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

Abstract

To provide: a resin composition which can provide a cured product having excellent dielectric properties and adhesion to a copper foil (copper foil adhesion); and a cured product, a resin sheet, a printed wiring board, and a semiconductor device, which are obtained using the resin composition.SOLUTION: The resin composition of the present invention comprises: (A) a curable resin; and (B) a compound having a hetero ring structure containing 2 or more nitrogen atoms and a cage-type silsesquioxane structure in the molecule.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition. The present invention further relates to a cured product, a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition. [Background technology]

[0002] Non-Patent Document 1 discloses a polyimide made from a double-decker silsesquioxane compound. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Shouming Wu et al., “Synthesis and Characterization of Semiaromatic Polyimides Containing POSS in Main Chain Derived from Double-Decker-Shaped Silsesquioxane”, “Macromolecules”, 2007, vol. 40, p. 5698-5705 Summary of the Invention [Problem to be solved by the invention]

[0004] Incidentally, in recent years, insulating layers used in wiring boards having buried wiring layers, for example, are required to have excellent dielectric properties and adhesion to copper foil.

[0005] An object of the present invention is to provide a resin composition capable of producing a cured product having excellent dielectric properties and adhesion to copper foil (copper foil adhesion); and a cured product, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition. [Means for solving the problem]

[0006] As a result of intensive research aimed at solving the above-mentioned problems, the inventors have found that the above-mentioned problems can be solved by a resin composition containing (A) a curable resin and (B) a compound having in its molecule a heterocyclic structure containing two or more nitrogen atoms and a cage-type silsesquioxane structure, and have thus completed the present invention.

[0007] That is, the present invention includes the following. [1] A resin composition comprising: (A) a curable resin; and (B) a compound having, in the molecule, a heterocyclic structure containing two or more nitrogen atoms and a cage-type silsesquioxane structure. [2] The resin composition according to [1], wherein the heterocyclic structure contains three nitrogen atoms. [3] The resin composition according to [1] or [2], wherein the component (B) contains, in the molecule, an aromatic ring structure which may have a substituent and is bonded to the heterocyclic structure via a linking group. [4] The resin composition according to any one of [1] to [3], wherein the cage silsesquioxane structure is a double-decker silsesquioxane structure. [5] The resin composition according to any one of [1] to [4], wherein the cage silsesquioxane structure includes a cage structure represented by the following formula (B1): [ka] [In the above formula (B1), X's are each independently a group selected from an alkyl group having 1 to 40 carbon atoms, whose hydrogen atom may be replaced by a halogen atom, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group, whose hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 20 carbon atoms, and an arylalkyl group in which an aryl group, whose hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 20 carbon atoms, is bonded to an alkylene group having 1 to 8 carbon atoms; Y's each independently represent an alkyl group having 1 to 40 carbon atoms, whose hydrogen atom may be replaced by a halogen atom, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group, whose hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group in which an aryl group, whose hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 20 carbon atoms, is bonded to an alkylene group having 1 to 8 carbon atoms; * is a bond; When X or Y is an alkyl group having 1 to 40 carbon atoms, -CH2- contained in the alkyl group may be replaced by -O- or -CH=CH-; When X or Y is an aryl group, and a hydrogen atom of the aryl group is replaced by an alkyl group having 1 to 20 carbon atoms, a hydrogen atom of the alkyl group having 1 to 20 carbon atoms may be replaced by a halogen atom, and -CH2- contained in the alkyl group having 1 to 20 carbon atoms may be replaced by -O- or -CH=CH-; When X or Y is an arylalkyl group, -CH2- contained in the arylalkyl group may be replaced by -O-.] [6] The resin composition according to [5], wherein each of X's is a phenyl group. [7] The resin composition according to any one of [1] to [6], wherein an imide bond is present between the heterocyclic structure and the cage silsesquioxane structure. [8] The resin composition according to any one of [1] to [7], further comprising (C) an inorganic filler. [9] The resin composition according to [8], wherein the content of the (C) component is 10 mass% or more, relative to 100 mass% of the non-volatile components in the resin composition.

[10] The resin composition according to [8] or [9], wherein the content of component (C) is 90 mass% or less, when the total amount of non-volatile components in the resin composition is 100 mass%.

[11] The resin composition according to any one of [8] to

[10] , wherein the content of the component (C) is 40 mass% or less, relative to 100 mass% of the non-volatile components in the resin composition.

[12] The resin composition according to any one of [8] to

[11] , wherein the total content of the (B) component and the (C) component is 50 mass% or more, relative to 100 mass% of the non-volatile components in the resin composition.

[13] The resin composition according to any one of [1] to

[12] , wherein the component (A) contains an (A-2) radical polymerizable resin.

