represents an integer of 1 to 10;

[ chemical formula 15]

[ chemical formula 16]

Specific examples of the component (D-1) include "BMI 1500" (a compound of the formula (D-i) ")," BMI1700 "(a compound of the formula (D-ii)") and "BMI 689" (a compound of the formula (D-iii)), which are manufactured by Designer Molecules Inc.

The weight average molecular weight (Mw) of the component (D-1) is preferably 150 to 5000, more preferably 300 to 2500.

The maleimide group equivalent of the component (D-1) is preferably 50g/eq to 2000g/eq, more preferably 100g/eq to 1000g/eq, and still more preferably 150g/eq to 500g/eq, from the viewpoint of significantly obtaining the desired effect of the present invention. The maleimide group equivalent is the mass of the (D-1) component containing 1 equivalent of maleimide group.

The component (D-2) is a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide compound. The component (D-2) can be obtained, for example, by subjecting a component containing an aromatic amine compound (such as an aromatic diamine compound) and maleic anhydride to an imidization reaction.

The aromatic ring may be carbocyclic or heterocyclic. Examples of the aromatic ring include monocyclic aromatic rings such as benzene ring, furan ring, thiophene ring, pyrrole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, and pyrazine ring; a fused ring formed by fusing at least 2 monocyclic aromatic rings such as a naphthalene ring, an anthracene ring, a benzofuran ring, an isobenzofuran ring, an indole ring, an isoindole ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, a benzoxazole ring, a benzisoxazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, and a phthalazine ring; a fused ring in which 1 or more monocyclic non-aromatic rings are fused to 1 or more monocyclic aromatic rings, such as an indane ring, a fluorene ring, and a tetralin ring. Among these, as the aromatic ring, a monocyclic aromatic ring is preferable, and a benzene ring is more preferable.

As the component (D-2), a maleimide compound represented by the following formula (D-2-1);

[ chemical formula 17]

In the formula, R^cEach independently represents a substituent; x^cEach independently represents a single bond, alkylene, alkenylene, -O-, -CO-, -S-, -SO-, -SO₂-, -CONH-, -NHCO-, -COO-, or-OCO- (preferably a single bond or alkylene); z^cEach independently represents a non-aromatic ring optionally having a substituent, or an aromatic ring optionally having a substituent (preferably an aromatic ring optionally having a substituent, particularly preferably a benzene ring optionally having a substituent); s represents an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and further preferably an integer of 1 to 20); t1 each independently represents 0 or an integer of 1 or more; u each independently represents an integer of 0 to 2 (preferably 0). Particularly preferred are compounds represented by the formulae (D-2-2) to (D-2-5).

[ chemical formula 18]

In the formula, R^c1、R^c2And R^c3Each independently represents an alkyl group; x^c1And X^c2Each independently represents a single bond or an alkylene group; s represents an integer of 1 or more (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and further preferably an integer of 1 to 20); t' represents an integer of 1 to 5; v1, v2 and v3 each independently represent an integer of 0 to 2 (preferably 0). The s unit, t' unit, v1 unit, v2 unit, and v3 unit may be the same or different.

In another embodiment, the component (D-2) is preferably a compound represented by the following formula (D-2-6);

[ chemical formula 19]

In the formula, R³¹And R³⁶Represents a maleimido group, R³²、R³³、R³⁴And R³⁵Each independently represents a hydrogen atom, an alkyl group, or an aryl group, and each D independently represents a divalent aromatic group. m1 and m2 each independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

R in the formula (D-2-6)³²、R³³、R³⁴And R³⁵Each independently represents a hydrogen atom, an alkyl group, or an aryl group, preferably a hydrogen atom.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an isopropyl group.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a single ring or a condensed ring. Examples of such aryl groups include phenyl, naphthyl, and anthracenyl.

The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, -OH, -O-C_1-6Alkyl, -N (C)_1-10Alkyl radical)₂、C_1-10Alkyl radical, C_6-10Aryl, -NH₂、-CN、-C(O)O-C_1-10Alkyl, -COOH, -C (O) H, -NO₂And the like. Here, the term "C_p-q"(p and q are positive integers, and p < q) means that the organic group described immediately after the term has p to q carbon atoms. For example, "C_1-10The expression "alkyl" denotes 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 includes a spiro ring and a condensed ring.

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

D in the formula (D-2-6) represents a divalent aromatic group. Examples of the divalent aromatic group include phenylene, naphthylene, anthrylene, aralkyl, biphenylene, and biphenylaralkyl groups, and among them, biphenylene and biphenylaralkyl groups are preferable, and biphenylene is more preferable. The divalent aromatic group may have a substituent. As a substituent, with R in the formula (D-2-6)³²The same applies to the substituents which the alkyl group may have.

m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, still more preferably 1 to 2, and yet more preferably 1.

a represents an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, and further preferably 1 to 5.

As the component (D-2), a resin represented by the formula (D-2-7):

[ chemical formula 20]

In the formula, R³⁷And R³⁸Represents a maleimide group. a1 represents an integer of 1 to 100.

a1 is the same as a in the formula (D-2-6), and the preferred ranges are the same.

As the commercially available products of the component (D-2), there may be mentioned, for example: "MIR-3000-70 MT" manufactured by Nippon chemical company; "BMI-50P" manufactured by K.I. Kagaku Co., Ltd; "BMI-1000", "BMI-1000H", "BMI-1100H", "BMI-4000", "BMI-5100", manufactured by Dahe chemical industry Co., Ltd; "BMI-4, 4' -BPE" manufactured by K.I. Kabushiki Kaisha "," BMI-70 ", and" BMI-80 "manufactured by K.I. Kabushiki Kaisha.

The weight average molecular weight (Mw) of the component (D-2) is preferably 150 to 5000, more preferably 300 to 2500.

The equivalent weight of the functional group of the maleimide group of the component (D-2) is preferably 50 to 2000g/eq, more preferably 100 to 1000g/eq, still more preferably 150 to 500g/eq, and particularly preferably 200 to 300g/eq.

The component (D-3) is a maleimide compound having a trimethylindan skeleton. The trimethylindan skeleton is a skeleton represented by the following formula (D-3-1).

[ chemical formula 21]

A substituent may be bonded to the benzene ring included in the trimethylindane skeleton. Examples of the substituent include an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a halogen atom, a hydroxyl group, and a mercapto group; the number of carbon atoms of the alkyl group is preferably 1 to 10. Examples of the alkyl group include methyl, ethyl, propyl, n-butyl, tert-butyl, and the like;

the number of carbon atoms of the alkyloxy group is preferably 1 to 10. Examples of the alkyloxy group include methoxy, ethoxy, propoxy, butoxy, and the like;

the number of carbon atoms of the alkylthio group is preferably 1 to 10. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group;

the number of carbon atoms of the aryl group is preferably 6 to 10. Examples of the aryl group include phenyl, naphthyl, and the like;

the number of carbon atoms of the aryloxy group is preferably 6 to 10. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, and the like;

the number of carbon atoms of the arylthio group is preferably 6 to 10. Examples of the arylthio group include phenylthio group, naphthylthio group and the like; the number of carbon atoms of the cycloalkyl group is preferably 3 to 10. Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, and the like; examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom and the like.

