resin composition

Abstract

To provide a resin composition or the like that can give a cured product having excellent peel strength and high glass transition temperature despite low dielectric properties and small surface roughness.SOLUTION: A resin composition contains (A) a polyether ether ketone compound having a maleimide group, (B) an epoxy resin, and (C) an active ester-based curing agent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition. Furthermore, the present invention relates to a resin sheet, a printed circuit board, and a semiconductor device obtained using the resin composition. [Background technology]

[0002] As a manufacturing technology for printed circuit boards, a build-up method is known in which insulating layers and conductive layers are stacked alternately. In the build-up method, the insulating layer is generally formed by curing a resin composition. As an example of such a resin composition, the resin composition disclosed in Patent Document 1 is known. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2019-66792 [Overview of the project] [Problems that the invention aims to solve]

[0004] The cured product formed by curing a resin composition can be used as an insulating layer for printed circuit boards of semiconductor devices. Therefore, it is required that the dielectric properties (dielectric constant and dielectric loss tangent) of the cured product be low. Furthermore, it is desirable that the insulating layer formed from this cured product has a high glass transition temperature in order to have excellent peel strength between the insulating layer and the conductive layer, even with low surface roughness, and to have excellent heat resistance.

[0005] The present invention was devised in view of the above-mentioned problems, and aims to provide a resin composition that can produce a cured product with low dielectric properties, excellent peel strength even with low surface roughness, and a high glass transition temperature; a resin sheet comprising a resin composition layer containing the resin composition; a printed circuit board comprising an insulating layer formed of a cured product of the resin composition; and a semiconductor device comprising the printed circuit board. [Means for solving the problem]

[0006] As a result of diligent research to solve the aforementioned problems, the inventors have found that the aforementioned 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.

[0007] In other words, the present invention includes the following: [1] (A) Polyether ether ketone compounds having a maleimide group, (B) Epoxy resin, and (C) A resin composition containing an active ester-based curing agent. [2] The resin composition according to [1], wherein the number average molecular weight of component (A) is 10,000 or less. [3] The resin composition according to [1] or [2], wherein component (A) has a maleimide group at its terminus. [4] The resin composition according to any one of [1] to [3], wherein the content of component (A) is 5% by mass or more and 60% by mass or less when the total amount of resin components in the resin composition is 100% by mass. [5] A resin composition according to any one of [1] to [4], wherein component (B) is a naphthol-type epoxy resin. [6] The resin composition according to any one of [1] to [5], wherein component (C) is one or more selected from dicyclopentadiene-type active ester curing agents and naphthalene-type active ester curing agents containing a naphthalene structure. [7] The resin composition according to any one of [1] to [6], further comprising (D) a resin having polymerizable unsaturated groups. [8] The resin composition according to [7], wherein component (D) is a resin containing a maleimide group and an aromatic ring. [9] Furthermore, the resin composition according to any one of [1] to [8], comprising (E) an inorganic filler.

[10] The resin composition according to [9], wherein the content of component (E) is 40% by mass or more and 65% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

[11] A resin composition according to any one of [1] to

[10] for forming an insulating layer.

[12] A resin composition according to any one of [1] to

[11] , for forming an insulating layer for forming a conductive layer.

[13] A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising any of the resin compositions described in [1] to

[12] .

[14] A printed circuit board comprising an insulating layer formed of a cured product of any of the resin compositions described in [1] to

[12] .

[15]

[14] A semiconductor device including a printed circuit board. [Effects of the Invention]

[0008] The present invention provides a resin composition that can produce a cured product with low dielectric properties, excellent peel strength even with low surface roughness, and a high glass transition temperature; a resin sheet comprising a resin composition layer containing the resin composition; a printed circuit board comprising an insulating layer formed of a cured product of the resin composition; and a semiconductor device comprising the printed circuit board. [Modes for carrying out the invention]

[0009] 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 shown below, and may be implemented with modifications as appropriate without departing from the scope of the claims and equivalents of the present invention.

[0010] [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-based curing agent. With such a resin composition, it is possible to obtain a cured product with low dielectric properties, excellent peel strength even with low surface roughness, and a high glass transition temperature.

[0011] The resin composition may further optionally contain any components such as (D) a resin containing radically polymerizable unsaturated groups, (E) an inorganic filler, (F) a curing agent, (G) a curing accelerator, and (H) other additives.

[0012] <(A) Polyether ether ketone compounds having a maleimide group> The resin composition contains a polyether ether ketone compound having a maleimide group as component (A). The maleimide group is represented by the following formula (A-1). By including component (A) in the resin composition, a cured product with a high glass transition temperature can be obtained. [ka]

[0013] Component (A) can be a compound having a maleimide group and a polyether ether ketone (PEEK) structure. Preferably, there is one or more maleimide groups per molecule of component (A), more preferably two or more, preferably 10 or fewer, more preferably 5 or fewer, and even more preferably 3 or fewer. From the viewpoint of obtaining a cured product with excellent dielectric properties, it is preferable that component (A) has a maleimide group at its terminal end, and more preferably that it has maleimide groups at both terminal ends.

[0014] Component (A) has a polyether ether ketone structure. Preferably, the polyether ether ketone structure has the structure represented by the following formula (A-2). [ka] In equation (A-2), Ar 1 Ar 2 Ar 3 Ar 4 , and Ar 5 Each of these independently represents a divalent aromatic hydrocarbon group. n is an integer from 2 to 50. * represents a bond.

[0015] An aromatic hydrocarbon group refers to a hydrocarbon group that contains an aromatic ring. However, an aromatic hydrocarbon group does not have to consist solely of an aromatic ring; it may also contain a chain-like structure or an alicyclic hydrocarbon group as part of it, and the aromatic ring may be monocyclic, polycyclic, or heterocyclic.

[0016] Examples of divalent aromatic hydrocarbon groups include arylene groups, aralkylene groups, and groups having an arylene-alkylene-arylene structure.

[0017] The arylene group is preferably one having 6 to 30 carbon atoms, more preferably one having 6 to 20 carbon atoms, and even more preferably one having 6 to 10 carbon atoms. Examples of such arylene groups include phenylene, naphthylene, anthracenylene, and biphenylene groups.

[0018] The aralkylene group is preferably one having 7 to 30 carbon atoms, more preferably one having 7 to 20 carbon atoms, and even more preferably one having 7 to 15 carbon atoms. Examples of such aralkylene groups include bendiylene groups and groups having a biphenylene-methylene structure.

[0019] In the group having an arylene-alkylene-arylene structure, arylene is the same as the above-described arylene group. As the alkylene, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is even more preferable. Examples of such alkylene include methylene, ethylene, propylene, and the like. Further, the alkylene may have a substituent. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms; a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; a halogenated alkyl group, etc. An alkyl group having 1 to 3 carbon atoms and a halogenated alkyl group are preferable, a methyl group and a trifluoromethyl group are more preferable, and a methyl group is even more preferable. Specific examples of the group having such an arylene-alkylene-arylene structure include, for example, the structures represented by the following formulas (1) to (2). Among them, the group represented by formula (1) is preferable. [Chemical formula] In the formula, “*” represents a bond.

[0020] Among these, Ar 1 , Ar 2 , Ar 4 , and Ar 5 are preferably an arylene group or a group having an arylene-alkylene-arylene structure, more preferably an arylene group, and even more preferably a phenylene group. Ar 3 is preferably an arylene group or a group having an arylene-alkylene-arylene structure, more preferably a group having an arylene-alkylene-arylene structure, and even more preferably a group having a phenylene-dimethylmethylene-phenylene structure (the group represented by formula (1)).

[0021] n represents an integer of 2 to 50, preferably represents an integer of 3 to 40, more preferably represents an integer of 4 to 30, and even more preferably represents an integer of 5 to 20.

[0022] Specific examples of structures represented by equation (A-2) include, but are not limited to, the structures represented by equations (A1) to (A2) below (where * represents a bond). [ka]

[0023] n1 and n2 are the same as n in equation (A-2).

[0024] (A) Component is preferably a compound represented by the following formula (A-3). [ka] In the formula, D 1 and D 2 Each of these independently represents a single bond or a divalent linking group. 11 Ar 12 Ar 14 , and Ar 15 Each of these independently corresponds to Ar in equation (A-2) 1 Ar 2 Ar 4 , and Ar 5 It is the same as Ar 13 Each of these independently corresponds to Ar in equation (A-2) 3 This is the same as the previous example. m is the same as n in equation (A-2).

[0025] D 1 and D 2 Each of these independently represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent hydrocarbon groups, divalent heterocyclic groups, carbonyl groups, ether bonds, ester bonds, carbonate bonds, amide bonds, imide bonds, and groups formed by the linkage of multiple such groups. Divalent hydrocarbon groups include divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon groups.

[0026] Examples of divalent aliphatic hydrocarbon groups include linear or branched alkylene groups having 1 to 18 carbon atoms, and linear or branched alkenylene groups having 2 to 18 carbon atoms. Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene. Examples of linear or branched alkenylene groups having 2 to 18 carbon atoms include vinylene, 1-methylvinylene, propenylene, 1-butenylene, and 2-butenylene.

[0027] Examples of divalent alicyclic hydrocarbon groups include divalent alicyclic hydrocarbon groups having 3 to 18 carbon atoms, such as cycloalkylene groups (including cycloalkylidene groups) like 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene.

[0028] Examples of divalent aromatic hydrocarbon groups include arylene groups having 6 to 14 carbon atoms, such as 1,2-phenylene, 1,4-phenylene, 1,3-phenylene, 4,4'-biphenylene, 3,3'-biphenylene, 2,6-naphthylene, 2,7-naphthylene, 1,8-naphthylene, and anthracenylene.

[0029] The heterocycles constituting the divalent heterocyclic group include aromatic heterocycles and non-aromatic heterocycles. Examples of heterocycles include 3- to 10-membered rings having a carbon atom and at least one heteroatom as constituent atoms, and fused rings thereof. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, etc. 3- to 10-membered heterocycles are preferred, and 4- to 6-membered rings are more preferred. Examples of heterocyclic groups constituting a divalent heterocyclic group include: three-membered rings such as oxirane rings; four-membered rings such as oxetane rings; five-membered rings such as furan rings, tetrahydrofuran rings, oxazole rings, isoxazole rings, γ-butyrolactone rings, thiophene rings, thiazole rings, isothiazole rings, thiadiazole rings, pyrrole rings, pyrrolidine rings, pyrazole rings, imidazole rings, and triazole rings; six-membered rings such as 4-oxo-4H-pyran rings, tetrahydropyran rings, morpholine rings, 4-oxo-4H-thiopyran rings, isocyanuric rings, pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, piperidine rings, and piperazine rings; and 3-oxatricyclo[4.3.1.1 4,8 ]Undecane-2-one ring, 3-oxatricyclo[4.2.1.0 4,8 Examples include bridged rings such as nonane-2-one rings; fused rings such as benzofuran rings, isobenzofuran rings, 4-oxo-4H-chromene rings, chroman rings, isochroman rings, benzothiophene rings, indole rings, indoline rings, quinoline rings, acridine rings, naphthyridine rings, quinazoline rings, and purine rings. Divalent heterocyclic groups are groups obtained by removing two hydrogen atoms from the structural formula of the above heterocyclic rings.

[0030] Among them, D 1 and D 2 From the viewpoint of significantly obtaining the effects of the present invention, it is preferable to represent a divalent aromatic hydrocarbon group, more preferably an arylene group having 6 to 16 carbon atoms, even more preferably a 1,2-phenylene group, 1,4-phenylene group, 1,3-phenylene group, 4,4'-biphenylene group, 3,3'-biphenylene group, 2,6-naphthylene group, 2,7-naphthylene group, 1,8-naphthylene group, or anthracenylene group, and particularly preferably a 1,2-phenylene group, 1,4-phenylene group, or 1,3-phenylene group.

[0031] (A) Specific examples of component (A) are listed below, but the present invention is not limited thereto. In the following formula, na and nb each independently represent an integer from 2 to 50. [ka]

[0032] (A) Component may be a commercially available product or synthesized by a known method. (A) Component can be synthesized, for example, using the synthesis method described in Polymer 1989, p978. (A) Component may be used alone or in combination of two or more types.