[14] The resin composition according to any one of [1] to

[13] , wherein the content of component (B) is 0.01% by mass or more and 60% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass.

[15] The resin composition according to any one of [1] to

[14] , wherein the cured product of the resin composition has a dielectric constant (Dk) value of less than 3.2.

[16] The resin composition according to any one of [1] to

[15] , wherein a dielectric loss tangent (Df) value of a cured product of the resin composition is less than 0.0032.

[17] The resin composition according to any one of [1] to

[16] , which is for use in an insulating layer of a printed wiring board.

[18] A cured product of the resin composition according to any one of [1] to

[17] .

[19] 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 [1] to

[17] .

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

[17] .

[21] A semiconductor device comprising the printed wiring board according to

[20] . Effect of the Invention

[0008] According to the present invention, it is possible to provide a resin composition that can provide dielectric properties and adhesion to copper foil (copper foil adhesion); and a cured product, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention will be described in detail below with reference to preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be modified and implemented as desired without departing from the scope of the claims of the present invention and their equivalents.

[0010] [Resin composition] The resin composition of the present invention contains (A) a curable resin and (B) a compound having a heterocyclic structure containing two or more nitrogen atoms and a cage-type silsesquioxane structure in the molecule, and thus the resin composition of the present invention can provide a cured product having excellent dielectric properties and adhesion to copper foil (copper foil adhesion).

[0011] The resin composition of the present invention may further contain optional components in addition to the components (A) and (B). Examples of the optional components include an inorganic filler (C), a curing agent (D) (excluding the components (A) and (B)), a curing accelerator (E), a polymerization initiator (F), other additives (G), and an organic solvent (H). Each component contained in the resin composition of the present invention will be described in detail below.

[0012] <(A) Curing resin> The resin composition contains (A) a curable resin. As the (A) curable resin, one or more resins selected from a thermosetting resin, a photocurable resin, and a radical polymerizable resin can be used. The radical polymerizable resin is a resin in which radical polymerization proceeds by heat or light, optionally in the presence of a polymerization initiator, and may be classified as a thermosetting resin or a photocurable resin. The (A) component may be used alone or in combination of two or more types in any ratio. From the viewpoint of forming an insulating layer of a printed wiring board, it is preferable that the (A) curable resin contains one or more resins selected from (A-1) thermosetting resins. From the viewpoint of providing a cured product with a lower dielectric tangent, it is preferable that the (A) curable resin contains one or more resins selected from (A-2) radical polymerizable resins in addition to one or more resins selected from thermosetting resins. However, the (A) component does not include those corresponding to the (B) component described later.

[0013] Examples of the (A-1) thermosetting resin include epoxy resin, epoxy acrylate resin, urethane acrylate resin, urethane resin, cyanate resin, polyimide resin, benzoxazine resin, unsaturated polyester resin, phenol resin, melamine resin, silicone resin, and phenoxy resin. In one embodiment, the (A) curable resin includes an epoxy resin. When the resin composition includes the (A-1) component, it is preferable that the resin composition includes the (D) component described below.

[0014] Examples of epoxy resins include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, hydrogenated bisphenol A type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl esters, and the like. Examples of epoxy resins that can be used include aryl epoxy resins, cresol novolac epoxy resins, phenol aralkyl epoxy resins, biphenyl epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane epoxy resins, cyclohexane dimethanol epoxy resins, naphthylene ether epoxy resins, trimethylol epoxy resins, tetraphenylethane epoxy resins, isocyanurate epoxy resins, phenolphthalimidine epoxy resins, and phenolphthalein epoxy resins.

[0015] The resin composition preferably contains, as an epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on 100% by mass of the non-volatile components of the epoxy resin.

[0016] Epoxy resins include epoxy resins that are solid at a temperature of 25° C. (hereinafter sometimes referred to as "solid epoxy resins") and epoxy resins that are liquid at a temperature of 25° C. (hereinafter sometimes referred to as "liquid epoxy resins"). The resin composition of the present invention may contain, as the epoxy resin, only a solid epoxy resin, or only a liquid epoxy resin, or may contain a combination of a solid epoxy resin and a liquid epoxy resin.

[0017] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0018] Preferred solid epoxy resins include bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, phenol aralkyl type epoxy resins, tetraphenylethane type epoxy resins, phenolphthalimidine type epoxy resins, and phenolphthalein type epoxy resins.

[0019] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy resins) manufactured by DIC Corporation; and "EXA-73" manufactured by DIC Corporation. 11", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN475V" manufactured by Nippon Steel Chemical & Material Co., Ltd. (Naphthalene type epoxy resin); "ESN485" (Naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (Dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (Bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YL6121" (Biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX8800" (Anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX77" manufactured by Mitsubishi Chemical Co., Ltd. Examples of epoxy resins include "PG-100" (phenol aralkyl type epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals, "YX7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical, "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical, "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical, "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical, and "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more types.