Among the above substituents, hydrogen atoms of alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, and cycloalkyl groups may be substituted with halogen atoms.

The number of substituents bonded to 1 benzene ring included in the trimethylindane skeleton may be 1 or 2 or more. The number of substituents bonded to the benzene ring included in the trimethylindane skeleton is usually 0 or more and 3 or less. When the number of the substituents is 2 or more, these 2 or more substituents may be the same or different. Among them, it is preferable that no substituent is bonded to the benzene ring contained in the trimethylindane skeleton.

The number of trimethylindan skeletons contained in 1 molecule of the component (D-3) may be 1, or 2 or more. The upper limit may be, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

The component (D-3) preferably contains not only the above-mentioned trimethylindan skeleton but also an aromatic ring skeleton. The number of ring-forming carbon atoms of the aromatic ring skeleton is preferably 6 to 10. Examples of the aromatic ring skeleton include a benzene ring skeleton and a naphthalene ring skeleton. The number of the aromatic ring skeleton contained in 1 molecule of the component (D-3) is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 4 or less, and particularly preferably 3 or less. When the component (D-3) contains not only a trimethylindan skeleton but also 2 or more aromatic ring skeletons, these aromatic ring skeletons may be the same or different.

The aromatic ring in the aromatic ring skeleton may have a substituent bonded thereto. Examples of the substituent include a substituent which can be bonded to a benzene ring included in the trimethylindane skeleton, and a nitro group. The number of substituents bonded to 1 aromatic ring may be 1, or 2 or more. The number of substituents bonded to the aromatic ring is usually 0 or more and 4 or less. When the number of the substituents is 2 or more, these 2 or more substituents may be the same or different.

The component (D-3) preferably contains not only the above-mentioned trimethylindan skeleton but also a divalent aliphatic hydrocarbon group. In particular, when the (D-3) component contains an aromatic ring skeleton other than the benzene ring contained in the trimethylindane skeleton, the (D-3) component preferably contains a divalent aliphatic hydrocarbon group. In this case, the divalent aliphatic hydrocarbon group preferably links a benzene ring included in the trimethylindane skeleton and an aromatic ring skeleton. In addition, the divalent aliphatic hydrocarbon group preferably connects the aromatic ring skeletons to each other.

The number of carbon atoms of the divalent aliphatic hydrocarbon group is preferably 1 or more, preferably 12 or less, more preferably 8 or less, and particularly preferably 5 or less. The divalent aliphatic hydrocarbon group is more preferably an alkylene group which is a saturated aliphatic hydrocarbon group. Examples of the divalent aliphatic hydrocarbon group include: linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; ethylidene (-CH (CH)₃) -) propylidene (-CH (CH)₂CH₃) -) isopropylidene (-COOR-), C (-CH (CH)₃)₂-) ethylmethylmethylene (-C (CH)₃)(CH₂CH₃) -) diethyl methylene (-C (CH)₂CH₃)₂-) and the like; and the like. When (B2-3) the maleimide compound containing a trimethylindan skeleton contains not only a trimethylindan skeleton but also 2 or more divalent aliphatic hydrocarbon groups, these divalent aliphatic hydrocarbon groups may be the same or different.

The component (D-3) preferably has a structure represented by the following formula (D-3-2). The entirety of the (D-3) component may have a structure represented by formula (D-3-2), or a part of the (D-3) component may have a structure represented by formula (D-3-2);

[ chemical formula 22]

(wherein Ar is^a1Represents a divalent aromatic hydrocarbon group optionally having a substituent; r^a1Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; r^a2Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; r^a3Each independently represents a divalent aliphatic hydrocarbon group; n is_a1Represents a positive integer; n is_a2Each independently represents an integer of 0 to 4; n is_a3Each independently represents an integer of 0 to 3. R^a1The hydrogen atoms of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group, and the cycloalkyl group in (a) may be substituted with a halogen atom. R^a2The hydrogen atoms of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group, and the cycloalkyl group in (a) may be substituted with a halogen atom. n is_a2When 2 to 4, R^a1May be the same or different within the same ring. n is_a3When 2 to 3, R^a2May be the same or different within the same ring).

In the formula (D-3-2), Ar^a1Represents a divalent aromatic hydrocarbon group optionally having a substituent. The number of carbon atoms of the divalent aromatic hydrocarbon group is preferably 6 or more, preferably 20 or less, and more preferablyPreferably 16 or less. Examples of the divalent aromatic hydrocarbon group include phenylene and naphthylene. Examples of the substituent which the divalent aromatic hydrocarbon group may have include an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, and a mercapto group. The hydrogen atom of each substituent may be further substituted with a halogen atom. Specific examples of these substituents include, for example, the same substituents as those that can be bonded to the benzene ring contained in the trimethylindane skeleton. When the divalent aromatic hydrocarbon group has a substituent, the number of the substituent is preferably 1 to 4. When the number of substituents contained in the divalent aromatic hydrocarbon group is 2 or more, these 2 or more substituents may be the same or different. Wherein Ar is^a1Divalent aromatic hydrocarbon groups having no substituent are preferable.

In the formula (D-3-2), R^a1Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group. The hydrogen atoms of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group, and the cycloalkyl group may be substituted with a halogen atom. Specific examples of these groups include the same ones as those of the substituents which can be bonded to the benzene ring contained in the trimethylindane skeleton. Wherein R is^a1More preferably 1 or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

In the formula (D-3-2), R^a2Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atomsA group, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group. The hydrogen atoms of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group, and the cycloalkyl group may be substituted with a halogen atom. Specific examples of these groups include the same ones as those of the substituents which can be bonded to the benzene ring contained in the trimethylindane skeleton. Wherein R is^a2More preferably 1 or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

In the formula (D-3-2), R^a3Each independently represents a divalent aliphatic hydrocarbon group. Preferred ranges of divalent aliphatic hydrocarbon groups are as described above.

In the formula (D-3-2), n_a1Representing a positive integer. n is_a1Preferably 1 or more, preferably 10 or less, and more preferably 8 or less.

In the formula (D-3-2), n_a2Each independently represents an integer of 0 to 4. n is_a2Preferably 2 or 3, more preferably 2. A plurality of n_a2Although it may be different, it is preferably the same. n is_a2When it is 2 or more, plural R^a1May be the same or different within the same ring.

In the formula (D-3-2), n_a3Each independently represents an integer of 0 to 3. A plurality of n_a3Although it may be different, it is preferably the same. n is_a3Preferably 0.