[0033] (A) The weight-average molecular weight of component (A) is preferably 1000 or more, more preferably 1200 or more, even more preferably 1400 or more, preferably 10000 or less, more preferably 7500 or less, and even more preferably 5000 or less, from the viewpoint of obtaining a cured product with low dielectric properties and excellent adhesion to copper foil. The weight-average molecular weight of a resin can be measured as a polystyrene equivalent using gel permeation chromatography (GPC).

[0034] (A) The number average molecular weight of component (A) is preferably 1000 or more, more preferably 1200 or more, even more preferably 1400 or more, preferably 10000 or less, more preferably 7500 or less, and even more preferably 5000 or less, from the viewpoint of obtaining a cured product with low dielectric properties and excellent adhesion to copper foil. The number-average molecular weight of the resin can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC).

[0035] (A) In terms of the content of component (A), from the viewpoint of obtaining a cured product with low dielectric properties and excellent adhesion to copper foil, when the nonvolatile component in the resin composition is considered to be 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. In this invention, unless otherwise specified, the content of each component in the resin composition is the value when the non-volatile component in the resin composition is taken as 100% by mass.

[0036] (A) As for the content of component (A), from the viewpoint of obtaining a cured product with low dielectric properties and excellent adhesion to copper foil, when the resin component in the resin composition is considered as 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, even more 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 even more preferably 30% by mass or less. The resin component refers to the nonvolatile components in the resin composition, excluding (E) inorganic filler.

[0037] <(B) Epoxy resin> The resin composition contains an epoxy resin as component (B). By incorporating epoxy resin (B) into the resin composition, a cured product with low dielectric properties and excellent peel strength can be obtained.

[0038] Examples of component (B) include bixylenol-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol novolac-type epoxy resin, phenol novolac-type epoxy resin, tert-butyl-catechol-type epoxy resin, naphthalene-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, cresol novolac-type epoxy resin, biphenyl-type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro-ring-containing epoxy resin, cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, and the like. Among these, naphthol-type epoxy resin is preferred as component (B) from the viewpoint of significantly obtaining the effects of the present invention.

[0039] The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as component (B). From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule, relative to 100% by mass of the nonvolatile component (B), is preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more.

[0040] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only liquid epoxy resin as component (B), only solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin. However, from the viewpoint of significantly obtaining the desired effects of the present invention, it is preferable to contain only solid epoxy resin.

[0041] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups per molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups per molecule is more preferred.

[0042] Preferred solid epoxy resins include bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin, with naphthol-type epoxy resin being more preferred.

[0043] Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin); DIC's "N-690" (cresol novolac-type epoxy resin); DIC's "N-695" (cresol novolac-type epoxy resin); DIC's "HP-7200", "HP-7200HH", and "HP-7200H" (dicyclopentadi EN-type epoxy resins); DIC Corporation's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC3000H", "NC3000", "NC3000L" "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; Examples include "YX8800" (anthracene-type epoxy resin); "PG-100" and "CG-500" from Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin) from Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy resin) from Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A-type epoxy resin) from Mitsubishi Chemical Corporation; and "jER1031S" (tetraphenylethane-type epoxy resin) from Mitsubishi Chemical Corporation. These can be used individually or in combination of two or more types.

[0044] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0045] Preferred liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure, with naphthalene type epoxy resin being more preferred.

[0046] Specific examples of liquid epoxy resins include DIC's "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US," "jER828EL," "825," and "Epicote 828EL" (bisphenol A-type epoxy resin); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F-type epoxy resin); Mitsubishi Chemical's "jER152" (phenol novolac-type epoxy resin); and Mitsubishi Chemical's "630" and "630LSD" (glycidylamine-type epoxy resin). Examples include: "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd.; "Celoxide 2021P" (alicyclic epoxy resin with an ester skeleton) manufactured by Daicel Corporation; "PB-3600" (epoxy resin with a butadiene structure) manufactured by Daicel Corporation; and "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd. These may be used individually or in combination of two or more types.

[0047] (B) When a liquid epoxy resin and a solid epoxy resin are used in combination as component (B), their mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 1:1 to 1:20, more preferably 1:1.5 to 1:15, and particularly preferably 1:2 to 1:10. By having the mass ratio of the liquid epoxy resin and the solid epoxy resin within this range, the desired effects of the present invention can be remarkably obtained. Furthermore, when used in the form of a resin sheet, appropriate tackiness is provided. Also, when used in the form of a resin sheet, sufficient flexibility is obtained, improving handling. Furthermore, a cured product with sufficient breaking strength can usually be obtained.

[0048] The epoxy equivalent of component (B) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. This range ensures sufficient crosslinking density in the cured resin layer, resulting in an insulating layer with low surface roughness. The epoxy equivalent is the mass of epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0049] The weight-average molecular weight (Mw) of component (B) is preferably 100 to 5000, more preferably 200 to 3000, and even more preferably 250 to 1500, from the viewpoint of significantly obtaining the desired effects of the present invention.

[0050] (B) The content of component (B) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, when the non-volatile components in the resin composition are considered to be 100% by mass, from the viewpoint of obtaining an insulating layer that exhibits good mechanical strength and insulating reliability. The upper limit of the epoxy resin content 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 significantly obtaining the desired effects of the present invention.

[0051] (B) The content of component (B) is preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, when the total resin component in the resin composition is considered to be 100% by mass.

[0052] <(C) Active ester-based curing agent> The resin composition contains (C) an active ester-based curing agent. Using an active ester-based curing agent can improve dielectric properties and result in superior peel strength. Component (C) may be used alone or in combination of two or more types.

[0053] (C) As the active ester curing agent, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by the condensation of two phenol molecules with one dicyclopentadiene molecule.

[0054] Specifically, the (C) component can be a dicyclopentadiene-type active ester curing agent, a naphthalene-type active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated phenol novolac, or an active ester curing agent containing a benzoylated phenol novolac. Among these, the (C) component is more preferably one or more selected from a dicyclopentadiene-type active ester curing agent and a naphthalene-type active ester curing agent containing a naphthalene structure, with a naphthalene-type active ester curing agent containing a naphthalene structure being even more preferable. As for the dicyclopentadiene-type active ester curing agent, an active ester curing agent containing a dicyclopentadiene-type diphenol structure is preferred. "Dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0055] (C) Commercially available active ester curing agents include, as active ester curing agents containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC); as naphthalene-type active ester curing agents containing a naphthalene structure, "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-65T", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC), "PC1300-02-65T" (E Examples include: "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing an acetylated phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing a benzoylated phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is a benzoylated phenol novolac; and "EXB-8500-65T" (manufactured by DIC Corporation).

[0056] (C) The equivalent amount of active ester groups in the active ester curing agent is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and even more preferably 100 g / eq. to 300 g / eq., from the viewpoint of being able to lower the dielectric loss tangent and obtain a cured product with excellent adhesion. The equivalent amount of active ester groups is the mass of the active ester curing agent containing 1 equivalent amount of active ester groups.

[0057] The ratio of (B) epoxy resin to (C) active ester-based curing agent is the ratio of [total number of active groups of the active ester-based curing agent] / [total number of epoxy groups of the epoxy resin], preferably 0.01 or more, more preferably 0.3 or more, even more preferably 0.5 or more, preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less. Here, "number of epoxy groups of epoxy resin" is the sum of all values ​​obtained by dividing the mass of nonvolatile components of the epoxy resin present in the resin composition by the epoxy equivalent. Active group of the agent The term "number" refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of the active ester-based curing agent present in the resin composition by the equivalent amount of active ester groups. By keeping the ratio of epoxy resin to active ester-based curing agent within this range, the effects of the present invention can be significantly achieved.

[0058] (C) The content of the active ester-based curing agent is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, when the non-volatile components in the resin composition are considered to be 100% by mass, from the viewpoint of being able to lower dielectric properties and obtain a cured product with excellent peel strength. Furthermore, the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0059] (C) As for the content of the active ester-based curing agent, from the viewpoint of being able to lower dielectric properties and obtain a cured product with excellent peel strength, when the resin component in the resin composition is considered to be 100% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0060] <(D) Resin containing radically polymerizable unsaturated groups> In addition to the components described above, the resin composition may also contain (D) a resin containing radical polymerizable unsaturated groups as an optional component. By including (D) a resin containing radical polymerizable unsaturated groups in the resin composition, a cured product with low dielectric properties and excellent peel strength can be obtained. Component (D) excludes components (A) to (C).

[0061] The radical polymerizable unsaturated group contained in component (D) represents a group containing an unsaturated bond that exhibits radical polymerizability. Examples of such radical polymerizable unsaturated groups include groups containing an ethylenic double bond. Component (D) containing such a radical polymerizable unsaturated group can undergo radical polymerization by heat or active energy rays, thereby curing the resin composition.

[0062] Examples of radically polymerizable unsaturated groups include maleimide groups, vinyl groups, vinylphenyl groups, acryloyl groups, methacryloyl groups, fumaroyl groups, maleoyl groups, benzocyclobutene groups, and allyl groups. Among these, maleimide groups are preferred as component (D) from the viewpoint of significantly obtaining the effects of the present invention. The number of radically polymerizable unsaturated groups contained in component (D) is usually 1 or more, preferably 2 or more. When component (D) contains 2 or more radically polymerizable unsaturated groups, these 2 or more radically polymerizable unsaturated groups may be the same or different.

[0063] Component (D) preferably uses a resin containing an aromatic ring in its molecule. Therefore, component (D) is preferably a resin containing an aromatic ring and a radically polymerizable unsaturated group. The aromatic ring contained in component (D) may be an aromatic carbon ring or an aromatic heterocycle. Furthermore, the aromatic ring may be a monocyclic aromatic ring, a condensed aromatic ring formed by the condensation of two or more monocyclic aromatic rings, or a condensed aromatic ring formed by the condensation of one or more monocyclic aromatic rings with one or more monocyclic non-aromatic rings. Examples of these aromatic rings include monocyclic aromatic rings such as benzene rings and pyridine rings; and condensed aromatic rings such as indan rings, fluorene rings, and naphthalene rings. Among these, aromatic carbon rings are preferred. The number of carbon atoms in the aromatic carbon ring is preferably 6 to 10.

[0064] (D) The aromatic rings contained in component (D) may have substituents attached. The number of substituents attached to one aromatic ring may be one or two or more. If the number of substituents is two or more, these two or more substituents may be the same or different.

[0065] Examples of substituents include alkyl groups, alkyloxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, cycloalkyl groups, halogen atoms, hydroxyl groups, and mercapto groups.

[0066] The number of carbon atoms in the alkyl group is preferably 1 to 10. Examples of alkyl groups include methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, and the like.

[0067] The number of carbon atoms in the alkyloxy group is preferably 1 to 10. Examples of alkyloxy groups include methoxy, ethoxy, propoxy, and butoxy groups.

[0068] The number of carbon atoms in the alkylthio group is preferably 1 to 10. Examples of alkylthio groups include methylthio group, ethylthio group, propylthio group, and butylthio group.

[0069] The number of carbon atoms in the aryl group is preferably 6 to 10. Examples of aryl groups include the phenyl group and the naphthyl group.

[0070] The number of carbon atoms in the aryloxy group is preferably 6 to 10. Examples of aryloxy groups include phenyloxy groups and naphthyloxy groups.

[0071] The number of carbon atoms in the arylthio group is preferably 6 to 10. Examples of arylthio groups include phenylthio groups and naphthylthio groups.

[0072] The number of carbon atoms in the cycloalkyl group is preferably 3 to 10. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and cycloheptyl groups.

[0073] Examples of halogen atoms include fluorine atoms, chlorine atoms, and iodine atoms.

[0074] In particular, the aromatic ring contained in component (D) is preferably either unsubstituted or with an alkyl group attached.

[0075] The number of aromatic rings contained in component (D) is usually one or more, preferably two or more. If component (D) contains two or more aromatic rings, these two or more aromatic rings may be the same or different.

[0076] (D) Component may be used alone or in combination of two or more types.