[0020] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0021] Preferred liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, hydrogenated bisphenol A type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, and epoxy resins having a butadiene structure.

[0022] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", and "825" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", and "604" (glycidylamine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycilol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resins) manufactured by ADEKA Corporation; and "EP-4088S" (glycidylamine type epoxy resins) manufactured by ADEKA Corporation. Examples of such epoxy resins include: "ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase Chemtex Corporation (glycidyl ester type epoxy resin); "Celloxide 2021P" manufactured by Daicel Corporation (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical & Material Co., Ltd. (1,4-glycidylcyclohexane type epoxy resin), "YX8000" manufactured by Mitsubishi Chemical Corporation (hydrogenated bisphenol A type epoxy resin), and "KF-101" manufactured by Shin-Etsu Chemical Co., Ltd. (epoxy modified silicone resin). These may be used alone or in combination of two or more types.

[0023] The epoxy resin may be any one of a liquid epoxy resin, a solid epoxy resin, or a combination thereof, but it is preferable to include a liquid epoxy resin, and it is particularly preferable to be a combination of a liquid epoxy resin and a solid epoxy resin.

[0024] When a solid epoxy resin and a liquid epoxy resin are used in combination as the epoxy resin, the mass ratio thereof (solid epoxy resin:liquid epoxy resin) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, and particularly preferably 3:1 to 1:3.

[0025] The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 1,000 g / eq., even more preferably 80 g / eq. to 500 g / eq., and even more preferably 100 g / eq. to 300 g / eq. The epoxy equivalent is the mass of the resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

[0026] The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, and further preferably from 400 to 1500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0027] The content of the epoxy resin exceeds 0% by mass, and from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are taken as 100% by mass, the content is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is not particularly limited, but can be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, or 25% by mass or less.

[0028] Furthermore, the content of the epoxy resin, when the resin component in the resin composition is taken as 100% by mass, is preferably 0.2% by mass or more, more preferably 2% by mass or more, even more preferably 6% by mass or more, and particularly preferably 10% by mass or more, from the viewpoint of obtaining the effects of the present invention significantly, and the upper limit is not particularly limited, but may be, for example, 85% by mass or less, 65% by mass or less, 55% by mass or less, or 50% by mass or less. The resin component refers to the non-volatile components in the resin composition excluding component (B).

[0029] <(A-2) Radical Polymerizable Resin> The resin composition may contain a radical polymerizable resin as the component (A-2). However, the component (A-2) does not include components (B) to (F) described below. The component (A-2) may be used alone or in combination of two or more. When the resin composition contains the component (A-2), it is preferable that the resin composition contains the component (F) described below.

[0030] The component (A-2) contains a compound having a radically polymerizable unsaturated group in the molecule (hereinafter referred to as "radical polymerizable compound"). The radically polymerizable compound is not particularly limited as long as it has a radically polymerizable unsaturated group in the molecule, but it is preferable to contain a compound having one or more radically polymerizable unsaturated groups selected from vinyl groups, allyl groups, styryl groups, vinylphenyl groups, acryloyl groups, methacryloyl groups, maleimide groups, fumaroyl groups, and maleoyl groups, and more preferably contains a compound containing one or more radically polymerizable unsaturated groups selected from allyl groups, styryl groups, vinylphenyl groups, acryloyl groups, and methacryloyl groups. An example of a resin containing a radically polymerizable unsaturated group is "SA9000-111" manufactured by SABIC.

[0031] The component (A-2) is preferably at least one selected from a maleimide resin, a styryl resin, a (meth)acrylic resin, an allyl resin, and a butadiene resin, more preferably at least one selected from a maleimide resin, a (meth)acrylic resin, and a styryl resin, and more preferably either a maleimide resin or a styryl resin.

[0032] The component (A-2) more preferably contains a compound having two or more radically polymerizable unsaturated groups in the molecule. There is no upper limit to the number, but it may be 10 or less.

[0033] (Maleimide resin) The resin composition of the present invention may contain a maleimide resin as the component (A-2).

[0034] The component (A-2) is (A2-1) a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to a nitrogen atom of the maleimide; (A2-2) Maleimide compounds containing a trimethylindane skeleton, and (A2-3) a maleimide compound having an aromatic ring directly bonded to a nitrogen atom of the maleimide; It is preferable that the compound is one or more selected from the following:

[0035] The term "directly" used herein means that, in the case of component (A2-1), there are no other groups between the nitrogen atom of the maleimide and the aliphatic group having 5 or more carbon atoms, and in the case of component (A2-3), there are no other groups between the nitrogen atom of the maleimide and the aromatic ring.

[0036] The maleimide resin, regardless of whether it is the (A2-1), (A2-2), or (A2-3) component, preferably has two or more maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule.