The component (D-3) particularly preferably has a structure represented by the following formula (D-3-3). The entirety of the (D-3) component may have a structure represented by formula (D-3-3), or a part of the (D-3) component may have a structure represented by formula (D-3-3);

[ chemical formula 23]

(in the formula, R^b1Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, or a C1 to E10 alkylthio groups, 6 to 10 aryl groups, 6 to 10 aryloxy groups, 6 to 10 arylthio groups, 3 to 10 cycloalkyl groups, halogen atoms, nitro groups, hydroxyl groups, or mercapto groups; r^b2Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; n is_b1Represents a positive integer; n is_b2Each independently represents an integer of 0 to 4; n is_b3Each independently represents an integer of 0 to 3. R^b1The hydrogen atoms of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group, and the cycloalkyl group in (a) may be substituted with a halogen atom. R^b2The hydrogen atoms of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group, and the cycloalkyl group in (a) may be substituted with a halogen atom. n is_b2When 2 to 4, R^b1May be the same or different within the same ring. n is_b3When 2 to 3, R^b2May be the same or different within the same ring).

In the formula (D-3-3), R^b1、R^b2、n_b1、n_b2And n_b3Respectively react with R in the formula (D-3-2)^a1、R^a2、n_a1、n_a2And n_a3The same is true.

The (D-3) component may further comprise a structure represented by the following formula (D-3-4):

[ chemical formula 24]

In the formula (D-3-4), R^c1、R^c2、n_c2And n_c3Respectively react with R in the formula (D-3-2)^a1、R^a2、n_a2And n_a3The same is true. In addition, in the formula (D-3-4), n_c1The number of the repeating units is an integer of 1 to 20. In addition, formula (D-3-4) represents a bond. For example, in the formula (D-3-2), n is_a2Is 3 or less, and R is not bonded to 2 or more of the ortho-position and the para-position of the benzene ring bonded to the maleimide group with respect to the maleimide group^a1In the case of (2), the structure represented by the formula (D-3-4) may be included in addition to the structure represented by the formula (D-3-2). Further, for example, in the formula (D-3-3), n is_b2Is 3 or less, and R is not bonded to 2 or more of the ortho-position and the para-position of the benzene ring bonded to the maleimide group with respect to the maleimide group^b1In the case of (2), the structure represented by the formula (D-3-4) may be included in addition to the structure represented by the formula (D-3-3).

The component (D-3) may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.

The maleimide group equivalent of the component (D-3) is preferably 50 g/eq.or more, more preferably 100 g/eq.or more, particularly preferably 200 g/eq.or more, preferably 2000 g/eq.or less, more preferably 1000 g/eq.or less, and particularly preferably 800 g/eq.or less. The maleimide group equivalent represents the mass of the maleimide compound per 1 equivalent of maleimide group. When the maleimide group equivalent of the component (D-3) is within the above range, the effects of the present invention can be remarkably obtained.

The method for producing the (D-3) component is not particularly limited. The component (D-3) can be produced, for example, by the method described in Japanese patent publication Kokai publication Hei-2020-500211. By the production method described in Japanese patent laid-open publication No. 2020-500211, a maleimide compound having a distribution of the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by this method has a structure represented by the following formula (D-3-5). Therefore, the component (D-3) may contain a maleimide compound having a structure represented by the formula (D-3-5).

[ chemical formula 25]

(in the formula, R¹Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; r²Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; n is₁Represents an average number of repeating units of 0.95 to 10.0; n is₂Each independently represents an integer of 0 to 4; n is₃Each independently represents an integer of 0 to 3. R¹The hydrogen atoms of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group, and the cycloalkyl group in (a) may be substituted with a halogen atom. R²The hydrogen atoms of the alkyl group, the alkyloxy group, the alkylthio group, the aryl group, the aryloxy group, the arylthio group, and the cycloalkyl group in (a) may be substituted with a halogen atom. n is₂When 2 to 4, R¹May be the same or different within the same ring. n is₃When 2 to 3, R²May be the same or different within the same ring).

In the formula (D-3-5), R¹、R²、n₂And n₃Respectively react with R in the formula (D-3-2)^a1、R^a2、n_a2And n_a3The same is true.

In the formula (D-3-5), n₁Represents the average number of repeating units, and is in the range of 0.95 to 10.0. A group of maleimide compounds having a structure represented by the formula (D-3-5) can be obtained by the production process described in Japanese patent laid-open publication No. 2020-500211. By the average number of repeating units n in the formula (D-3-5)₁When the content is less than 1.00, the maleimide compound having a structure represented by the formula (D-3-5) obtained as described above may contain a repeat of the trimethyl indane skeletonA maleimide compound having 0 units. Accordingly, the maleimide compound having a structure represented by the formula (D-3-5) is purified to remove the maleimide compound having a repeating unit number of 0 of trimethylindane skeleton to obtain the (D-3) component, and the resin composition may contain only the obtained (D-3) component. However, the effects of the present invention can be obtained even when a maleimide compound having a repeating unit of a trimethylindane skeleton of 0 number is contained in the resin composition. In addition, in the case of omitting purification, the cost can be suppressed. Therefore, it is preferable that the maleimide compound having a repeating unit number of 0 in the trimethylindane skeleton is not removed, and the resin composition contains a maleimide compound having a structure represented by the formula (D-3-5).

In the formula (D-3-5), the average number of repeating units n₁Preferably 0.95 or more, more preferably 0.98 or more, further preferably 1.0 or more, particularly preferably 1.1 or more, preferably 10.0 or less, more preferably 8.0 or less, further preferably 7.0 or less, and particularly preferably 6.0 or less. Average number of repeating units n₁Within the above range, the effects of the present invention can be remarkably obtained. In particular, the glass transition temperature of the resin composition can be effectively increased.

The following examples are given as examples of the structure represented by the formula (D-3-5).

[ chemical formula 26]

The maleimide compound comprising the structure represented by formula (D-3-5) may further comprise the structure represented by the aforementioned formula (D-3-4). For example, in the case of the maleimide compound comprising a structure represented by the formula (D-3-5), n is in the formula (D-3-5)₂Is 3 or less, and R is not bonded to 2 or more of the ortho-position and the para-position of the benzene ring bonded to the maleimide group with respect to the maleimide group¹In the case of (2), the structure represented by the formula (D-3-4) may be included in addition to the structure represented by the formula (D-3-5).

The molecular weight distribution Mw/Mn, calculated by Gel Permeation Chromatography (GPC) measurement, of the maleimide compound having a structure represented by the formula (D-3-5) is preferably within a specific range. The molecular weight distribution is a value obtained by dividing the weight average molecular weight Mw by the number average molecular weight Mn, and is represented by "Mw/Mn". Specifically, the molecular weight distribution Mw/Mn of the maleimide compound having a structure represented by the formula (D-3-5) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, still more preferably 1.2 to 3.6, and particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw/Mn of the maleimide compound having a structure represented by the formula (D-3-5) is within the above range, the effects of the present invention can be remarkably obtained.