[0077] A preferred embodiment of component (D) is a resin containing a maleimide group. The resin containing the maleimide group preferably further contains an aromatic ring. Since the resin containing the maleimide group belongs to component (D), those corresponding to component (A) are excluded. The resin containing the maleimide group may be used alone or in combination of two or more types.

[0078] Resins containing maleimide groups include: (D-1) Maleimide compounds containing an aliphatic group with 5 or more carbon atoms directly bonded to the nitrogen atom of the maleimide group. (D-2) Maleimide compounds having an aromatic ring directly bonded to the nitrogen atom of a maleimide group, and (D-3) Maleimide compounds containing a trimethylindane skeleton, It is preferable that it be one or more selected from the following.

[0079] Here, the term "direct" means that, in the case of component (D-1), there are no other groups between the nitrogen atom of the maleimide group and the aliphatic group having 5 or more carbon atoms, and in the case of component (D-2), there are no other groups between the nitrogen atom of the maleimide and the aromatic ring.

[0080] Component (D-1) is a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of maleimide. Component (D-1) can be obtained, for example, by imidizing a component containing an aliphatic amine compound (such as a diamine compound having a dimer acid skeleton), maleic anhydride, and optionally a tetracarboxylic dianhydride.

[0081] Examples of aliphatic groups with five or more carbon atoms include alkyl groups, alkylene groups, and alkenylene groups.

[0082] The alkyl group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. This alkyl group may be linear, branched, or cyclic, with linear being preferred. Examples of such alkyl groups include pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. The alkyl group having 5 or more carbon atoms may also be present as a substituent on an alkylene group having 5 or more carbon atoms.

[0083] The number of carbon atoms in an alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. This alkylene group may be linear, branched, or cyclic, with linear being preferred. Here, the term "cyclic alkylene group" includes both cases where it consists only of a cyclic alkylene group and cases where it includes both a linear alkylene group and a cyclic alkylene group. Examples of such alkylene groups include pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, hexatriacontinentylene, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

[0084] The number of carbon atoms in 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 even more preferably 40 or less. This alkenylene group may be linear, branched, or cyclic, with linear being preferred. Here, the term "cyclic alkenylene group" includes cases where only cyclic alkenylene groups are present, as well as cases where both linear and cyclic alkenylene groups are present. Examples of such alkenylene groups include pentynylene, hexynylene, heptyleneylene, octynylene, noninylene, desynylene, undecynylene, dodecynylene, tridecynylene, heptadecynylene, hexatriacontinylene, groups having an octynylene-cyclohexynylene structure, groups having an octynylene-cyclohexynylene-octynylene structure, and groups having a propynylene-cyclohexynylene-octynylene structure.

[0085] As component (D-1), a compound represented by the following formula (D-1-1) is preferred. [ka] In the general formula (D-1-1), M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

[0086] M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. The number of carbon atoms of the divalent aliphatic group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. This aliphatic group may be linear, branched or cyclic, and among them, a linear one is preferable. Here, the cyclic aliphatic group is a concept including both the case consisting only of a cyclic aliphatic group and the case including both a linear aliphatic group and a cyclic aliphatic group. Examples of the divalent aliphatic group include an alkylene group and an alkenylene group. The alkylene group and the alkenylene group are as described above.

[0087] Examples of the substituent of M include, for example, a halogen atom, -OH, -O-C 1-10 alkyl group, -N(C 1-10 alkyl group)2, C 1-10 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 6-10 aryl group, -NH2, -CN, -C(O)O-C 1-10 alkyl group, -COOH, -C(O)H, -NO2 and the like. Here, the term "C x-y "(x and y are positive integers and satisfy x < y) represents that the number of carbon atoms of the organic group described immediately after this term is x to y. For example, the expression "C 1-10 alkyl group" indicates 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 fused ring. The substituent is preferably an alkyl group having 5 or more carbon atoms.

[0088] L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C(=O)-, -C(=O)-O-, -NR 0-(R 0 (C) is a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, C(=O)NR 0 - Examples include divalent groups derived from phthalimide, divalent groups derived from pyromellitic acid diimide, and groups consisting of combinations of two or more of these divalent groups. Alkylene groups, alkenylene groups, alkynylene groups, arylene groups, divalent groups derived from phthalimide, divalent groups derived from pyromellitic acid diimide, and groups consisting of combinations of two or more divalent groups may have alkyl groups with 5 or more carbon atoms as substituents. Divalent groups derived from phthalimide refer to divalent groups derived from phthalimide, specifically the group represented by the general formula (D-1-2). Divalent groups derived from pyromellitic acid diimide refer to divalent groups derived from pyromellitic acid diimide, specifically the group represented by the general formula (D-1-3). In the formula, "*" represents a bond. [ka]

[0089] 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. This alkylene group may be linear, branched, or cyclic. Examples of such alkylene groups include methylethylene group, cyclohexylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, heptadecylene group, hexatriacontinente 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.

[0090] 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. This alkenylene group may be linear, branched, or cyclic. Examples of such alkenylene groups include methylethyleneylene, cyclohexenylene, pentenylene, hexenylene, heptenylene, and octenylene.

[0091] 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. This alkynylene group may be linear, branched, or cyclic. Examples of such alkynylene groups include methylethynylene, cyclohexynylene, pentynylene, hexynylene, heptynylene, and octynylene.

[0092] The arylene group as a 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, even more preferably an arylene group having 6 to 14 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of arylene groups include phenylene groups, naphthylene groups, anthracenylene groups, and the like.

[0093] The divalent linking groups in L, namely alkylene, alkenylene, alkynylene, and arylene groups, may have substituents. The substituents are the same as those of M in general formula (B2-1-1), and are preferably alkyl groups having 5 or more carbon atoms.

[0094] Examples of groups in L consisting of a combination of two or more divalent groups include: a divalent group consisting of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group consisting of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a divalent group consisting of an alkylene group and a divalent group derived from pyromellitic diimide; and so on. Groups consisting of a combination of two or more divalent groups may form rings such as fused rings depending on the combination of each group. Furthermore, groups consisting of a combination of two or more divalent groups may be repeating units with a number of repeating units from 1 to 10.

[0095] In particular, L in general formula (D-1-1) is preferably an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have substituents, an alkylene group having 1 to 50 carbon atoms which may have substituents, 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 consisting of two or more combinations of these groups. Among these, L is more preferably an alkylene group; a divalent group having the structure of an alkylene group-divalent group derived from phthalimide-oxygen atom-divalent group derived from phthalimide; a divalent group having the structure of an alkylene group-divalent group derived from phthalimide-oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-divalent group derived from phthalimide; a divalent group having the structure of an alkylene-pyromellitic acid diimide; a divalent group having the structure of an alkyline group-divalent group derived from phthalimide-oxygen atom-divalent group derived from phthalimide; a divalent group having the structure of an alkyline group-divalent group derived from phthalimide-oxygen atom-arylene group-arylene group-arylene group-oxygen atom-divalent group derived from phthalimide; or a divalent group having the structure of an alkyline-pyromellitic acid diimide.

[0096] The maleimide resin represented by general formula (D-1-1) is preferably a maleimide resin represented by general formula (D-1-4). [ka] In general formula (D-1-4), M 1 Each of the following independently represents a divalent aliphatic group having 5 or more carbon atoms, which may have substituents; each of the following independently represents a divalent aliphatic group having 5 or more carbon atoms, which may have substituents, or a divalent group having an aromatic ring, which may have substituents; and t represents an integer from 1 to 10.

[0097] M 1 Each of these independently represents a divalent aliphatic group having 5 or more carbon atoms, which may have substituents. 1 This is the same as M in general formula (D-1-1).

[0098] Each Z independently represents a divalent aliphatic group having 5 or more carbon atoms, which may have substituents, or a divalent group having an aromatic ring, which may have substituents. Examples of divalent aliphatic groups in Z include alkylene groups and alkenylene groups. The divalent aliphatic group may be linear, branched, or cyclic, with cyclic, i.e., a cyclic divalent aliphatic group having 5 or more carbon atoms, which may have substituents, being preferred.

[0099] The number of carbon atoms in the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. Examples of such alkylene groups include groups having an octylene-cyclohexylene structure, groups having an octylene-cyclohexylene-octylene structure, and groups having a propylene-cyclohexylene-octylene structure.

[0100] The number of carbon atoms in 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 even more preferably 40 or less. This alkenylene group may be linear, branched, or cyclic, with linear being preferred. Here, the term "cyclic alkenylene group" includes cases where only cyclic alkenylene groups are present, as well as cases where both linear and cyclic alkenylene groups are present. Examples of such alkenylene groups include pentynylene, hexynylene, heptyleneylene, octynylene, noninylene, desynylene, undecynylene, dodecynylene, tridecynylene, heptadecynylene, hexatriacontinylene, groups having an octynylene-cyclohexynylene structure, groups having an octynylene-cyclohexynylene-octynylene structure, and groups having a propynylene-cyclohexynylene-octynylene structure.

[0101] Examples of aromatic rings in a divalent group having an aromatic ring represented by Z include benzene rings, naphthalene rings, anthracene rings, phthalimide rings, pyromellitic acid diimide rings, aromatic heterocycles, etc., with benzene rings, phthalimide rings, and pyromellitic acid diimide rings being preferred. That is, preferred divalent groups having an aromatic ring include divalent groups having a benzene ring which may have substituents, divalent groups having a phthalimide ring which may have substituents, and divalent groups having a pyromellitic acid diimide ring which may have substituents. Examples of divalent groups having an aromatic ring include groups consisting of a combination of a phthalimide-derived divalent group and an oxygen atom; groups consisting of a combination of a phthalimide-derived divalent group, an oxygen atom, an arylene group, and an alkylene group; groups consisting of an alkylene group and a divalent group derived from pyromellitic acid diimide; divalent groups derived from pyromellitic acid diimide; and groups consisting of a combination of a phthalimide-derived divalent group and an alkylene group. The above arylene group is the same as the arylene group in the divalent linking group represented by L in general formula (D-1-1).

[0102] The divalent group represented by Z, which has an alkylene group and an aromatic ring, may have substituents. The substituents are the same as those that M in general formula (D-1-1) may have.

[0103] The following are specific examples of the group that Z represents. In the formula, "*" represents a bond. [ka] [ka]

[0104] The compound represented by general formula (D-1-1) is preferably one of the compounds represented by general formula (D-1-5) or the compound represented by general formula (D-1-6). [ka] In general formula (D-1-5), M 2 and M 3 Each of these independently represents a divalent aliphatic group having 5 or more carbon atoms, which may have substituents, and R 40 Each of these independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group consisting of two or more combinations of these groups. t1 represents an integer from 1 to 10. In general formula (D-1-6), M 4 M 6 and M 7 Each of these independently represents an aliphatic group having 5 or more carbon atoms, which may have substituents, and M 5 Each of these independently represents a divalent group having an aromatic ring which may have substituents, and R 41 and R 42 Each of these independently represents an alkyl group with 5 or more carbon atoms. t2 represents an integer from 0 to 10, and u1 and u2 independently represent integers from 0 to 4.

[0105] M 2 and M 3Each of these independently represents a divalent aliphatic group having 5 or more carbon atoms, which may have substituents. 2 and M 3 This is similar to a divalent aliphatic group with 5 or more carbon atoms represented by M in general formula (D-1-1), and a hexa-tria-continentylene group or a hexa-tria-continentylene group is preferred.

[0106] R 40 Each of these independently represents an oxygen atom, an arylene group, an alkylene group, or a group consisting of a combination of two or more of these divalent groups. The arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in general formula (D-1-1). 40 Preferably, the group is a combination of two or more divalent groups or an oxygen atom.

[0107] R 40 Examples of groups consisting of two or more divalent groups include combinations of an oxygen atom, an arylene group, and an alkylene group. Specific examples of groups consisting of two or more divalent groups are listed below. In the formula, "*" represents a bond. [ka]

[0108] M 4 M 6 and M 7 Each of these independently represents an aliphatic group having 5 or more carbon atoms, which may have substituents. 4 M 6 and M 7 This is similar to an aliphatic group having 5 or more carbon atoms which may have substituents represented by M in general formula (D-1-1), and is preferably a hexylene group, heptylene group, octylene group, nonylene group, or desilene group, with the octylene group being more preferred.