[0037] The following describes the components (A2-1), (A2-2), and (A2-3) which are suitable embodiments of the maleimide resin. In the following, the term "substituent" means, unless otherwise specified, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylthio group, a monovalent heterocyclic group, an alkenyl group, an alkylidene group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group. Examples of halogen atoms used as substituents include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group or alkenyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 14, even more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a t-butyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 3 to 14, even more preferably 3 to 12, still more preferably 3 to 6, and particularly preferably 3 to 4. Examples of the alkenyl group include an ethenyl group, a propenyl group, an n-butenyl group, and a t-butenyl group. The number of carbon atoms in the cycloalkyl group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. The alkoxy group used as a substituent may be either linear or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 6. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The cycloalkyloxy group used as a substituent preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and further preferably 3 to 6 carbon atoms.Examples of the cycloalkyloxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group. The number of carbon atoms of the alkylthio group used as a substituent is preferably 1 to 20, more preferably 1 to 14, even more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3. The aryl group used as a substituent is a group in which one hydrogen atom on an aromatic ring is removed from an aromatic hydrocarbon. The number of carbon atoms of the aryl group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryloxy group used as a substituent include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. The number of carbon atoms in the arylalkyl group used as a substituent is preferably 7 to 25, more preferably 7 to 19, further preferably 7 to 15, and further preferably 7 to 11. Examples of the arylalkyl group include phenyl-C1-C. 12 Alkyl groups, naphthyl-C1-C 12 Alkyl groups and anthracenyl-C1-C 12 The number of carbon atoms in the arylalkoxy group used as a substituent is preferably 7 to 25, more preferably 7 to 19, further preferably 7 to 15, and further preferably 7 to 11. Examples of the arylalkoxy group include phenyl-C1-C 12 Alkoxy groups and naphthyl-C1-C 12Examples of the monovalent heterocyclic group include an alkoxy group. The number of carbon atoms of the arylthio group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. The monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom from a heterocyclic ring of a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably 3 to 21, more preferably 3 to 15, and even more preferably 3 to 9. The monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocyclic ring include a thienyl group, a pyrrolyl group, a furanyl group, a furyl group, a pyridyl group, a pyridazinyl group, a pyrimidyl group, a pyrazinyl group, a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group. The alkylidene group used as a substituent refers to a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms in the alkylidene group is preferably 1 to 20, more preferably 1 to 14, even more preferably 1 to 12, still more preferably 1 to 6, and particularly preferably 1 to 3. The acyl group used as a substituent refers to a group represented by the formula: -C(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms in the acyl group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 7. The acyloxy group used as a substituent refers to a group represented by the formula: -OC(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms in the acyloxy group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 7. The above-mentioned substituents may further have a substituent (hereinafter, sometimes referred to as a "secondary substituent"). Unless otherwise specified, the secondary substituent may be the same as the above-mentioned substituent.

[0038] <(A2-1) component> The component (A2-1) is a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to a nitrogen atom of the maleimide. Such a maleimide compound can be obtained, for example, by subjecting a component containing an aliphatic amine compound (such as a dimer diamine compound), maleic anhydride, and, if necessary, tetracarboxylic dianhydride to an imidization reaction.

[0039] In one embodiment, the component (A2-1) includes a compound represented by the following formula (A2-1-1):

[0040] [ka]

[0041] In formula (A2-1-1), A 1 represents an aliphatic group having 5 or more carbon atoms which may have a substituent, L 1 represents a single bond or a divalent linking group, nB1 represents an integer from 0 to 20. 1 When there are multiple, they may be the same or different, and L 1 When there are multiple, they may be the same or different.

[0042] A 1 The number of carbon atoms in the aliphatic group represented by the formula (I) is 5 or more, and preferably 10 or more, 15 or more, or 20 or more. The upper limit of the number of carbon atoms is not particularly limited, and may be, for example, 100 or less, 80 or less, 60 or less, or 50 or less. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0043] In one embodiment, A 1 is a divalent group represented by the following formula (A2-1-2).

[0044] [ka]

[0045] In formula (A2-1-2), A 11 represents a single bond, an alkylene group, or an alkenylene group (preferably an alkylene group or an alkenylene group), Ring Z 1 represents a non-aromatic ring optionally having a group selected from an alkyl group and an alkenyl group (preferably a cycloalkane ring or cycloalkene ring optionally having a group selected from an alkyl group and an alkenyl group), nB11 represents an integer of 0 to 3 (preferably 0 or 1, more preferably 1); * indicates the binding site. 11 Or Z 1 Each of A may independently have a substituent. 11 When there are multiple rings, they may be the same or different. 1 When there are multiple, they may be the same or different.