The average number n of repeating units in the maleimide compound having a structure represented by the formula (D-3-5)₁The amount of the maleimide compound of 0 is preferably within a specific range. The average number of repeating units n in the GPC measurement of the maleimide compound having a structure represented by the formula (D-3-5)₁The amount of the maleimide compound of 0 can be expressed in area% based on the result of the GPC measurement. Specifically, in the chromatogram obtained by the GPC measurement described above, the "average repeating unit number n" can be used₁The ratio (% by area) of the area of the peak of the maleimide compound having a structure represented by the formula (D-3-5) to the total area of the peaks of the maleimide compound having a structure represented by the formula (D-3-5) is 0₁An amount of the maleimide compound of 0. Specifically, the average number of repeating units n is calculated based on 100 area% of the total amount of the maleimide compound having a structure represented by the formula (D-3-5)₁The amount of the maleimide compound of 0 is preferably 32 area% or less, more preferably 30 area% or less, and further preferably 28 area% or less. Average number of repeating units n₁When the amount of the maleimide compound of 0 is within the above range, the effect of the present invention can be remarkably obtained.

The maleimide group equivalent of the maleimide compound having a structure represented by the formula (D-3-5) is preferably in the same range as the maleimide group equivalent of the component (D-3). When the maleimide group equivalent of the maleimide compound having a structure represented by the formula (D-3-5) is within the above range, the effects of the present invention can be remarkably obtained.

From the viewpoint of obtaining a cured product having low dielectric properties and excellent peel strength, the content of the component (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less, assuming that the nonvolatile component in the resin composition is 100% by mass.

The content of the component (D) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less, based on 100% by mass of the resin component in the resin composition, from the viewpoint of obtaining a cured product having low dielectric properties and excellent peel strength.

(E) inorganic filler

The resin composition may contain (E) an inorganic filler as an optional component in addition to the above components. By containing (E) an inorganic filler in the resin composition, a cured product having excellent dielectric characteristics can be obtained.

As a material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate tungstate, and the like. Of these, silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. In addition, spherical silica is preferable as silica. (E) The inorganic filler may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Examples of commercially available products of (E) the inorganic filler include: UFP-30 manufactured by electrochemical chemical industry; "SP 60-05" and "SP 507-05" manufactured by Nissi iron-alloy materials Corp; "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by Admatech (Admatech); UFP-30 manufactured by DENKA corporation; "Silfil (シルフィル) NSS-3N", "Silfil NSS-4N" and "Silfil NSS-5N" manufactured by Deshan, K.K.; "SC 2500 SQ", "SO-C4", "SO-C2", "SO-C1", "SC 2050-SXF", manufactured by Yatoma corporation; and so on.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the average particle diameter of the (E) inorganic filler 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 further preferably 1 μm or less.

(E) The average particle diameter of the inorganic filler can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, the measurement can be performed by: the particle size distribution of the inorganic filler was prepared on a volume basis by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size was defined as an average particle size. For the measurement sample, 100mg of the inorganic filler and 10g of methyl ethyl ketone were weighed into a vial, and dispersed for 10 minutes by ultrasonic waves. For the measurement sample, the volume-based particle size distribution of the inorganic filler was measured by a flow cell method using a laser diffraction type particle size distribution measuring apparatus with the use light source wavelengths being blue and red, and the average particle size as the median particle size was calculated from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, Ltd., and "SALD-2200" manufactured by Shimadzu, Ltd.

The specific surface area of the (E) inorganic filler is preferably 1m from the viewpoint of remarkably obtaining the desired effect of the present invention²A value of at least g, more preferably 2m²A total of 3m or more, particularly 3m²More than g. For the upper limit do notIs particularly limited, preferably 60m²Less than 50 m/g²Less than or equal to 40 m/g²The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area can be obtained by: the specific surface area of the inorganic filler was measured by adsorbing nitrogen gas on the surface of the sample using a BET full-automatic specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mountech) and calculating the specific surface area by the BET multipoint method.

The inorganic filler (E) is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include: fluorine-containing silane coupling agents such as 3,3, 3-trifluoropropyltrimethoxysilane; aminosilane-based coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyl-trimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; epoxy silane coupling agents such as 3-glycidoxypropyltrimethoxysilane; mercaptosilane coupling agents such as 3-mercaptopropyltrimethoxysilane; a silane-based coupling agent; alkoxysilanes such as phenyltrimethoxysilane; and organic silazane compounds such as hexamethyldisilazane, and titanate-based coupling agents. The surface treatment agent may be used alone in 1 kind, or may be used in combination of 2 or more kinds as desired.

Examples of commercially available surface treatment agents include: "KBM 403" (3-glycidoxypropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "KBM 803" (3-mercaptopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "KBE 903" (3-aminopropyltriethoxysilane) manufactured by shin-Etsu chemical industries, "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "SZ-31" (hexamethyldisilazane) manufactured by shin-Etsu chemical industries, and "KBM 103" (phenyltrimethoxysilane) manufactured by shin-Etsu chemical industries, and "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by shin-Etsu chemical industries, and "KBM-7103" (3,3, 3-trifluoropropyltrimethoxysilane) manufactured by shin-Etsu chemical industries.

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

The degree of surface treatment based on the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler material. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon amount per unit surface area of the inorganic filler is preferably 0.02mg/m²Above, more preferably 0.1mg/m²Above, more preferably 0.2mg/m²The above. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is preferably 1mg/m²The concentration is more preferably 0.8mg/m or less²The concentration is more preferably 0.5mg/m or less²The following.

(E) The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after the surface treatment is subjected to a washing treatment with a solvent (for example, Methyl Ethyl Ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent may be added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic washing may be performed at 25 ℃ for 5 minutes. The supernatant liquid was removed, and after drying the solid content, the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, Ltd., can be used.

The content of the inorganic filler (E) is preferably 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, preferably 75% by mass or less, preferably 70% by mass or less, preferably 65% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less, based on 100% by mass of nonvolatile components in the resin composition, from the viewpoint of remarkably obtaining the effects of the present invention.

(F) curing agent

The resin composition may further contain (F) a curing agent as an optional component in addition to the above components. However, the curing agent (F) does not contain the active ester curing agent (C). Examples of the curing agent (F) include: phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, cyanate-based curing agents, carbodiimide-based curing agents, and the like. Among them, from the viewpoint of improving insulation reliability, the (F) curing agent is preferably any 1 or more of a phenol curing agent, a naphthol curing agent, a cyanate curing agent, and a carbodiimide curing agent, more preferably any of a phenol curing agent and a naphthol curing agent, and further preferably contains a phenol curing agent. (F) The curing agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a phenolic structure (novolak structure) or a naphthol-based curing agent having a phenolic structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol curing agent is preferable, and a phenol curing agent having a triazine skeleton is more preferable.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include: "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Minghem Kaisha, "NHN", "CBN", "GPH" manufactured by Nippon Kaisha, and "SN 170", "SN 180", "SN 190", "SN 475", "SN 485", "SN 495", "SN-495V", "SN 375", "SN 395", and "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA 3018-50P", and "EXB-9500" manufactured by Nippon Kaisha.

Specific examples of the benzoxazine-based curing agent include "HFB 2006M" manufactured by Showa Polymer Co., Ltd, "P-d" and "F-a" manufactured by Shikoku Industrial Co., Ltd.