[0109] M 5 Each of these independently represents a divalent group having an aromatic ring which may have substituents. 5The group is similar to the divalent group having an aromatic ring which may have substituents represented by Z in general formula (D-1-4), and is a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group is preferred, and a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide is more preferred. The above arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in general formula (D-1-1).

[0110] M 5 Specific examples of the group represented by include the following groups. In the formula, "*" represents a bond. [ka]

[0111] R 41 and R 42 Each of these independently represents an alkyl group with 5 or more carbon atoms. 41 and R 42 The alkyl group is similar to the alkyl group having 5 or more carbon atoms as described above, and is preferably a hexyl group, heptyl group, octyl group, nonyl group, or decyl group, with hexyl group or octyl group being more preferred.

[0112] u1 and u2 each independently represent integers between 1 and 15, preferably between 1 and 10.

[0113] Specific examples of component (D-1) include the following compounds (Di) to (D-iii), and are not limited to these specific examples. In the formulas, v represents an integer from 1 to 10. [ka] [ka]

[0114] Specific examples of component (D-1) include "BMI1500" (compound of formula (Di)), "BMI1700" (compound of formula (D-ii)), and "BMI689" (compound of formula (D-iii)), all manufactured by Designer Molecules.

[0115] The weight-average molecular weight (Mw) of component (D-1) is preferably 150 to 5000, more preferably 300 to 2500.

[0116] The maleimide group equivalent of component (D-1) is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., and even more preferably 150 g / eq. to 500 g / eq., from the viewpoint of significantly obtaining the desired effects of the present invention. The maleimide group equivalent is the mass of component (D-1) containing 1 equivalent of maleimide group.

[0117] Component (D-2) is a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of maleimide. Component (D-2) can be obtained, for example, by imidizing a component containing an aromatic amine compound (such as an aromatic diamine compound) and maleic anhydride.

[0118] Aromatic rings can be carbocyclic or heterocyclic. Examples of aromatic rings include monocyclic aromatic rings such as benzene rings, furan rings, thiophene rings, pyrrole rings, pyrazole rings, oxazole rings, isoxazole rings, thiazole rings, imidazole rings, pyridine rings, pyridazine rings, pyrimidine rings, and pyrazine rings; condensed rings formed by the fusion of two or more monocyclic aromatic rings such as naphthalene rings, anthracene rings, benzofuran rings, isobenzofuran rings, indole rings, isoindole rings, benzothiophene rings, benzimidazole rings, indazole rings, benzoxazole rings, benzoisoxazole rings, benzothiazole rings, quinoline rings, isoquinoline rings, quinoxaline rings, acridine rings, quinazoline rings, sinnoline rings, and phthalazine rings; and condensed rings formed by the fusion of one or more monocyclic aromatic rings with one or more monocyclic non-aromatic rings, such as indan rings, fluorene rings, and tetraline rings. Among these, monocyclic aromatic rings are preferred, and benzene rings are more preferred.

[0119] As component (D-2), a compound represented by the following formula (D-2-1) is preferred. [ka]

[0120] In the formula, R c Each of these independently indicates a substituent; X c Each of these independently represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO- (preferably a single bond or an alkylene group); Z cEach independently represents an optionally substituted non-aromatic ring or an optionally substituted aromatic ring (preferably an optionally substituted aromatic ring, particularly preferably an optionally substituted benzene ring); s represents an integer of 1 or more (preferably an integer from 1 to 100, more preferably an integer from 1 to 50, even more preferably an integer from 1 to 20); t1 each independently represents 0 or an integer of 1 or more; u each independently represents an integer from 0 to 2 (preferably 0). The maleimide compound is represented by formula (D-2-2) to (D-2-5):

[0121] [ka] In the formula, R c1 , R c2 and R c3 Each of these independently represents an alkyl group; X c1 and X c2 Each independently represents a single bond or an alkylene group; s represents an integer of 1 or more (preferably an integer from 1 to 100, more preferably an integer from 1 to 50, and even more preferably an integer from 1 to 20); t' represents an integer from 1 to 5; v1, v2, and v3 each independently represent an integer from 0 to 2 (preferably 0). Note that the s unit, t unit, t' unit, v unit, v1 unit, v2 unit, and v3 unit may be the same or different for each unit.

[0122] In another embodiment, the (D-2) component is preferably structured by, for example, the following formula (D-2-6). [ka] In the formula, R 31 and R 36 represents a maleimide group, R 32 , R 33 , R 34 and R 35Each 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 from 1 to 10, and a represents an integer from 1 to 100.

[0123] R in formula (D-2-6) 32 R 33 R 34 and R 35 each independently represents a hydrogen atom, an alkyl group, or an aryl group, and a hydrogen atom is preferred.

[0124] As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 3 carbon atoms is even more preferred. 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, an isopropyl group, and the like.

[0125] The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms. The aryl group may be a monocyclic ring or a condensed ring. Examples of such an aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and the like.

[0126] 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 1-6 alkyl group, -N(C 1-10 alkyl group)2, C 1-10 alkyl group, C 6-10 aryl group, -NH2, -CN, -C(O)O-C 1-10 alkyl group, -COOH, -C(O)H, -NO2, and the like. Here, the term "C p-q " (where p and q are positive integers and p < q) represents that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, "C 1-10The term "alkyl group" refers to an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and this ring structure includes spiro rings and fused rings.

[0127] The substituents described above may have further substituents (hereinafter sometimes referred to as "secondary substituents"). Unless otherwise specified, the same substituents described above may be used as secondary substituents.

[0128] In formula (D-2-6), D represents a divalent aromatic group. Examples of divalent aromatic groups include phenylene, naphthylene, anthracenylene, aralkyl, biphenylene, and biphenylaralkyl groups, among which biphenylene and biphenylaralkyl groups are preferred, and biphenylene groups are more preferred. The divalent aromatic group may have substituents. Examples of substituents include R in formula (D-2-6). 32 This is similar to the substituents that the alkyl group represented may have.

[0129] m1 and m2 each independently represent integers from 1 to 10, preferably from 1 to 6, more preferably from 1 to 3, even more preferably from 1 to 2, and most preferably from 1.

[0130] 'a' represents an integer between 1 and 100, preferably between 1 and 50, more preferably between 1 and 20, and even more preferably between 1 and 5.

[0131] As component (D-2), a resin represented by formula (D-2-7) is preferred. [ka] In the formula, R 37 and R 38 represents a maleimide group. a1 represents an integer between 1 and 100.

[0132] a1 is the same as a in equation (D-2-6), and the preferred range is also the same.

[0133] Examples of commercially available products containing component (D-2) include "MIR-3000-70MT" from Nippon Kayaku Co., Ltd.; "BMI-50P" from Kei-I Kasei Co., Ltd.; "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", and "BMI-5100" from Yamato Kasei Kogyo Co., Ltd.; "BMI-4,4'-BPE", "BMI-70", and "BMI-80" from Kei-I Kasei Co., Ltd.

[0134] The weight-average molecular weight (Mw) of component (D-2) is preferably 150 to 5000, more preferably 300 to 2500.

[0135] The functional group equivalent of the maleimide group in component (D-2) is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., even more preferably 150 g / eq. to 500 g / eq., and particularly preferably 200 g / eq. to 300 g / eq.

[0136] Component (D-3) is a maleimide compound containing a trimethylindane skeleton. The trimethylindane skeleton is the skeleton shown in the following formula (D-3-1).

[0137] [ka]

[0138] The benzene ring in the trimethylindane skeleton may have substituents attached. Examples of substituents include alkyl groups, alkyloxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, cycloalkyl groups, halogen atoms, hydroxyl groups, and mercapto groups. The number of carbon atoms in the alkyl group is preferably 1 to 10. Examples of alkyl groups include methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, and the like. The number of carbon atoms in the alkyloxy group is preferably 1 to 10. Examples of alkyloxy groups include methoxy, ethoxy, propoxy, and butoxy groups. The number of carbon atoms in the alkylthio group is preferably 1 to 10. Examples of alkylthio groups include methylthio group, ethylthio group, propylthio group, and butylthio group. The number of carbon atoms in the aryl group is preferably 6 to 10. Examples of aryl groups include the phenyl group and the naphthyl group. The number of carbon atoms in the aryloxy group is preferably 6 to 10. Examples of aryloxy groups include phenyloxy groups and naphthyloxy groups. The number of carbon atoms in the arylthio group is preferably 6 to 10. Examples of arylthio groups include phenylthio groups and naphthylthio groups. The number of carbon atoms in the cycloalkyl group is preferably 3 to 10. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and cycloheptyl groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, and iodine atoms.

[0139] Of the substituents mentioned above, the hydrogen atoms of alkyl groups, alkyloxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, and cycloalkyl groups may be substituted with halogen atoms.

[0140] The number of substituents attached to a single benzene ring in the trimethylindan skeleton may be one or two or more. Typically, the number of substituents attached to a benzene ring in the trimethylindan skeleton is between zero and three. If the number of substituents is two or more, these two or more substituents may be the same or different. In particular, it is preferable that no substituents are attached to the benzene ring in the trimethylindan skeleton.

[0141] The number of trimethylindane skeletons contained in one molecule of 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.

[0142] Component (D-3) preferably further contains an aromatic ring skeleton in addition to the trimethylindane skeleton described above. The number of ring constituent carbons of the aromatic ring skeleton is preferably 6 to 10. Examples of aromatic ring skeletons include a benzene ring skeleton and a naphthalene ring skeleton. The number of aromatic ring skeletons contained in one molecule of 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 component (D-3) contains two or more aromatic ring skeletons in addition to the trimethylindane skeleton, these aromatic ring skeletons may be the same or different.

[0143] The aromatic ring contained in the aforementioned aromatic ring skeleton may have substituents attached to it. Examples of substituents that can be attached to the benzene ring contained in the trimethylindane skeleton include the substituents mentioned above and nitro groups. The number of substituents attached to one aromatic ring may be one or two or more. The number of substituents attached to an aromatic ring is usually between 0 and 4. If the number of substituents is two or more, these two or more substituents may be the same or different.

[0144] Component (D-3) preferably contains a divalent aliphatic hydrocarbon group in addition to the trimethylindane skeleton described above. In particular, it is preferable that component (D-3) contains a divalent aliphatic hydrocarbon group when component (D-3) contains an aromatic ring skeleton other than the benzene ring contained in the trimethylindane skeleton. In this case, it is preferable that the divalent aliphatic hydrocarbon group connects the benzene ring contained in the trimethylindane skeleton with the aromatic ring skeleton. It is also preferable that the divalent aliphatic hydrocarbon group connects the aromatic ring skeletons with each other.

[0145] The number of carbon atoms in 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. Alkylene groups as saturated aliphatic hydrocarbon groups are more preferred as the divalent aliphatic hydrocarbon group. Examples of divalent aliphatic hydrocarbon groups include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; and branched alkylene groups such as ethylidene (-CH(CH3)-), propylidene (-CH(CH2CH3)-), isopropylidene (-C(CH3)2-), ethylmethylmethylene (-C(CH3)(CH2CH3)-), and diethylmethylene (-C(CH2CH3)2-). (B2-3) When a maleimide compound containing a trimethylindane skeleton contains two or more divalent aliphatic hydrocarbon groups in addition to the trimethylindane skeleton, these divalent aliphatic hydrocarbon groups may be the same or different.

[0146] The (D-3) component preferably includes the structure shown by the following formula (D-3-2). The entire (D-3) component may have the structure shown by formula (D-3-2), or a portion of the (D-3) component may have the structure shown by formula (D-3-2). [ka]

[0147] (In the formula, Ar a1 R represents a divalent aromatic hydrocarbon group which may have substituents; a1 Each 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 a3 Each of these independently represents a divalent aliphatic hydrocarbon group; n a1 n represents a positive integer; a2 Each of these independently represents an integer from 0 to 4; n a3 Each of these independently represents an integer from 0 to 3. a1 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. a2 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. a2 If R is 2-4, a1 n may be the same or different within the same ring. a3 If it is 2 or 3, R a2 (These may be the same or different within the same ring.)