[0046] L 1 Examples of the divalent linking group represented by the formula (A2-1-3) include divalent organic groups (preferably divalent ring-containing organic groups (e.g., aromatic rings or non-aromatic rings)) consisting of two or more (e.g., 2 to 3000, 2 to 1000, 2 to 100, or 2 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, and among these, divalent groups represented by the following formula (A2-1-3) are preferred.

[0047] [ka]

[0048] In formula (A2-1-3), A 12 represents a single bond or a divalent group consisting of one or more (e.g., 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms, R B1 and R B2 each independently represents a substituent, nB12 represents 0 or 1; nB13 and nB14 each independently represent an integer of 0 to 3 (preferably 0 or 1), * indicates the binding site. B1 When there are multiple, they may be the same or different, and R B2 When there are multiple, they may be the same or different.

[0049] When nB12 is 0, the divalent group represented by formula (A2-1-3) is a divalent group having a structure represented by the following formula (A2-1-4): B1 , nB13 and * are as explained in formula (A2-1-3).

[0050] [ka]

[0051] In the embodiment of formula (A2-1-3) where nB12 is 1, A 12 The divalent group represented by the following formula (A2-1-5) is preferable.

[0052] [ka]

[0053] In formula (A2-1-5), Y 1 represents a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; Ring Z 2 represents an optionally substituted non-aromatic ring or an optionally substituted aromatic ring, nB15 represents an integer of 0 to 5 (preferably 0 to 3), * indicates the binding site. 1 Or Z 2 Each of Y may independently have a substituent. 1 When there are multiple rings, they may be the same or different. 2When there are multiple, they may be the same or different.

[0054] A 12 Specific examples of the divalent group represented by the formula (I) include, but are not limited to, -CH-, -CH(CH)-, -CH(CHCH)-, -C(CH)-, -C(CH)(CHCH)-, -C(CHCH)-, -O-, -CO-, -S-, -SO-, and -SO-, as well as divalent organic groups represented by the formula (I) below. [ka]

[0055] The weight average molecular weight (Mw) of the component (A2-1) is not particularly limited, but is preferably 150 to 50,000, more preferably 300 to 20,000, and more specifically, in an embodiment in which nB1 in formula (A2-1-1) is an integer of 1 or more, it is preferably 500 to 50,000, more preferably 1,000 to 20,000, and in an embodiment in which nB1 is 0, it is preferably 150 to 5,000, more preferably 300 to 1,000. The Mw of the component (A2-1) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0056] Furthermore, with respect to the component (A2-1), the functional group equivalent of the maleimide group is preferably 50 to 20,000 g / eq, more preferably 100 to 20,000 g / eq.; more specifically, in an embodiment in which nB1 in formula (A2-1-1) is an integer of 1 or greater, it is preferably 300 g / eq. to 20,000 g / eq., more preferably 500 g / eq. to 10,000 g / eq.; and in an embodiment in which nB1 is 0, it is preferably 50 g / eq. to 2,000 g / eq., more preferably 100 g / eq. to 1,000 g / eq., even more preferably 200 g / eq. to 600 g / eq., and particularly preferably 300 g / eq. to 400 g / eq.

[0057] In order to achieve the intended effects of the present invention, the component (A2-1) preferably contains a maleimide compound having any of a structure represented by formula (A2-1-6), a structure represented by formula (A2-1-7), or a structure represented by formula (A2-1-8):

[0058] [ka]

[0059] In formula (A2-1-6), A 11 and ring Z 1 As explained above, A 11 -Ring Z 1 -A 11 The number of carbon atoms per block is preferably 20 to 100 (more preferably 30 to 60 or 30 to 50), and it is particularly preferably a so-called dimer acid skeleton (C36 skeleton; C36 aliphatic skeleton derived from dimer diamine). nB16 represents an integer of 1 to 10.

[0060] [ka] In formula (A2-1-7), A 11 , Y 1 , ring Z 1 , ring Z 2 and nB15 are as described above, and A 11 -Ring Z 1 -A 11 The number of carbon atoms per block is preferably 20 to 100 (more preferably 30 to 60 or 30 to 50), and it is particularly preferably a so-called dimer acid skeleton (C36 skeleton; C36 aliphatic skeleton derived from dimer diamine). 2 The block consisting of the divalent group A 12 Among them, a divalent group containing an oxygen atom is preferable. nB17 represents an integer of 1 to 10.

[0061] [ka]

[0062] In formula (A2-1-8), A 11 and ring Z 1 As explained above, A 11 -Ring Z 1 -A 11 The number of carbon atoms per block is preferably 20 to 100 (more preferably 30 to 60 or 30 to 50), and it is particularly preferably a so-called dimer acid skeleton (C36 skeleton; C36 aliphatic skeleton derived from dimer diamine). nB11 represents an integer of 0 to 3.