Examples of the cyanate ester-based curing agent include: bifunctional cyanate ester resins such as bisphenol A dicyanate, polyphenol cyanate ester, oligo (3-methylene-1, 5-phenylene cyanate ester), 4 '-methylenebis (2, 6-dimethylphenyl cyanate ester), 4' -ethylenediphenyldicyanate ester, hexafluorobisphenol A dicyanate ester, 2-bis (4-cyanate ester) phenylpropane, 1-bis (4-cyanate ester phenylmethane), bis (4-cyanate ester-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate ester-phenyl-1- (methylethylidene)) benzene, bis (4-cyanate ester-phenyl) sulfide, and bis (4-cyanate ester-phenyl) ether, polyfunctional cyanate ester resins derived from phenol novolac resin, cresol novolac resin, and the like, Prepolymers obtained by partially triazinating these cyanate ester resins, and the like. Specific examples of the cyanate ester-based curing agent include "PT 30" and "PT 60" (phenol novolac-type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), "BA 230" and "BA 230S 75" (prepolymer in which a part or all of bisphenol a dicyanate is triazinized to form a trimer), which are manufactured by Lonza Japan.

Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo chemical Co.

When the curing agent is contained as the component (F), the amount ratio of the epoxy resin to the active ester-based curing agent (B) and the curing agent (F) is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.3 to 1:3, and further preferably 1:0.5 to 1:2, in terms of the ratio of [ the total number of epoxy groups of the epoxy resin ]: the total number of active groups of the active ester-based curing agent (B) and the curing agent (F) ]. The "number of epoxy groups of the epoxy resin" herein is a value obtained by adding all the values obtained by dividing the mass of the nonvolatile components of the epoxy resin present in the resin composition by the epoxy equivalent weight. The term "(active group number of the active ester-based curing agent (B) and the curing agent (F)) means a value obtained by adding all of the values obtained by dividing the mass of nonvolatile components of the active ester-based curing agent and the curing agent present in the resin composition by the active group equivalent. The effect of the present invention can be remarkably obtained by adjusting the amount ratio of the component (B) and the component (F) to the epoxy resin within the above range.

When the curing agent is contained as the component (F), the amount ratio of the epoxy resin to the total curing agent (F) is preferably 1:0.01 to 1:1, more preferably 1:0.03 to 1:0.5, and still more preferably 1:0.05 to 1:0.3 in terms of the ratio of [ total number of epoxy groups of epoxy resin ]: total number of active groups of [ (F) curing agent ]. The term "(active group of F) curing agent" as used herein means a value obtained by adding all the values obtained by dividing the mass of nonvolatile components of the F curing agent present in the resin composition by the active group equivalent. When the amount ratio of the epoxy resin to the curing agent is within the above range as the component (F), the effect of the present invention can be remarkably obtained.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the (F) curing agent is preferably 1 mass% or more, more preferably 1.5 mass% or more, and still more preferably 2 mass% or more, assuming that the nonvolatile content in the resin composition is 100 mass%. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the (F) curing agent is preferably 1 mass% or more, more preferably 2 mass% or more, further preferably 3 mass% or more, preferably 10 mass% or less, more preferably 8 mass% or less, and further preferably 5 mass% or less, assuming that the resin component in the resin composition is 100 mass%.

(G) curing Accelerator

The resin composition may further contain a curing accelerator as the (G) component as an optional component in addition to the above components.

Examples of the component (G) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. (G) The components can be used singly or in combination of 2 or more.

Examples of the phosphorus-based curing accelerator include: triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., with triphenylphosphine, tetrabutylphosphonium decanoate being preferred.

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

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

As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi chemical corporation.

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

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

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the component (G) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, preferably 3% by mass or less, more preferably 1.5% by mass or less, and further preferably 1% by mass or less, when the nonvolatile component in the resin composition is taken as 100% by mass.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the component (G) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

< (H) other additives

The resin composition may contain other additives as optional components in addition to the above components. Examples of such additives include thermoplastic resins, elastomers, organic fillers, thickeners, defoaming agents, leveling agents, adhesion imparting agents, and flame retardants. These can be used alone in 1 kind, also can be used in any ratio of combination of 2 or more.

The resin composition can be produced by, for example, mixing the above components in an arbitrary order. In addition, heating and/or cooling can be performed by appropriately adjusting the temperature during the process of mixing the components. During or after the mixing of the respective components, the components may be uniformly dispersed by stirring with a stirring device such as a mixer. Further, the resin composition may be subjected to a defoaming treatment as necessary.

< Properties and uses of resin composition >

Since the resin composition contains the component (a), the component (B), and the component (C) in combination, a cured product having low dielectric characteristics, excellent peel strength even with small surface roughness, and a high glass transition temperature can be obtained.

A cured product of the resin composition obtained by heat curing at 200 ℃ for 90 minutes has a low dielectric constant Dk. Therefore, when an insulating layer is formed from the cured product, an insulating layer having a low dielectric constant can be obtained. For example, the dielectric constant Dk of a cured product obtained by curing the resin composition under the conditions described in the examples described later is preferably 3.0 or less, more preferably 2.9 or less, and still more preferably 2.8 or less. The lower limit of the dielectric constant Dk of the cured product is not particularly limited, and may be 0.1 or more. The dielectric constant of the cured product can be measured by the method described in examples.

A cured product obtained by thermally curing the resin composition at 200 ℃ for 90 minutes has a low dielectric loss tangent. Therefore, when an insulating layer is formed from the cured product, an insulating layer having a low dielectric loss tangent can be obtained. For example, the dielectric loss tangent Df of a cured product obtained by curing the resin composition under the conditions described in the examples described later is preferably 0.010 or less, more preferably 0.005 or less, and still more preferably 0.004 or less. The lower limit of the dielectric loss tangent Df of the cured product is not particularly limited, and may be 0.001 or more. The dielectric loss tangent of the cured product can be measured by the method described in examples.

The cured product obtained by thermally curing the resin composition at 200 ℃ for 90 minutes can improve the peel strength of the plating layer, which indicates the adhesion strength with the plated conductor layer. Therefore, when the insulating layer is formed from the cured product, an insulating layer having high peel strength with respect to the conductor layer can be obtained. For example, when the insulating layer and the plated conductor layer are formed by the method described in the later-described examples, the peel strength between the insulating layer and the conductor layer may be preferably 0.2kgf/cm or more, more preferably 0.3kgf/cm or more, and particularly preferably 0.4kgf/cm or more. The upper limit of the adhesiveness is not particularly limited, and may be, for example, 10.0kgf/cm or less. The peel strength can be measured by the method described in examples.

A cured product obtained by thermally curing the resin composition at 200 ℃ for 90 minutes exhibits such a characteristic that the arithmetic average roughness (Ra) of the surface of the cured product after the roughening treatment can be reduced. Therefore, the insulating layer having a surface with a small arithmetic average roughness (Ra) after the roughening treatment can be obtained. The arithmetic average roughness (Ra) is preferably 100nm or less, more preferably 80nm or less, and still more preferably 50nm or less. The lower limit is not particularly limited, and may be 1nm or more. The arithmetic average roughness (Ra) can be measured by the method described in the examples described later.