[0148] In equation (D-3-2), Ar a1represents a divalent aromatic hydrocarbon group which may have substituents. The number of carbon atoms in this divalent aromatic hydrocarbon group is preferably 6 or more, preferably 20 or less, and more preferably 16 or less. Examples of divalent aromatic hydrocarbon groups include phenylene groups and naphthylene groups. Examples of substituents that a divalent aromatic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms, alkyloxy groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, arylthio groups having 6 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, halogen atoms, hydroxyl groups, and mercapto groups. The hydrogen atoms of each substituent may be further substituted with halogen atoms. Specific examples of these substituents include, for example, the same substituents that can be bonded to the benzene ring contained in the trimethylindane skeleton. When a divalent aromatic hydrocarbon group has substituents, the number of substituents is preferably 1 to 4. When a divalent aromatic hydrocarbon group has two or more substituents, these two or more substituents may be the same or different. In particular, Ar a1 It is preferable that this is a divalent aromatic hydrocarbon group without substituents.

[0149] In equation (D-3-2), R a1 Each of these 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 alkyl groups, alkyloxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, and cycloalkyl groups may be substituted with halogen atoms. Specific examples of these groups include, for example, the same examples as substituents that can be bonded to the benzene ring contained in the trimethylindane skeleton. Among these, R a1It is more preferably one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 10 carbon atoms, with alkyl groups having 1 to 4 carbon atoms being particularly preferred.

[0150] In equation (D-3-2), R a2 Each of these 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. The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. Specific examples of these groups include, for example, the same examples as substituents that can be bonded to the benzene ring contained in the trimethylindane skeleton. Among these, R a2 It is more preferable that this is one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 10 carbon atoms.

[0151] In equation (D-3-2), R a3 Each of these independently represents a divalent aliphatic hydrocarbon group. The preferred range of divalent aliphatic hydrocarbon groups is as described above.

[0152] In equation (D-3-2), n a1 n represents a positive integer. a1 It is preferably 1 or more, preferably 10 or less, and more preferably 8 or less.

[0153] In equation (D-3-2), n a2 Each of these independently represents an integer from 0 to 4. a2 The number is preferably 2 or 3, more preferably 2. a2 They may be different, but it is preferable that they be the same.a2 If there are 2 or more, multiple R a1 Within the same ring, they may be the same or different.

[0154] In equation (D-3-2), n a3 Each of these independently represents an integer from 0 to 3. a3 They may be different, but it is preferable that they be the same. a3 It is preferably 0.

[0155] Component (D-3) is particularly preferably to include the structure shown by the following formula (D-3-3). The entire component (D-3) may have the structure shown by formula (D-3-3), or a portion of component (D-3) may have the structure shown by formula (D-3-3). [ka] (In the formula, R b1 Each 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 b2 Each of these 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 b1 n represents a positive integer; b2 Each of these independently represents an integer from 0 to 4; n b3 Each of these independently represents an integer from 0 to 3. b1 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. b2The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. b2 If R is 2-4, b1 n may be the same or different within the same ring. b3 If it is 2 or 3, R b2 (These may be the same or different within the same ring.)

[0156] In equation (D-3-3), R b1 , R b2 , n b1 , n b2 and n b3 These are R in equation (D-3-2), respectively. a1 , R a2 , n a1 , n a2 and n a3 It is the same as this.

[0157] Component (D-3) may further include the structure shown by the following formula (D-3-4). [ka] In equation (D-3-4), R c1 , R c2 , n c2 and n c3 These are R in equation (D-3-2), respectively. a1 , R a2 , n a2 and n a3 It is the same as. Also, in equation (D-3-4), n c1 is the number of repeating units and represents an integer from 1 to 20. Furthermore, in equation (D-3-4), * represents a combination. For example, the (D-3) component is n in equation (D-3-2). a2 The ratio is 3 or less, and of the ortho and para positions of the maleimide group on the benzene ring to which the maleimide group is attached, R is present in two or more positions. a1When not bonded, the structure represented by formula (D-3-2) may include the structure represented by formula (D-3-4) in combination with the structure represented by formula (D-3-4). Also, for example, the (D-3) component is, in formula (D-3-3), n b2 The ratio is 3 or less, and of the ortho and para positions of the maleimide group on the benzene ring to which the maleimide group is attached, R is present in two or more positions. b1 When they are not bonded, the structure represented by formula (D-3-3) may be combined with the structure represented by formula (D-3-4).

[0158] (D-3) Component may be used alone, or two or more may be used in any ratio.

[0159] The maleimide group equivalent of 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 equivalent of maleimide group. When the maleimide group equivalent of component (D-3) is within the above range, the effects of the present invention can be remarkably obtained.

[0160] There are no particular restrictions on the method for producing component (D-3). Component (D-3) can be produced, for example, by the method described in the Japan Institute of Invention and Innovation Published Technical Report No. 2020-500211. According to the production method described in this Japan Institute of Invention and Innovation Published Technical Report No. 2020-500211, a maleimide compound having a distribution in the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by this method contains a structure represented by the following formula (D-3-5). Therefore, component (D-3) may contain a maleimide compound containing a structure represented by formula (D-3-5).

[0161] [ka]

[0162] (In the formula, R1 Each 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 2 Each of these 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; n1 represents the average number of repeating units from 0.95 to 10.0; n2 independently represents an integer from 0 to 4; and n3 independently represents an integer from 0 to 3. 1 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. 2 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atoms. When n2 is 2 to 4, R 1 These can be the same or different within the same ring. When n3 is 2 to 3, R 2 (These may be the same or different within the same ring.)

[0163] In equation (D-3-5), R 1 , R 2 n2 and n3 are, respectively, R in equation (D-3-2). a1 , R a2 , n a2 and n a3 It is the same as this.

[0164] In formula (D-3-5), n1 represents the average number of repeating units, and its range is 0.95 to 10.0. According to the manufacturing method described in the Japan Institute of Invention and Innovation Publication No. 2020-500211, a group of maleimide compounds containing the structure represented by formula (D-3-5) can be obtained. As can be seen from the fact that the average number of repeating units n1 in formula (D-3-5) can be less than 1.00, the maleimide compounds containing the structure represented by formula (D-3-5) thus obtained may include maleimide compounds in which the number of repeating units of the trimethylindane skeleton is 0. Therefore, the (D-3) component may be obtained by purification from the maleimide compound containing the structure represented by formula (D-3-5) to remove the maleimide compound in which the number of repeating units of the trimethylindane skeleton is 0, and the resin composition may contain only the obtained (D-3) component. However, even if the resin composition contains a maleimide compound in which the number of repeating units of the trimethylindane skeleton is 0, the effects of the present invention can be obtained. Furthermore, if purification is omitted, costs can be reduced. Therefore, it is preferable that the resin composition contains maleimide compounds with a structure represented by formula (D-3-5) without excluding maleimide compounds with zero repeating units in the trimethylindane skeleton.

[0165] In formula (D-3-5), the average number of repeating units n1 is preferably 0.95 or more, more preferably 0.98 or more, even more preferably 1.0 or more, particularly preferably 1.1 or more, preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, and particularly preferably 6.0 or less. When the average number of repeating units n1 is within the above range, the effects of the present invention can be significantly obtained. In particular, the glass transition temperature of the resin composition can be effectively increased.

[0166] Examples of structures represented by formula (D-3-5) include the following:

[0167] [ka]

[0168] A maleimide compound containing the structure represented by formula (D-3-5) may further contain the structure shown in formula (D-3-4). For example, a maleimide compound containing the structure represented by formula (D-3-5) is one in which n2 is 3 or less, and two or more of the ortho and para positions of the benzene ring to which the maleimide group is bonded are R 1 When they are not bonded, the structure represented by formula (D-3-5) may be combined with the structure represented by formula (D-3-4).

[0169] Maleimide compounds containing the structure represented by formula (D-3-5) preferably have a molecular weight distribution Mw / Mn calculated from gel permeation chromatography (GPC) measurements 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 expressed as "Mw / Mn". Specifically, the molecular weight distribution Mw / Mn of maleimide compounds containing the structure represented by formula (D-3-5) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, even more preferably 1.2 to 3.6, and particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw / Mn of maleimide compounds containing the structure represented by formula (D-3-5) is within the above range, the effects of the present invention can be significantly obtained.

[0170] Among the maleimide compounds containing the structure represented by formula (D-3-5), the amount of the maleimide compound with an average repeat unit number n1 of 0 is preferably within a specific range. When the GPC measurement of the maleimide compound containing the structure represented by formula (D-3-5) is performed, the amount of the maleimide compound with an average repeat unit number n1 of 0 can be expressed in area% based on the results of the GPC measurement. Specifically, in the chromatogram obtained by the above GPC measurement, the ratio (area%) of the peak area of the maleimide compound with an average repeat unit number n1 of 0 to the total peak area of the maleimide compound containing the structure represented by formula (D-3-5) can represent the amount of the maleimide compound with an average repeat unit number n1 of 0. Specifically, with respect to 100 area% of the total amount of the maleimide compound containing the structure represented by formula (D-3-5), the amount of the maleimide compound with an average repeat unit number n1 of 0 is preferably 32 area% or less, more preferably 30 area% or less, and still more preferably 28 area% or less. When the amount of the maleimide compound with an average repeat unit number n1 of 0 is within the above range, the effects of the present invention can be significantly obtained.

[0171] The maleimide group equivalent of the maleimide compound containing the structure represented by formula (D-3-5) is preferably in the same range as the maleimide group equivalent of the (D-3) component described above. When the maleimide group equivalent of the maleimide compound containing the structure represented by formula (D-3-5) is within the above range, the effects of the present invention can be significantly obtained.

[0172] From the viewpoint of obtaining a cured product with low dielectric properties and excellent peel strength, the content of component (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less when the non-volatile components in the resin composition are 100% by mass.

[0173] As the content of the (D) component, from the viewpoint of obtaining a cured product with low dielectric properties and excellent peel strength, when the resin component in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.

[0174] <(E) Inorganic filler> In addition to the components described above, the resin composition may contain an (E) inorganic filler as an optional component. By including the (E) inorganic filler in the resin composition, it becomes possible to obtain a cured product with excellent dielectric properties.

[0175] As the 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 carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungsten phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. Also, as silica, spherical silica is preferred. The (E) inorganic filler may be used alone or in combination of two or more.

[0176] (E) Examples of commercially available inorganic fillers include "UFP-30" from Denka Chemical Industries, Ltd.; "SP60-05" and "SP507-05" from Nippon Steel & Sumitomo Metal Materials Corporation; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" from Admatex Corporation; "UFP-30" from Denka Corporation; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" from Tokuyama Corporation; and "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", and "SC2050-SXF" from Admatex Corporation.

[0177] (E) The average particle size of the 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 even more preferably 1 μm or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

[0178] (E) The average particle size of inorganic fillers can be measured by the laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis using a laser diffraction-scattering particle size distribution analyzer, and the average particle size can be measured by taking the median diameter as the average particle size. A sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them with ultrasound for 10 minutes. The sample is measured using a laser diffraction-type particle size distribution analyzer with blue and red light source wavelengths, and the volume-based particle size distribution of the inorganic filler is measured using a flow cell method. The average particle size is then calculated from the obtained particle size distribution as the median diameter. Examples of laser diffraction-type particle size distribution analyzers include the "LA-960" manufactured by Horiba, Ltd. and the "SALD-2200" manufactured by Shimadzu Corporation.

[0179] (E) The specific surface area of ​​the inorganic filler is preferably 1 m², from the viewpoint of significantly obtaining the desired effects of the present invention. 2 / g or more, more comfortably 2m 2 / g or more, particularly preferably 3m 2It must be 1 / g or more. There is no particular upper limit, but preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 The specific surface area is less than or equal to / g. The specific surface area of ​​the inorganic filler is obtained by using a fully automated BET specific surface area analyzer (Macsorb HM-1210, manufactured by Mountec Co., Ltd.) to adsorb nitrogen gas onto the sample surface and calculating the specific surface area using the BET multi-point method.