[0063] Commercially available maleimide compounds having a structure represented by formula (A2-1-6) include, for example, "BMI-3000J" and "BMI-5000" manufactured by Designer Molecules. Commercially available maleimide compounds having a structure represented by formula (A2-1-7) include, for example, "BMI-1400", "BMI-1500", and "BMI-1700" manufactured by Designer Molecules. Commercially available maleimide compounds having a structure represented by formula (A2-1-8) include, for example, "BMI-689" manufactured by Designer Molecules. Examples of such materials include "BMI-1500" and "BMI-1700" manufactured by Designer Molecules, Inc., as disclosed in Annika Wagner et al., "Cure kinetics of bismaleimides as basis for polyimide-like inks for PolyJet (registered trademark)-3D-printing," J. APPL. POLYM. SCI., 2018, p. 47244.

[0064] <(A2-2) component> The component (A2-2) is a maleimide compound containing a trimethylindane skeleton, which is represented by the following formula (A2-2-1).

[0065] [ka]

[0066] The benzene ring in the trimethylindane skeleton may have a substituent. When the benzene ring in the trimethylindane skeleton has a substituent, the number of the substituent may be 1 or 2 or more. The upper limit of the number of the substituents that the benzene ring in the trimethylindane skeleton has is usually 3 or less. When the number of the substituents is 2 or more, they may be the same or different from each other. Among them, it is preferable that the benzene ring in the trimethylindane skeleton does not have a substituent.

[0067] The number of trimethylindane structures contained in one molecule of the component (A2-2) may be 1, or may be equal to or greater than 2. The upper limit can be, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

[0068] The (A2-2) component preferably further contains an aromatic ring skeleton in addition to the above-mentioned trimethylindane skeleton. The aromatic ring skeleton may be either a carbon ring skeleton or a heterocyclic skeleton, but a carbon ring skeleton is more preferable. The number of ring carbon atoms of the aromatic ring skeleton is preferably 3 to 20, more preferably 4 to 16, 5 to 14, or 6 to 10. Examples of the aromatic ring skeleton include a benzene ring skeleton, a naphthalene ring skeleton, and an anthracene ring skeleton. The number of aromatic ring skeletons contained in one molecule of the (A2-2) component is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. When the (A2-2) component contains two or more aromatic ring skeletons in addition to the trimethylindane skeleton, the aromatic ring skeletons may be the same or different from each other.

[0069] The aromatic ring skeleton may have a substituent. When the aromatic ring skeleton has a substituent, the number of the substituent may be 1 or 2 or more. The upper limit of the number of the substituent that the aromatic ring skeleton has is usually 4 or less. When the number of the substituents is 2 or more, they may be the same or different from each other.

[0070] The (A2-2) component preferably further contains a divalent aliphatic hydrocarbon group in addition to the trimethylindane skeleton. In particular, when the (A2-2) component contains an aromatic ring skeleton in addition to the benzene ring in the trimethylindane skeleton, the (A2-2) component preferably contains a divalent aliphatic hydrocarbon group. In this case, the divalent aliphatic hydrocarbon group preferably connects the benzene ring and the aromatic ring skeleton in the trimethylindane skeleton. In addition, the divalent aliphatic hydrocarbon group preferably connects the aromatic ring skeletons together.

[0071] The number of carbon atoms of the divalent aliphatic hydrocarbon group is preferably 1 or more, preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The divalent aliphatic hydrocarbon group may be either a divalent saturated hydrocarbon group or a divalent unsaturated hydrocarbon group, but is preferably a divalent saturated hydrocarbon group, and more preferably an alkylene group. Examples of the divalent aliphatic hydrocarbon group include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; and branched alkylene groups such as monomethylmethylene (-CH(CH3)-), monoethylmonomethylene (-CH(CH2CH3)-), dimethylmethylene (-C(CH3)2-), ethylmethylmethylene (-C(CH3)(CH2CH3)-), and diethylmethylene (-C(CH2CH3)2-). When the component (A2-2) contains two or more divalent aliphatic hydrocarbon groups in addition to the trimethylindane skeleton, those divalent aliphatic hydrocarbon groups may be the same or different.

[0072] The component (A2-2) may contain a structure represented by the following formula (A2-2-2): The entire component (A2-2) may have a structure represented by formula (A2-2-2), or only a part of the component (A2-2) may have a structure represented by formula (A2-2-2).

[0073] [ka]

[0074] In formula (A2-2-2), Ar a1 represents a divalent aromatic ring group which may have a substituent, R a1 and R a2 each independently represents a substituent, R a3 represents a divalent aliphatic hydrocarbon group, n a1 represents a positive integer, n a2 each independently represents an integer of 0 to 4, n a3 R each independently represents an integer of 0 to 3. a1 When there are multiple, they may be the same or different, and R a2 If there are multiple R a3 may be the same or different from each other.