The cured product obtained by thermally curing the resin composition at 200 ℃ for 90 minutes has a high glass transition temperature. Therefore, when an insulating layer is formed from the cured product, an insulating layer having a high glass transition temperature and excellent heat resistance can be obtained. The glass transition temperature is preferably 140 ℃ or higher, more preferably 145 ℃ or higher, and still more preferably 150 ℃ or higher. The upper limit is not particularly limited, and may be 300 ℃ or lower. The glass transition temperature can be measured by the method described in examples described later.

The resin composition according to one embodiment of the present invention is suitable as a resin composition for insulation applications, and particularly suitable as a resin composition for forming an insulation layer. Therefore, for example, the resin composition is suitable as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). In addition, the resin composition is suitable as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductor layer including a rewiring layer) for forming a conductor layer formed on the insulating layer (resin composition for forming an insulating layer). The resin composition is also widely used in applications where the resin composition can be used, such as a sheet-like laminate material such as a resin sheet or a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a filling resin (a hole filling resin), a component embedding resin, a multi-chip Package, a Package on Package, a wafer level Package, a panel level Package, and a system level Package.

For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to the present embodiment is also suitable as: a resin composition for forming a rewiring layer as an insulating layer (a resin composition for forming a rewiring layer), the insulating layer being an insulating layer for forming a rewiring layer; and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When the semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer;

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

(2) a step of temporarily fixing the semiconductor chip on the temporary fixing film,

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

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

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

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

The resin composition can be used also in the case where the printed wiring board is a component-embedded circuit board.

[ resin sheet ]

The resin sheet of the present invention comprises a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

From the viewpoint of reducing the thickness of the printed wiring board and providing a cured product having excellent insulation even when the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be usually 5 μm or more.

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

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

When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferable. As the copper foil, a foil formed of a single metal of copper may be used, and a foil formed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, or the like) may also be used.

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

In addition, as the support, a support with a release layer having a release layer on a surface to be bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support having a release layer include 1 or more release agents selected from the group consisting of alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support having a release layer, commercially available products can be used, and examples thereof include: examples of the PET film having a release layer containing an alkyd resin-based release agent as a main component include "SK-1", "AL-5" and "AL-7" manufactured by Lindcaceae, "Lumiror T60" manufactured by Toray, Purex "manufactured by Diiten, and" Unipel "manufactured by Unitika.

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

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

The resin sheet can be produced, for example, by: a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and the resin varnish is applied to a support using a die coater or the like and dried 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, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

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

The resin sheet can be wound into a roll and stored. In the case where the resin sheet has a protective film, the protective film can be used by peeling off the protective film.

[ printed Wiring Board ]

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

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

(I) laminating a resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate; (II) curing the resin composition layer to form an insulating layer.

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

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

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

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

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

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

In the step (II), the resin composition layer is cured to form an insulating layer formed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions that can be employed in forming the insulating layer of the printed wiring board can be used. The resin composition layer can be cured by irradiation with active energy rays such as ultraviolet rays, and is usually thermally cured by heating.

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

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

The method of manufacturing a printed wiring board may further include: (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. 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). If necessary, the insulating layer and the conductor layer in steps (I) to (V) may be repeatedly formed to form a multilayer wiring board.

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

The step (IV) is a step of roughening the insulating layer. In general, in this step (IV), stain (smear) is also removed. The step and conditions of the roughening treatment are not particularly limited. For example, the roughening treatment may be performed on the insulating layer by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid.

Examples of the swelling solution used for the roughening treatment include an alkali solution and a surfactant solution, and an alkali solution is preferable. The alkali solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available Swelling liquids include "spinning Dip securigant P" and "spinning Dip securigant SBU" manufactured by atmott JAPAN (ato ech JAPAN). The swelling treatment with the swelling solution is not particularly limited, and may be performed, for example, by immersing the insulating layer in the swelling solution at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, the insulating layer is preferably immersed in a swelling solution at 40 to 80 ℃ for 5 to 15 minutes.

As the oxidizing agent used in the roughening treatment, for example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide is exemplified. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution securigant P" manufactured by anmant japan.

The neutralizing Solution used for the roughening treatment is preferably an acidic aqueous Solution, and examples of commercially available products include "Reduction Solution securigant P" manufactured by anmant japan ltd. The treatment with the neutralizing solution may be performed by immersing the treated surface on which the roughening treatment with the oxidizing agent is performed in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. From the viewpoint of workability, the object after the roughening treatment with the oxidizing agent is preferably immersed in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.

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

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains 1 or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include layers formed of an alloy of 2 or more metals selected from the above-described group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper is further preferable.

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

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

The conductor layer is preferably formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a method such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, the formation is preferably performed by a semi-additive method. An example of forming a conductor layer by a semi-additive method is shown below.

Electroless plating is used to form a plating seed layer on the surface of the insulating layer (メッキシード the body frame). Next, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer in accordance with a desired wiring pattern. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

[ semiconductor device ]

A semiconductor device according to an embodiment of the present invention includes the printed wiring board. The semiconductor device can be manufactured using the printed wiring board described above.

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

Examples

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "part" and "%" representing amounts mean "part by mass" and "% by mass", respectively, unless otherwise explicitly stated. Unless otherwise explicitly stated, the operations described below are performed under an ambient temperature and pressure environment.

< preparation of Maleimide resin A >

An MEK solution (nonvolatile content: 70 mass%) of maleimide resin A synthesized by the method described in Synthesis example 1 of Japanese patent application laid-open Specification No. 2020-500211 was prepared. The maleimide resin A has a structure represented by the following formula.

[ chemical formula 27]

When the FD-MS spectrum of maleimide resin a was determined, peaks at M + ═ 560, 718, and 876 were confirmed. These peaks correspond to n, respectively₁In the case of 0, 1 and 2. Further, when the maleimide resin A was analyzed by GPC, the number n of repeating units in the indane skeleton part was determined based on the number average molecular weight₁When the value of (1) is n₁Molecular weight distribution (Mw/Mn) 1.81. Further, the average number of repeating units n in 100 area% of the total amount of the maleimide resin A₁The content ratio of the maleimide resin of 0 was 26.5 area%.

The FD-MS spectrum of the maleimide resin a represents the result of measurement using the following measurement apparatus and measurement conditions:

(FD-MS Spectrum measuring apparatus and measuring conditions)

A measuring device: JMS-T100GCAccuTOF

Measurement conditions

Measurement range: m/z is 4.00-2000.00

Rate of change: 51.2mA/min

Final current value: 45mA

Cathode voltage: -10kV

Recording interval: 0.07 sec.