[0180] (E) From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably treated with a surface treatment agent. Examples of surface treatment agents include fluorine-containing silane coupling agents such as 3,3,3-trifluoropropyltrimethoxysilane; aminosilane coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyl-trimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; epoxysilane coupling agents such as 3-glycidoxypropyltrimethoxysilane; mercaptosilane coupling agents such as 3-mercaptopropyltrimethoxysilane; silane coupling agents; alkoxysilanes such as phenyltrimethoxysilane; organosilazane compounds such as hexamethyldisilazane; titanate coupling agents, etc. Furthermore, the surface treatment agent may be used alone or in any combination of two or more types.

[0181] Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane), "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy-type silane coupling agent), and "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), all manufactured by Shin-Etsu Chemical Co., Ltd.

[0182] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent, preferably with 0.2 to 3 parts by mass, and preferably with 0.3 to 2 parts by mass.

[0183] The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler should be 0.02 mg / m². 2 The above is preferred, and 0.1 mg / m² 2 The above is more preferable, 0.2 mg / m² 2 The above is even more preferable. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in sheet form, 1 mg / m 2 The following is preferred: 0.8 mg / m² 2 The following is more preferable: 0.5 mg / m² 2 The following is even more preferable.

[0184] (E) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after cleaning the inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)) following surface treatment. Specifically, a sufficient amount of MEK is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0185] (E) As for the content of inorganic filler, from the viewpoint of significantly obtaining the effects of the present invention, when the nonvolatile components in the resin composition are taken as 100% by mass, it is preferably 40% by mass or more, more preferably 45% by mass or more, even more 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 even more preferably 55% by mass or less.

[0186] <(F) Hardener> In addition to the components described above, the resin composition may further contain (F) a curing agent as an optional component. However, (C) active ester curing agents are not included in the (F) curing agent. Examples of (F) curing agents include phenolic curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, and carbodiimide curing agents. In particular, from the viewpoint of improving insulation reliability, the (F) curing agent is preferably one or more of the phenolic curing agent, naphthol curing agent, cyanate ester curing agent, and carbodiimide curing agent, more preferably either a phenolic curing agent or a naphthol curing agent, and even more preferably contains a phenolic curing agent. The (F) curing agent may be used alone or two or more may be used in combination.

[0187] From the viewpoint of heat resistance and water resistance, phenolic curing agents having a novolac structure or naphthol curing agents having a novolac structure are preferred. Furthermore, from the viewpoint of adhesion to the conductive layer, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic curing agents are more preferred.

[0188] Specific examples of phenol-based and naphthol-based curing agents include, for example, "MEH-7700," "MEH-7810," and "MEH-7851" from Meiwa Chemical Co., Ltd., "NHN," "CBN," and "GPH" from Nippon Kayaku Co., Ltd., "SN170," "SN180," "SN190," "SN475," "SN485," "SN495," "SN-495V," "SN375," and "SN395" from Nippon Steel & Sumitomo Metal Chemical Co., Ltd., and "TD-2090," "LA-7052," "LA-7054," "LA-1356," "LA3018-50P," and "EXB-9500" from DIC Corporation.

[0189] Specific examples of benzoxazine-based curing agents include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemicals Co., Ltd.

[0190] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) thioether, and bis(4-cyanatephenyl) ether; polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs; and prepolymers in which these cyanate resins are partially triazined. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), "BA230", and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazined and trimerized), all manufactured by Lonza Japan.

[0191] Specific examples of carbodiimide-based curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

[0192] When containing a curing agent as the (F) component, the quantitative ratio of the epoxy resin to the (B) active ester-based curing agent and the (F) curing agent is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.3 to 1:3, and even more preferably 1:0.5 to 1:2, in the ratio of [total number of epoxy groups of the epoxy resin]:[total number of active groups of the (B) active ester-based curing agent and the (F) curing agent]. Here, the "total number of epoxy groups of the epoxy resin" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. Also, the "total number of active groups of the (B) active ester-based curing agent and the (F) curing agent" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the active ester-based curing agent and the curing agent present in the resin composition by the active group equivalent. By setting the quantitative ratio of the epoxy resin to the (B) component and the (F) component within such a range, the effects of the present invention can be significantly obtained.

[0193] When containing a curing agent as the (F) component, the quantitative ratio of the epoxy resin to all of the (F) curing agents is preferably in the range of 1:0.01 to 1:1, more preferably 1:0.03 to 1:0.5, and even more preferably 1:0.05 to 1:0.3, in the ratio of [total number of epoxy groups of the epoxy resin]:[total number of active groups of the (F) curing agent]. Here, the "total number of active groups of the (F) curing agent" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the (F) curing agent present in the resin composition by the active group equivalent. By setting the quantitative ratio of the epoxy resin to the curing agent as the (F) component within such a range, the effects of the present invention can be significantly obtained.

[0194] From the viewpoint of significantly obtaining the desired effects of the present invention, when the non-volatile component in the resin composition is 100% by mass, the content of the (F) curing agent is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

[0195] (F) From the viewpoint of significantly obtaining the desired effects of the present invention, the content of the curing agent is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, when the resin component in the resin composition is considered to be 100% by mass.

[0196] <(G) Curing accelerator> In addition to the components described above, the resin composition may further contain a curing accelerator as component (G) as an optional component.

[0197] Examples of component (G) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Component (G) may be used alone or in combination of two or more types.

[0198] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0199] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0200] Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-Cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-Cyanoethyl-2-ethyl-4-methylimidazole, 1-Cyanoethyl-2-phenylimidazole, 1-Cyanoethyl-2-undecylimidazolium trimellitate, 1-Cyanoethyl-2-phenylimidazolium trimellitate, 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2, 4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-F Examples include imidazole compounds such as 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, as well as adducts of imidazole compounds with epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

[0201] Commercial imidazole-based curing accelerators may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0202] Examples of guanidine-based curing accelerators 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]deca-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene. Examples include ro[4.4.0]deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]deca-5-ene being preferred.

[0203] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0204] (G) The content of component (G) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, preferably 3% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1% by mass or less, when the nonvolatile components in the resin composition are considered to be 100% by mass, based on the viewpoint of significantly obtaining the desired effects of the present invention.

[0205] (G) The content of component (G) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, when the total amount of resin components in the resin composition is 100% by mass.

[0206] <(H) Other additives> In addition to the components described above, the resin composition may also contain other additives as optional components. Examples of such additives include thermoplastic resins, elastomers, organic fillers, thickeners, defoamers, leveling agents, adhesion promoters, and flame retardants. These may be used individually or in combination of two or more in any ratio.

[0207] The resin composition can be manufactured, for example, by mixing the above-mentioned components in any order. Furthermore, heating and / or cooling may be performed during the mixing process by appropriately adjusting the temperature. Additionally, stirring may be performed using a stirring device such as a mixer during or after mixing to ensure uniform dispersion of each component. Furthermore, if necessary, the resin composition may be subjected to a degassing treatment.

[0208] <Physical properties and applications of resin compositions> Since the resin composition contains a combination of components (A), (B), and (C), it is possible to obtain a cured product with low dielectric properties, excellent peel strength even with low surface roughness, and a high glass transition temperature.

[0209] The cured product obtained by heat-curing the resin composition at 200°C for 90 minutes has a low dielectric constant Dk. Therefore, when an insulating layer is formed with this cured product, an insulating layer with a low dielectric constant can be obtained. For example, the dielectric constant Dk of the cured product obtained by curing the resin composition under the conditions described in the examples below is preferably 3.0 or less, more preferably 2.9 or less, and even more preferably 2.8 or less. The lower limit of the dielectric constant Dk of the cured product is not particularly limited, but can be 0.1 or more. The dielectric constant of the cured product can be measured by the method described in the examples.

[0210] The cured product obtained by heat-curing the resin composition at 200°C for 90 minutes has a low dielectric loss tangent. Therefore, when an insulating layer is formed with this cured product, an insulating layer with a low dielectric loss tangent can be obtained. For example, the dielectric loss tangent Df of the cured product obtained by curing the resin composition under the conditions described in the examples below is preferably 0.010 or less, more preferably 0.005 or less, and even more preferably 0.004 or less. The lower limit of the dielectric loss tangent Df of the cured product is not particularly limited, but may be 0.001 or more. The dielectric loss tangent of the cured product can be measured by the method described in the examples.

[0211] The cured product obtained by heat-curing the resin composition at 200°C for 90 minutes can have high plating peel strength between it and the plating. Therefore, when an insulating layer is formed with this cured product, an insulating layer with high peel strength between it and 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 examples below, the peel strength between the insulating layer and the conductor layer can be preferably 0.2 kgf / cm or more, more preferably 0.3 kgf / cm or more, and particularly preferably 0.4 kgf / cm or more. The upper limit of adhesion is not particularly limited, but for example, it can be 10.0 kgf / cm or less. The peel strength can be measured by the method described in the examples.

[0212] A cured product obtained by heat-curing a resin composition at 200°C for 90 minutes exhibits the characteristic of having a low arithmetic mean roughness (Ra) on the surface of the cured product after roughening treatment. Therefore, an insulating layer with a low arithmetic mean roughness (Ra) on the surface after roughening treatment can be obtained. The arithmetic mean roughness (Ra) is preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 50 nm or less. The lower limit is not particularly limited, but can be 1 nm or more, for example. The arithmetic mean roughness (Ra) can be measured according to the method described in the examples below.

[0213] The cured product obtained by heat-curing the resin composition at 200°C for 90 minutes exhibits the characteristic of a high glass transition temperature. Therefore, when an insulating layer is formed with this cured product, an insulating layer with a high glass transition temperature and excellent heat resistance can be obtained. The glass transition temperature is preferably 140°C or higher, more preferably 145°C or higher, and even more preferably 150°C or higher. There is no particular upper limit, but it can be 300°C or lower. The glass transition temperature can be measured according to the method described in the examples below.

[0214] The resin composition according to one embodiment of the present invention is suitable as a resin composition for insulating applications, and is particularly suitable as a resin composition for forming an insulating layer. Therefore, for example, the resin composition is suitable as a resin composition for forming an insulating layer of a printed circuit board (a resin composition for forming an insulating layer of a printed circuit board). Furthermore, the resin composition is suitable as a resin composition for forming an insulating layer for forming a conductor layer (including a redistribution layer) formed on the insulating layer (a resin composition for forming an insulating layer for forming a conductor layer). The resin composition can also be used in a wide range of applications where a resin composition can be used, such as sheet-like laminated materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, multi-chip packages, package-on-packages, wafer-level packages, panel-level packages, and system-in-packages.

[0215] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to this embodiment is also suitable as a resin composition for forming a redistribution layer as an insulating layer for forming a redistribution layer (resin composition for forming a redistribution layer), and as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When the semiconductor chip package is manufactured, a redistribution layer may be further formed on the encapsulation layer. (1) A step of laminating a temporary fixing film onto the substrate, (2) A step of temporarily fixing the semiconductor chip onto a temporary fixing film, (3) A step of forming a sealing layer on a semiconductor chip, (4) Steps to peel off the substrate and temporary fixing film from the semiconductor chip, (5) A step of forming a rewiring layer as an insulating layer on the surface from which the substrate and temporary fixing film of the semiconductor chip have been peeled off, and (6) Step of forming a redistribution layer as a conductor layer on the redistribution formation layer.

[0216] The resin composition described above can also be used when the printed circuit board is a circuit board with embedded components.

[0217] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention, provided on the support.

[0218] The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less, from the viewpoint of thinning the printed circuit board and providing a cured product with excellent insulating properties even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

[0219] Examples of support materials include films made of plastic materials, metal foils, and release paper, with films made of plastic materials and metal foils being preferred.

[0220] When using a film made of plastic material as a support, examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketones, and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0221] When using metal foil as a support, examples of metal foil include copper foil and aluminum foil, with copper foil being preferred. As for copper foil, foil made of single-metal copper may be used, or foil made of an alloy of copper with another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0222] The support may have a matte finish, corona treatment, or antistatic treatment applied to the surface that bonds with the resin composition layer.