[0075] Ar a1 represents a divalent aromatic ring group which may have a substituent. The number of carbon atoms in the divalent aromatic ring group is preferably 6 or more, and preferably 20 or less, more preferably 16 or less, 14 or less, or 10 or less. Examples of the divalent aromatic ring group include a phenylene group and a naphthylene group. Examples of the substituent that the divalent aromatic ring group may have include the above-mentioned substituents, and among them, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, and a mercapto group are preferred. The hydrogen atom of each substituent may be further substituted with a halogen atom. When the divalent aromatic ring group has a substituent, the number of the substituent is preferably 1 to 4. When the divalent aromatic ring group has two or more substituents, the two or more substituents may be the same or different. a1 is preferably a divalent aromatic ring group having no substituent.

[0076] R a1 R represents a substituent. a1 Examples of the substituent represented by the formula (I) include the aforementioned substituents, and among them, 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, and a mercapto group are preferred. The hydrogen atom of each of the substituents may be further substituted with a halogen atom.

[0077] Among them, R a1 is more preferably one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and is further preferably an alkyl group having 1 to 4 carbon atoms.

[0078] R a2 R represents a substituent. a2 Examples of the substituent represented by the formula (I) include the aforementioned substituents, and among them, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, and a mercapto group are preferred. The hydrogen atom of each of the substituents may be further substituted with a halogen atom.

[0079] Among them, R a2 is more preferably one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0080] R a3 represents a divalent aliphatic hydrocarbon group. The preferred range of the divalent aliphatic hydrocarbon group is as described above.

[0081] na1 represents a positive integer. a1 is preferably 1 or more, and preferably 10 or less, more preferably 8 or less.

[0082] n a2 Each independently represents an integer of 0 to 4. a2 is preferably 2 or 3, more preferably 2. a2 may be different from each other, but are preferably the same. a2 If is 2 or more, multiple R a1 may be the same or different from each other.

[0083] n a3 represents an integer of 0 to 3. a3 When there are a plurality of n, they may be different from each other, but are preferably the same as each other. a3 is preferably 0.

[0084] The component (A2-2) may contain a structure represented by the following formula (A2-2-3): The entire component (A2-2) may have a structure represented by formula (A2-2-3), or only a part of the component (A2-2) may have a structure represented by formula (A2-2-3).

[0085] [ka]

[0086] In formula (A2-2-3), R a1 , R a2 , n a1 , n a2 and n a3 is as explained in formula (A2-2-2).

[0087] The component (A2-2) may further contain a structure represented by the following formula (A2-2-4):

[0088] [ka]

[0089] In formula (A2-2-4), R a1 , R a2 , n a2 and n a3 is as explained in formula (A2-2-2). c1 is the number of repeating units and represents an integer of 1 to 20. * represents a bond.

[0090] For example, the component (A2-2) is a compound represented by the formula (A2-2-2): a2 is 3 or less, and R is present at two or more of the ortho and para positions relative to the maleimide group bonding position of the benzene ring to which the maleimide group is bonded. a1 When is not bonded, the structure represented by formula (A2-2-2) may include a structure represented by formula (A2-2-4) in combination with the structure represented by formula (A2-2-2).

[0091] For example, the component (A2-2) is a compound represented by the formula (A2-2-3), a2 is 3 or less, and R is present at two or more of the ortho and para positions relative to the maleimide group bonding position of the benzene ring to which the maleimide group is bonded. a1 When is not bonded, the structure represented by formula (A2-2-4) may be included in combination with the structure represented by formula (A2-2-3).

[0092] The method for producing the component (A2-2) is not particularly limited, and may be produced, for example, by the method described in the Japan Institute of Invention and Innovation Disclosure Technical Bulletin No. 2020-500211. According to the production method described in the Japan Institute of Invention and Innovation Disclosure Technical Bulletin 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 (A2-2-5). Therefore, the maleimide resin may contain a maleimide compound containing a structure represented by formula (A2-2-5).

[0093] [ka]

[0094] In formula (A2-2-5), R 1 , R 2 , n2 and n3 are R in formula (A2-2-2), a1 , R a2 , n a2 and n a3 The preferred types and ranges are also the same as those in the above. n1 represents the average number of repeating units of 0.95 to 10.0.

[0095] In formula (A2-2-5), n1 represents the average number of repeating units and is in the range of 0.95 to 10.0. According to the production method described in the Technical Bulletin No. 2020-500211 of the Japan Institute of Invention and Innovation, a group of maleimide compounds containing a structure represented by formula (A2-2-5) can be obtained.

[0096] In formula (A2-2-5), 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, and is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, particularly preferably 6.0 or less.

[0097] Specific examples of the structure of the component (A2-2) are shown below.