The GPC of the maleimide resin a described above represents the result of measurement using the following measurement apparatus and measurement conditions: a measuring device: HLC-8320GPC, manufactured by Tosoh Corporation "

Column: "HXL-L" from Guard Column of Tosoh corporation, "TSK-GEL G2000 HXL" from Tosoh corporation, "TSK-GEL G3000 HXL" from Tosoh corporation, and "TSK-GEL G4000 HXL" from Tosoh corporation "

A detector: RI (differential refractometer)

Data processing: "EcoSEC-WorkStation" of Tosoh corporation "

The measurement conditions were as follows: column temperature 40 deg.C

Tetrahydrofuran as developing solvent

Flow rate 1.0 ml/min

The standard is as follows: according to the aforementioned manual for the determination of "EcoSeC-WorkStation at GPC WorkStation", monodisperse polystyrene having a known molecular weight was used;

sample preparation: a1.0 mass% tetrahydrofuran solution of the maleimide compound in terms of nonvolatile matter was filtered through a microfilter to obtain a product (50. mu.l).

The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the maleimide resin A, and the average number of repeating units "n" that contribute to the indane skeleton in the maleimide resin₁"indicates the result calculated from a GPC chart obtained by the aforementioned GPC measurement. In addition, the average number of repeating units "n₁"represents the result calculated based on the number average molecular weight (Mn). In particular, for n₁The theoretical molecular weight and the molecular weight actually measured in GPC are plotted on a scattergram for compounds of 0 to 4, and an approximate straight line is drawn. Then, the number average molecular weight (Mn) is determined from the point represented by the actually measured value Mn (1) on the straight line, and the average number of repeating units "n" is calculated₁". Further, based on the results of GPC measurement, the average number of repeating units n in 100 area% of the total amount of the maleimide resin A was calculated₁The content ratio (area%) of the maleimide resin was 0. For details, reference may be made to japanese invention association public technical bulletin technical number 2020-.

< Synthesis of PEEK (polyether Ether Ketone) Compound A >

A500 mL flask (three-necked flask) equipped with a stirrer, an argon introduction tube, and a Dean-Stark apparatus was charged with 31.443g of 4, 4' -difluorobenzophenone, 13.223g of resorcinol, 29.894g of anhydrous potassium carbonate, 180mL of N-methylpyrrolidone, and 90mL of toluene, heated under stirring under an argon atmosphere, and refluxed with toluene at 130 to 140 ℃ for 4 hours. Then, the mixture is further heated, and toluene is distilled off at 170 to 180 ℃. And further stirring for 10 hours at 170-180 ℃, and then returning to room temperature to obtain a product 1.

5.233g of 4-aminophenol, 6.628g of anhydrous potassium carbonate, 18mL of N-methylpyrrolidone, and 90mL of toluene were added to a flask containing product 1, and the mixture was heated again under stirring under an argon atmosphere, and toluene was refluxed at 130 to 140 ℃ for 3 hours. Then, the mixture was heated to distill off toluene at 170 to 180 ℃, and further, the stirring was continued for 4 hours while maintaining the temperature. Then, the reaction mixture was cooled to room temperature, and added to 5000mL of methanol, followed by filtration to obtain a powdery solid. The powdery solid was repeatedly washed with methanol and water, and then dried at 100 ℃ for 8 hours to obtain 37.461g of powdery solid (Diamine-A).

A500 mL flask (three-necked flask) equipped with a stirrer and an argon introduction tube was charged with 0.878g of diamine-A, 4.943g of maleic anhydride, and 240mL of N-methylpyrrolidone, and stirred at room temperature for 18 hours under an argon atmosphere. Then, 8.576g of acetic anhydride and 0.689g of sodium acetate were added thereto, and the mixture was stirred at 60 ℃ for 6 hours. After the reaction solution was returned to room temperature, the reaction solution was added to 5000mL of methanol, whereby a powdery solid was obtained. This powdery solid was repeatedly washed with methanol and water, and then dried at 100 ℃ for 8 hours to obtain 28.434g of a PEEK compound represented by the following formula. The number average molecular weight of the PEEK compound a calculated by GPC measurement was 2230;

[ chemical formula 28]

[ example 1]

A PEEK compound A14 parts, a naphthalene type epoxy resin ("ESN 475V" manufactured by Nippon Tekken chemical Co., Ltd., epoxy equivalent of about 332g/eq.)20 parts, an active ester type curing agent ("HPC-8000-65T" manufactured by DIC Co., Ltd., active group equivalent of 223, solid content of 65 mass% toluene solution) 30 parts, and an inorganic filler (spherical silica surface-treated with an amine type alkoxysilane compound ("KBM 573" manufactured by shin-Etsu chemical Co., Ltd.) (SO-C2 "manufactured by Yadu Ma Co., average particle diameter of 0.5 μm, specific surface area of 5.8 m)²(g)) 60 parts and 0.5 part of a curing accelerator (1B 2PZ, 2-phenyl-1-benzyl-1H-imidazole, manufactured by Sikko chemical Co., Ltd.) were mixed and uniformly dispersed in a high-speed rotary mixer to obtain a resin varnish.

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

[ example 2]

In example 1, 30 parts of an active ester-based curing agent (HPC-8000-65T, manufactured by DIC, having an active base equivalent of 223 and a solid content of 65 mass% in toluene) was changed to 30 parts of an active ester-based curing agent (HPC-8150-62T, manufactured by DIC, having an active base equivalent of 229 and a solid content of 62 mass% in toluene);

in the same manner as in example 1 except for the above matters, a resin varnish and a resin sheet were obtained.

[ example 3]

In the case of the example 2, the following examples were conducted,

the amount of the PEEK compound a was changed from 14 parts to 10.5 parts, and 5 parts of a radical polymerizable compound (a mixed MEK/toluene solution containing 70% of nonvolatile components, and having a maleimide equivalent of 275g/eq, MIR-3000-70MT, manufactured by japan chemical company)) was used;

in the same manner as in example 2 except for the above matters, a resin varnish and a resin sheet were obtained.

[ example 4]

In the case of the example 2, the following examples were conducted,

the amount of the PEEK compound a was changed from 14 parts to 12.6 parts, and 2 parts of a radical polymerizable compound ("BMI-1500" manufactured by Designer polymers inc., maleimide equivalent 750g/eq.) was used;

[ example 5]

In example 2, the amount of the active ester-based curing agent (HPC-8150-62T manufactured by DIC Co., Ltd., "229 active base equivalent, 62 mass% solid content in toluene solution) was changed from 30 parts to 25 parts,

the amount of the curing accelerator (1B 2PZ, 2-phenyl-1-benzyl-1H-imidazole, manufactured by Sikkaido chemical Co., Ltd.) was changed from 0.5 part to 0.1 part,

5 parts of a triazine skeleton-containing cresol novolak-based curing agent ("LA 3018-50P" manufactured by DIC corporation, having a hydroxyl group equivalent of 151 and a nonvolatile content of 50% in a 1-methoxy-2-propanol solution) was used;

[ example 6]

In the case of the example 2, the following examples were conducted,

the amount of the PEEK compound a was changed from 14 parts to 10.5 parts, and 5 parts of maleimide resin a was used;

[ example 7]

In example 1, 30 parts of an active ester-based curing agent (HPC-8000-65T manufactured by DIC, having an active group equivalent of 223 and a solid content of 65 mass% in toluene) was changed to 30 parts of an active ester-based curing agent having a naphthalene structure (PC 1300-02-65MA manufactured by Air Water, having an active group equivalent of 200 and a solid content of 65 mass% in methyl amyl ketone solution); in the same manner as in example 1 except for the above matters, a resin varnish and a resin sheet were obtained.