[0223] Furthermore, as the support, a support with a release layer may be used, which has a release layer on the surface that is bonded to the resin composition layer. Examples of release agents used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may be used as the support with a release layer, for example, PET films having a release layer mainly composed of an alkyd resin-based release agent, such as "SK-1", "AL-5", and "AL-7" from Lintec Corporation, "Lumirror T60" from Toray Industries, Inc., "Purex" from Teijin Corporation, and "Unipeel" from Unitika Corporation.

[0224] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When using a support with a release layer, it is preferable that the overall thickness of the support with the release layer is within the above range.

[0225] In one embodiment, the resin sheet may further include other layers as needed. Such other layers include, for example, a protective film similar to the support, provided on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, but for example, it is 1 μm to 40 μm. By laminating the protective film, the adhesion of dust and other debris and scratches to the surface of the resin composition layer can be suppressed.

[0226] A resin sheet can be manufactured, for example, by preparing a resin varnish by dissolving a resin composition in an organic solvent, applying this resin varnish to a support using a die coater or the like, and then drying it to form a resin composition layer.

[0227] Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetic acid esters 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; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. Organic solvents may be used individually or in combination of two or more.

[0228] Drying may be carried out by known methods such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer should be dried so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% to 60% by mass of organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0229] The resin sheet can be stored by rolling it up. If the resin sheet has a protective film, it can be used after removing the protective film.

[0230] [Printed wiring board] A printed circuit board according to one embodiment of the present invention includes an insulating layer formed of a cured product obtained by curing the above-described resin composition.

[0231] Printed circuit boards can be manufactured, for example, using the resin sheet described above, by a method including the following steps (I) and (II). (I) A process of laminating a resin sheet onto an inner layer substrate such that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A process of curing the resin composition layer to form an insulating layer.

[0232] The "internal layer substrate" used in process (I) refers to a material that serves as the substrate for a printed wiring board, and examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. The substrate may also have a conductive layer on one or both sides, and this conductive layer may be patterned. An internal layer substrate with conductive layers formed on one or both sides is sometimes called an "internal layer circuit board." Intermediate products on which an insulating layer and / or a conductive layer is further formed during the manufacturing of a printed wiring board are also included in the "internal layer substrate." If the printed wiring board is a component-embedded circuit board, an internal layer substrate with embedded components may be used.

[0233] Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet onto the inner layer substrate from the support side. Examples of the member used to heat and press the resin sheet onto the inner layer substrate (hereinafter also referred to as the "heat-pressing member") include a heated metal plate (such as a SUS end plate) or a metal roll (such as a SUS roll). It is preferable to press the resin sheet via an elastic material such as heat-resistant rubber, rather than directly pressing the heat-pressing member onto the resin sheet, so that the resin sheet can adequately follow the surface irregularities of the inner layer substrate.

[0234] Lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the heat-pressure temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heat-pressure pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the heat-pressure time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination may preferably be carried out under reduced pressure conditions of 26.7 hPa or less.

[0235] Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressure laminators manufactured by Meiki Seisakusho Co., Ltd., vacuum applicators manufactured by Nikko Materials Co., Ltd., and batch-type vacuum pressure laminators.

[0236] After lamination, the laminated resin sheets may be smoothed by pressing a heat-sealing member from the support side under atmospheric pressure, for example. The pressing conditions for the smoothing process can be the same as the heat-sealing conditions for lamination. The smoothing process can be performed using a commercially available laminator. Lamination and smoothing may be performed continuously using the commercially available vacuum laminator mentioned above.

[0237] The support may be removed between steps (I) and (II), or after step (II).

[0238] In step (II), the resin composition layer is cured to form an insulating layer made of the cured resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions used when forming the insulating layer of a printed circuit board may be used. The resin composition layer may be cured by irradiation with active energy rays such as ultraviolet light, but is usually cured by heat.

[0239] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but in one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0240] Prior to thermal curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermal curing the resin composition layer, it may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0241] A method for manufacturing a printed circuit board may further include (III) a step of drilling holes in an insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. If the support is removed after step (II), the removal of the support may be carried out between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer circuit board.

[0242] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be carried out using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed circuit board.

[0243] Step (IV) is a process for roughening the insulating layer. Typically, smear removal is also performed in this step (IV). The procedure and conditions for the roughening process are not particularly limited. For example, the insulating layer can be roughened by performing swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution in this order.

[0244] Examples of swelling solutions used for roughening treatment include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Sodium hydroxide solution and potassium hydroxide solution are more preferred as alkaline solutions. Examples of commercially available swelling solutions include "Swelling Dip Security P" and "Swelling Dip Security SBU" manufactured by Atotec Japan. The swelling treatment with the swelling solution is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0245] Examples of oxidizing agents used in the roughening treatment include alkaline permanganate solutions obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotec Japan.

[0246] As the neutralizing solution used for roughening treatment, an acidic aqueous solution is preferred, and a commercially available example is "Reduction Solution Securigant P" manufactured by Attec Japan. Treatment with the neutralizing solution can be carried out by immersing the treated surface, which has been roughened with an oxidizing agent, in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the viewpoint of workability, it is preferable to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0247] In one embodiment, the arithmetic mean roughness Ra of the insulating layer surface after roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. Also, the root mean square roughness (Rq) of the insulating layer surface after roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0248] Step (V) is a step of forming a conductive layer, in which a conductive layer is formed on an insulating layer. The conductive material used for the conductive layer is not particularly limited. In a preferred embodiment, the conductive layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductive layer may be a single-metal layer or an alloy layer, and examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). In particular, from the viewpoint of versatility in conductor layer formation, cost, and ease of patterning, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy are preferred, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy are more preferred, and single metal layers of copper are even more preferred.

[0249] The conductive layer may be a single-layer structure, or it may be a multi-layer structure in which two or more single-metal layers or alloy layers made of different types of metals or alloys are stacked. When the conductive layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0250] The thickness of the conductor layer depends on the desired printed circuit board design, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0251] 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 using methods such as the semi-additive method or the fully additive method. From the viewpoint of ease of manufacture, it is preferable to form it by the semi-additive method. An example of forming the conductor layer by the semi-additive method is shown below.

[0252] A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. Subsequently, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having the desired wiring pattern.

[0253] [Semiconductor device] A semiconductor device according to one embodiment of the present invention includes the printed circuit board described above. This semiconductor device can be manufactured using the printed circuit board described above.

[0254] Examples of semiconductor devices include various types of semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft). [Examples]

[0255] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" refer to "parts by mass" and "mass%" respectively, unless otherwise specified. Furthermore, the operations described below were carried out in an environment of normal temperature and pressure unless otherwise specified.

[0256] <Preparation of Maleimide Resin A> A MEK solution (70% by mass of non-volatile components) of maleimide resin A, synthesized by the method described in Synthesis Example 1 of the Japan Institute of Invention and Innovation, Technical Report No. 2020-500211, was prepared. This maleimide resin A has a structure represented by the following formula.

[0257] [ka]

[0258] When the FD-MS spectrum of maleimide resin A is measured, peaks at M+=560, 718, and 876 are observed. These peaks correspond to the cases where n1 is 0, 1, and 2, respectively. Furthermore, when maleimide resin A is analyzed by GPC and the value of the number of repeating units n1 of the indane skeleton is determined based on the number-average molecular weight, n1 = 1.47 and the molecular weight distribution (Mw / Mn) = 1.81. In addition, the content of maleimide resin with an average number of repeating units n1 of 0 in the total amount of maleimide resin A is 26.5 area%.

[0259] The FD-MS spectrum of the maleimide resin A mentioned above represents the spectrum obtained using the following measuring device and conditions. (FD-MS spectrum measurement equipment and measurement conditions) Measuring device: JMS-T100GC AccuTOF Measurement conditions Measurement range: m / z = 4.00~2000.00 Rate of change: 51.2 mA / min Final current value: 45mA Cathode voltage: -10kV Recording interval: 0.07 sec

[0260] The GPC of the aforementioned maleimide resin A represents the value obtained by measuring under the following measuring equipment and conditions. Measurement device: Tosoh Corporation "HLC-8320 GPC" Columns: Tosoh Corporation's Guard Columns "HXL-L", "TSK-GEL G2000HXL", "TSK-GEL G2000HXL", "TSK-GEL G3000HXL", and "TSK-GEL G4000HXL" Detector: RI (Differential Refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent: tetrahydrofuran Flow rate 1.0ml / min Standard: Use monodisperse polystyrene with a known molecular weight in accordance with the measurement manual of the "GPC Workstation EcoSEC-WorkStation". Sample: A 1.0 mass% tetrahydrofuran solution of the maleimide compound in terms of non-volatile components, filtered through a microfilter (50 μl).

[0261] The molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of maleimide resin A and the average number of repeating units "n1" contributing to the indane skeleton in the maleimide resin are represented by those calculated from the GPC chart obtained by the above GPC measurement. Also, the average number of repeating units "n1" is represented by that calculated based on the number-average molecular weight (Mn). Specifically, for compounds with n1 from 0 to 4, the theoretical molecular weight and the measured molecular weight in GPC are plotted on a scatter diagram, and an approximate straight line is drawn. Then, the number-average molecular weight (Mn) is determined from the point indicated by the measured Mn(1) on this straight line, and further the average number of repeating units "n1" is calculated. Furthermore, based on the results of the GPC measurement, the content ratio (area%) of the maleimide resin with an average number of repeating units n1 of 0 in 100 area% of the total amount of maleimide resin A is calculated. For details, reference can be made to the Japan Institute of Invention and Innovation Publication Technical Report Publication No. 2020-500211.

[0262] <Synthesis of PEEK (Polyetheretherketone) Compound A> Into a 500 mL flask (three-necked) equipped with a stirrer, an argon inlet tube, and a Dean-Stark apparatus, add 31.443 g of 4,4'-difluorobenzophenone, 27.419 g of bisphenol A, 29.894 g of potassium carbonate anhydrous, 180 mL of N-methylpyrrolidone, and 90 mL of toluene. Heat with stirring under an argon atmosphere, and reflux toluene at 130 - 140 °C for 4 hours. Then, further heat to distill off toluene at 170 - 180 °C. Furthermore, continue stirring at 170 - 180 °C for 10 hours, then return to room temperature to obtain Product 1.

[0263] To a flask containing product 1, 5.233 g of 4-aminophenol, 6.628 g of anhydrous potassium carbonate, 18 mL of N-methylpyrrolidone, and 90 mL of toluene were added. The mixture was heated again under an argon atmosphere with stirring, and the toluene was refluxed at 130-140°C for 3 hours. Subsequently, the mixture was heated to 170-180°C to distill off the toluene, and stirring was continued for 4 hours while maintaining the aforementioned temperature. After cooling to room temperature, the reaction mixture was added to 5000 mL of methanol and filtered to obtain a powdered solid. This powdered solid was repeatedly washed with methanol and water, and then dried at 100°C for 8 hours to obtain 37.461 g of powdered solid (Diamine-A).

[0264] In a 500 mL three-necked flask equipped with a stirrer and an argon inlet tube, 0.878 g of Diamine-A, 4.943 g of maleic anhydride, and 240 mL of N-methylpyrrolidone were added and stirred at room temperature under an argon atmosphere for 18 hours. Subsequently, 8.576 g of acetic anhydride and 0.689 g of sodium acetate were added and the mixture was stirred at 60°C for 6 hours. After the reaction mixture was allowed to return to room temperature, it was added to 5000 mL of methanol to obtain a powdered solid. This powdered solid was repeatedly washed with methanol and water, and then dried at 100°C for 8 hours to obtain 28.434 g of PEEK compound A, represented by the following formula. The number-average molecular weight of PEEK compound A, calculated by GPC measurement, was 2230. [ka]

[0265] [Example 1] 14 parts PEEK compound A, 20 parts naphthalene-type epoxy resin (ESN475V, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent approximately 332 g / eq.), 30 parts active ester-based curing agent (HPC-8000-65T, manufactured by DIC Corporation, active group equivalent 223, toluene solution with 65% solids by mass), inorganic filler (spherical silica (SO-C2, manufactured by Admatex Corporation, surface-treated with amine-based alkoxysilane compound (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.)), average particle size 0.5 μm, specific surface area 5.8 m²) 260 parts of (1g) and 0.5 parts of a curing accelerator (Shikoku Chemicals Co., Ltd. "1B2PZ", 2-phenyl-1-benzyl-1H-imidazole) were mixed and uniformly dispersed using a high-speed rotary mixer to obtain a resin varnish.