Comparative example 1

In the case of the example 2, the following examples were conducted,

a spherical silica (SO-C2, product of Yadoma, average particle diameter: 0.5 μm, specific surface area: 5.8 m) surface-treated with an inorganic filler (a surface-treated with an amine-based alkoxysilane compound ("KBM 573", product of shin-Etsu chemical Co., Ltd.) without using 14 parts of a PEEK compound A²/g)) was changed from 60 parts to 45 parts;

Comparative example 2

In the case of the example 3, the following examples were conducted,

the amount of a radical polymerizable compound (biphenylaralkyl type maleimide compound ("MIR-3000-70 MT", maleimide group equivalent: 275g/eq., MEK/toluene mixed solution having a nonvolatile content of 70%) was changed from 5 parts to 20 parts without using 10.5 parts of the PEEK compound A;

in the same manner as in example 3 except for the above matters, a resin varnish and a resin sheet were obtained.

Comparative example 3

In the case of the example 4, the following examples were conducted,

the amount of a radical polymerizable compound (BMI-1500 manufactured by Designer polymers inc., maleimide equivalent of 750g/eq.) was changed from 2 parts to 14 parts without using 12.6 parts of the PEEK compound a;

in the same manner as in example 4 except for the above matters, a resin varnish and a resin sheet were obtained.

[ measurement of dielectric characteristics (dielectric constant and dielectric loss tangent) ]

The resin sheets prepared in examples and comparative examples were heated at 200 ℃ for 90 minutes to thermally cure the resin composition layer. Then, the support was peeled off to obtain "cured product a of the resin composition". The cured product A of the resin composition was cut into test pieces having a width of 2mm and a length of 80 mm. For the test piece, the dielectric constant Dk and the dielectric loss tangent Df were measured by a resonance cavity perturbation method using HP8362B manufactured by agilent technologies, inc, at a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃. The average value of the measurements of the 3 test pieces is shown in the following table.

[ measurement of peeling Strength of plating ]

(1) Base treatment of the inner layer circuit substrate:

as an inner layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate having inner layer circuits (copper foils) on both sides was prepared (the thickness of the copper foil was 18 μm, the thickness of the substrate was 0.4mm, manufactured by Sonar corporation "R1515A"). Both surfaces of the inner layer circuit board were etched by 1 μm using "CZ 8101" manufactured by MEC to roughen the copper surface.

(2) Lamination of resin sheets:

the resin sheet was laminated on both surfaces of the inner layer circuit board using a batch type vacuum press laminator (CVP 700, 2-stage stack laminator, manufactured by Nikko Materials co., ltd.). The lamination is performed in such a manner that the resin composition layer of the resin sheet is in contact with the inner circuit substrate. In addition, the lamination is carried out by: the pressure was reduced for 30 seconds to 13hPa or less, and the pressure was bonded for 45 seconds at 130 ℃ and a pressure of 0.74 MPa. Next, hot pressing was performed at 120 ℃ and a pressure of 0.5MPa for 75 seconds.

(3) Curing of the resin composition:

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

(4) Roughening treatment:

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

(5) Plating based on the semi-additive method:

evaluation substrate A was coated with PdCl₂The electroless copper plating solution of (1) was immersed at 40 ℃ for 5 minutes, and then immersed at 25 ℃ for 20 minutes in an electroless copper plating solution. Then, the resultant was heated at 150 ℃ for 30 minutes to perform annealing treatment. Then, a resist layer is formed, and pattern formation by etching is performed. Then, electrolytic plating with copper sulfate was performedThe conductor layer was formed to a thickness of 20 μm. Next, annealing treatment was performed at 200 ℃ for 60 minutes to obtain "evaluation substrate B".

(6) Determination of peel strength of plating:

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

[ measurement of surface roughness Ra ]

The arithmetic average roughness Ra of the surface of the insulating layer of the evaluation substrate a was measured. The measurement was performed by: the measurement was carried out in a VSI mode using a 50-fold lens using a non-contact surface roughness meter (WYKO NT3300 manufactured by Veeco Instruments Inc.) so that the measurement range was 121 μm × 92 μm. The measurement was performed at 10 measurement points, and the average value thereof is shown in the following table.

[ measurement of glass transition temperature ]

The cured product A of the resin composition was cut into test pieces having a width of about 5mm and a length of about 15mm, and subjected to thermomechanical analysis by a tensile load method using a dynamic viscoelasticity measuring apparatus (EXSTAR6000, manufactured by SII Nanotechnology Co., Ltd.). After the test piece was mounted on the apparatus, the measurement was carried out under the measurement conditions of a load of 200mN and a temperature rise rate of 2 ℃/min.

The peak term of tan δ thus obtained was calculated as the glass transition temperature (. degree. C.).

[ Table 1]

(Table 1)

In the table, the content of the component (a) represents the content of the component (a) when the resin component in the resin composition is 100 mass%. (E) The content of component (c) represents the content of component (E) assuming that the nonvolatile content in the resin composition is 100 mass%. (C) component/(B) represents the quantitative ratio of component (C) to component (B).

Claims

1. A resin composition comprising:

(A) a polyether ether ketone compound having a maleimide group,

(B) An epoxy resin, and

(C) an active ester curing agent.

2. The resin composition according to claim 1, wherein the number average molecular weight of the component (A) is 10000 or less.

3. The resin composition according to claim 1, wherein component (A) has a maleimide group at a terminal.

4. The resin composition according to claim 1, wherein the content of the component (A) is 5% by mass or more and 60% by mass or less, assuming that the resin component in the resin composition is 100% by mass.

5. The resin composition according to claim 1, wherein the component (B) comprises a naphthol type epoxy resin.

6. The resin composition according to claim 1, wherein the component (C) is at least 1 active ester-based curing agent selected from the group consisting of a dicyclopentadiene active ester-based curing agent and a naphthalene active ester-based curing agent.

7. The resin composition according to claim 1, further comprising (D) a resin having a polymerizable unsaturated group.

8. The resin composition according to claim 7, wherein the component (D) is a resin containing a maleimide group and an aromatic ring.

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

10. The resin composition according to claim 9, wherein the content of the component (E) is 40% by mass or more and 65% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

11. The resin composition according to claim 1, which is used for forming an insulating layer.

12. The resin composition according to claim 1, which is used for forming an insulating layer, the insulating layer being an insulating layer for forming a conductor layer.

13. A resin sheet, comprising:

support body, and

a resin composition layer comprising the resin composition according to any one of claims 1 to 12 provided on the support.

14. A printed wiring board comprising an insulating layer formed by using a cured product of the resin composition according to any one of claims 1 to 12.

15. A semiconductor device comprising the printed wiring board of claim 14.