[0266] A polyethylene terephthalate film (Lintec Corporation's "AL5", 38 μm thick) with a release layer was prepared as a support. The aforementioned resin varnish was uniformly applied to the release layer of this support so that the thickness of the resin composition layer after drying was 40 μm. The resin varnish was then dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet containing the support and the resin composition layer.

[0267] [Example 2] In Example 1, 30 parts of an active ester curing agent (DIC Corporation's "HPC-8000-65T", a toluene solution with an active group equivalent of 223 and a solid content of 65% by mass) were replaced with 30 parts of an active ester curing agent (DIC Corporation's "HPC-8150-62T", a toluene solution with an active group equivalent of 229 and a solid content of 62% by mass). Except for the matters mentioned above, a resin varnish and a resin sheet were obtained in the same manner as in Example 1.

[0268] [Example 3] In Example 2, Change the amount of PEEK compound A from 14 parts to 10.5 parts. Furthermore, 5 parts of a radical polymerizable compound (biphenylaralkyl-type maleimide compound (MIR-3000-70MT, manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq., MEK / toluene mixed solution with 70% non-volatile content)) were used. Except for the matters mentioned above, a resin varnish and a resin sheet were obtained in the same manner as in Example 2.

[0269] [Example 4] In Example 2, Change the amount of PEEK compound A from 14 parts to 12.6 parts. Furthermore, two parts of a radical polymerizable compound (BMI-1500, manufactured by Designer Molecules, with a maleimide group equivalent of 750 g / eq.) were used. Except for the matters mentioned above, a resin varnish and a resin sheet were obtained in the same manner as in Example 2.

[0270] [Example 5] In Example 2, The amount of the activated ester curing agent (DIC Corporation's "HPC-8150-62T", a toluene solution with an active group equivalent of 229 and a solid content of 62% by mass) was changed from 30 parts to 25 parts. The amount of curing accelerator (Shikoku Chemicals Co., Ltd. "1B2PZ", 2-phenyl-1-benzyl-1H-imidazole) was changed from 0.5 parts to 0.1 parts. Furthermore, 5 parts of a triazine skeleton-containing cresol novolac curing agent (DIC Corporation's "LA3018-50P", hydroxyl group equivalent 151, 1-methoxy-2-propanol solution with 50% non-volatile components) were used. Except for the matters mentioned above, a resin varnish and a resin sheet were obtained in the same manner as in Example 2.

[0271] [Example 6] In Example 2, Change the amount of PEEK compound A from 14 parts to 10.5 parts. Furthermore, 5 parts of a MEK solution of maleimide resin A (70% by mass of non-volatile components) were used. Except for the matters mentioned above, a resin varnish and a resin sheet were obtained in the same manner as in Example 2.

[0272] [Example 7] In Example 1, 30 parts of an active ester curing agent (DIC Corporation's "HPC-8000-65T", a toluene solution with an active group equivalent of 223 and a solid content of 65% by mass) were replaced with 30 parts of an active ester curing agent containing a naphthalene structure (Air Water Corporation's "PC1300-02-65MA", a methyl amyl ketone solution with an active group equivalent of 200 and a solid content of 65% by mass). Except for the matters mentioned above, a resin varnish and a resin sheet were obtained in the same manner as in Example 1.

[0273] [Comparative Example 1] In Example 2, Without using 14 parts of PEEK compound A, Spherical silica (SO-C2, manufactured by Admatex Corporation, with average particle size 0.5 μm and specific surface area 5.8 m²) surface-treated with an inorganic filler (amine-based alkoxysilane compound (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.)). 2 The amount ( / g) was changed from 60 parts to 45 parts. Except for the matters mentioned above, a resin varnish and a resin sheet were obtained in the same manner as in Example 2.

[0274] [Comparative Example 2] In Example 3, Without using 10.5 parts of PEEK compound A, The amount of the radical polymerizable compound (biphenylaralkyl type maleimide compound (MIR-3000-70MT, manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq., MEK / toluene mixed solution with 70% non-volatile content)) was changed from 5 parts to 20 parts. Except for the matters mentioned above, a resin varnish and a resin sheet were obtained in the same manner as in Example 3.

[0275] [Comparative Example 3] In Example 4, Without using 12.6 parts of PEEK compound A, The amount of radical polymerizable compound (BMI-1500, manufactured by Designer Molecules, with a maleimide group equivalent of 750 g / eq.) was changed from 2 parts to 14 parts. Except for the matters mentioned above, a resin varnish and a resin sheet were obtained in the same manner as in Example 4.

[0276] [Measurement of dielectric properties (dielectric constant and dielectric loss tangent)] The resin sheets prepared in the examples and comparative examples were heated at 200°C for 90 minutes to heat-cur the resin composition layer. The support was then peeled off to obtain "Cured Resin Composition A". This cured resin composition A was cut into test pieces 2 mm wide and 80 mm long. The dielectric constant Dk and dielectric loss tangent Df of these test pieces were measured using the cavity resonance perturbation method with an Agilent Technologies HP8362B at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurements were performed on three test pieces, and the average values ​​are shown in the table below.

[0277] [Measurement of plating peel strength] (1) Surface preparation of the inner layer circuit board: As the inner layer circuit board, a glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") with inner layer circuits (copper foil) on both sides was prepared. Both sides of this inner layer circuit board were etched to 1 μm using MEC's ​​"CZ8101" to roughen the copper surface.

[0278] (2) Lamination of resin sheets: A resin sheet was laminated to both sides of the inner circuit board using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator, CVP700). This lamination was performed so that the resin composition layer of the resin sheet was in contact with the inner circuit board. This lamination was carried out by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing at 130°C and a pressure of 0.74 MPa for 45 seconds. Subsequently, a hot press was performed at 120°C and a pressure of 0.5 MPa for 75 seconds.

[0279] (3) Curing of the resin composition: The laminated resin sheet and the inner circuit board were heated at 130°C for 30 minutes, and then heated at 170°C for another 30 minutes to cure the resin composition and form an insulating layer. Subsequently, the support was peeled off to obtain a laminated substrate comprising the insulating layer, the inner circuit board, and the insulating layer in that order.

[0280] (4) Roughening treatment: The aforementioned laminated substrate was immersed in a swelling solution (Swelling Dip Securigant P (aqueous solution of glycol ethers and sodium hydroxide) containing diethylene glycol monobutyl ether, manufactured by Atotec Japan) at 60°C for 10 minutes. Next, the laminated substrate was immersed in a roughening solution (Concentrate Compact P (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L) manufactured by Atotec Japan) at 80°C for 20 minutes. After that, the laminated substrate was immersed in a neutralizing solution (Reduction Sulfuric Acid Securigant P (aqueous solution of sulfuric acid) manufactured by Atotec Japan) at 40°C for 5 minutes. After that, the laminated substrate was dried at 80°C for 30 minutes to obtain "Evaluation Substrate A".

[0281] (5) Plating using the semi-additive method: Evaluation substrate A was immersed in an electroless plating solution containing PdCl2 at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. After that, it was heated at 150°C for 30 minutes to perform annealing. Subsequently, an etching resist was formed and a pattern was formed by etching. Then, copper sulfate electroplating was performed to form a conductive layer with a thickness of 20 μm. Next, annealing was performed at 200°C for 60 minutes to obtain "Evaluation substrate B".

[0282] (6) Measurement of plating peel strength: A rectangular section measuring 10 mm wide and 100 mm long was cut into the conductive layer of evaluation substrate B. One end of the rectangular section was peeled off and grasped with a gripper (Autocom type tester "AC-50C-SL" manufactured by TSE Corporation). The rectangular section was peeled off vertically at a speed of 50 mm / min at room temperature using the gripper, and the load (kgf / cm) when 35 mm was peeled off was measured as the plating peel strength.

[0283] [Measurement of surface roughness Ra] The arithmetic mean roughness Ra of the insulating layer surface of evaluation substrate A was measured. The measurement was performed using a non-contact surface roughness meter (WYKO NT3300, B-In Instruments) in VSI mode with a 50x lens, and a measurement range of 121 μm × 92 μm. This measurement was performed at 10 points, and the average values ​​are shown in the table below.

[0284] [Measurement of glass transition temperature] A cured resin composition A was cut into test pieces approximately 5 mm wide and 15 mm long, and thermomechanical analysis was performed using a dynamic viscoelasticity analyzer (EXSTAR6000, manufactured by SII Nanotechnology Co., Ltd.) with tensile loading. After mounting the test pieces in the apparatus, measurements were taken under the conditions of a load of 200 mN and a heating rate of 2 °C / min. The peak top of the obtained tanδ was calculated as the glass transition temperature (°C).

[0285] [Table 1] *In the table, the content of component (A) represents the content of component (A) when the total resin components in the resin composition are assumed to be 100% by mass. The content of component (E) represents the content of component (E) when the non-volatile components in the resin composition are assumed to be 100% by mass. Component (C) / Component (B) represents the ratio of [total number of active groups of the active ester curing agent] / [total number of epoxy groups of the epoxy resin], where [total number of epoxy groups of the epoxy resin] is the sum of all values ​​obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent, and [total number of active groups of the active ester curing agent] is the sum of all values ​​obtained by dividing the mass of the non-volatile components of the active ester curing agent present in the resin composition by the active ester group equivalent.

Claims

1. (A) Polyether ether ketone compounds having a maleimide group, (B) Epoxy resin, and (C) Contains an active ester-based curing agent, (A) The content of component (A) is 1% by mass or more and 25% by mass or less, when the nonvolatile components in the resin composition are considered to be 100% by mass. The content of component (B) is 5% by mass or more and 30% by mass or less, when the nonvolatile components in the resin composition are considered to be 100% by mass. (C) A resin composition in which the content of component is 1% by mass or more and 30% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

2. The resin composition according to claim 1, wherein the number average molecular weight of component (A) is 10,000 or less.

3. The resin composition according to claim 1 or 2, wherein component (A) has a maleimide group at its terminus.

4. The resin composition according to any one of claims 1 to 3, wherein the content of component (A) is 5% by mass or more and 60% by mass or less, when the resin component, which is the non-volatile component of the resin composition excluding inorganic fillers, is taken as 100% by mass.

5. The resin composition according to any one of claims 1 to 4, wherein component (B) comprises a naphthol-type epoxy resin.

6. The resin composition according to any one of claims 1 to 5, wherein component (C) is one or more selected from dicyclopentadiene-type active ester curing agents and naphthalene-type active ester curing agents containing a naphthalene structure.

7. The ratio of component (B) to component (C) is 0.01 or more and 5 or less, expressed as the ratio of the total number of active groups in component (C) to the total number of epoxy groups in component (B). The total number of epoxy groups in component (B) is the sum of all values ​​obtained by dividing the mass of the nonvolatile components of component (B) present in the resin composition by the epoxy equivalent. The resin composition according to any one of claims 1 to 6, wherein the total number of active groups of component (C) is the sum of all values ​​obtained by dividing the mass of the nonvolatile component of component (C) present in the resin composition by the equivalent amount of active ester groups.

8. Furthermore, the resin composition according to any one of claims 1 to 7, comprising a resin having a polymerizable unsaturated group (D) different from component (A).

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

10. Furthermore, the resin composition according to any one of claims 1 to 9, further comprising (E) an inorganic filler.

11. A resin composition according to any one of claims 1 to 10, for forming an insulating layer.

12. A resin composition for forming an insulating layer when forming a conductive layer on an insulating layer, as described in any one of claims 1 to 11.

13. A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of claims 1 to 12.

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

15. A semiconductor device comprising a printed circuit board as described in claim 14.

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