[0098] [ka]

[0099] The maleimide compound having the structure represented by formula (A2-2-5) may further have the structure represented by formula (A2-2-4) above. For example, the maleimide compound having the structure represented by formula (A2-2-5) may have n2 of 3 or less and R at two or more of the ortho and para positions relative to the maleimide group bonding position of the benzene ring to which the maleimide group is bonded. 1 When is not bonded, the structure represented by formula (A2-2-5) may include a structure represented by formula (A2-2-4) in combination with the structure represented by formula (A2-2-5).

[0100] The maleimide compound having a structure represented by formula (A2-2-5) preferably has a molecular weight distribution Mw / Mn calculated by gel permeation chromatography (GPC) measurement in a specific range. Specifically, the molecular weight distribution Mw / Mn of the maleimide compound having a structure represented by formula (A2-2-5) 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.

[0101] With respect to the component (A2-2), the functional group equivalent of the maleimide group is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, even more preferably 200 g / eq. or more, and is preferably 2000 g / eq. or less, more preferably 1000 g / eq. or less, even more preferably 800 g / eq. or less.

[0102] <(A2-3) component> The component (A2-3) is a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide. Such a maleimide compound can be obtained, for example, by subjecting a component containing an aromatic amine compound (such as an aromatic diamine compound) and maleic anhydride to an imidization reaction.

[0103] In one embodiment, the component (A2-3) includes a compound represented by the following formula (A2-3-1):

[0104] [ka]

[0105] In formula (A2-3-1), Ring Ar 1 represents an aromatic ring which may have a substituent, L 2 represents a single bond or a divalent linking group, nB2 represents an integer of 1 to 100. 1 may be the same or different, L2 When there are multiple, they may be the same or different.

[0106] Ring Ar 1 The aromatic ring represented by the formula (I) may be either a carbocyclic ring or a heterocyclic ring, but is preferably a carbocyclic ring. 1 The number of carbon atoms in the aromatic ring represented by the following formula is preferably 3 to 20, and more preferably 5 to 14 or 6 to 10. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0107] L 2 The divalent linking group represented by the formula (A2-1-3) is not particularly limited as long as it is a divalent group consisting of one or more (for example, 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. For example, A 12 Examples of the divalent group include the divalent group shown in

[0108] Ring Ar 1 is, for example, an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent (more preferably, a benzene ring which may have a substituent), and L 2 (L 2 If there are multiple L, at least one 2 is preferably a divalent group having a biphenyl skeleton. Thus, in one embodiment, the component (A2-3) has a biphenyl skeleton.

[0109] In the (A2-3) component, the nitrogen atom of the maleimide is directly bonded to the aromatic ring. The bonding position of the maleimide and the aromatic ring is the same as that of the L bonded to the aromatic ring. 2 For example, when the aromatic ring is a benzene ring, the bonding position of the maleimide to the benzene ring may be any position based on the position of L bonded to the benzene ring. 2 Based on this reference, the bond may be at any of the ortho, meta, and para positions, and in one embodiment, the bond is at the para position.

[0110] In a preferred embodiment, the component (A2-3) includes a compound represented by the following formula (A2-3-2):

[0111] [ka]

[0112] In formula (A2-3-2), R B3 , R B4 , R B5 and R B6 each independently represents a substituent, nB21 represents an integer from 1 to 100, nB22 and nB23 each independently represent an integer of 1 to 10; nB24 and nB25 each independently represent an integer of 0 to 3; nB26 and nB27 each independently represent an integer of 0 to 4. B3 When there are multiple, they may be the same or different, which means that R B4 , R B5 and R B6 The same applies to.

[0113] nB21 is preferably 1-50, more preferably 1-20, and further preferably 1-5.

[0114] nB22 and nB23 each independently represent preferably 1 to 6, more preferably 1 to 3, and further preferably 1 or 2.

[0115] nB24 and nB25 are each independently preferably an integer of 0 to 2, more preferably 0 or 1. When nB24 and nB25 are 1 or more, R B3 and R B4 It is preferable that each of the substituents represented by the following formula (I) is independently an alkyl group or an aryl group.

[0116] nB26 and nB27 are each independently preferably an integer of 0 to 2, more preferably 0 or 1. When nB26 and nB27 are 1 or more, RB5 and R B6 It is preferable that each of the substituents represented by the following formula (I) is independently an alkyl group or an aryl group.

[0117] Of these, nB26 and nB27 are preferably 0. Therefore, in a preferred embodiment, the component (A2-3) includes a compound represented by the following formula (A2-3-3).

[0118] [ka]

[0119] In formula (A2-3-3), R B3 , R B4 , nB21, nB22, nB23, nB24, and nB25 are as explained in formula (A2-3-2).

[0120] When the component (A2-3) has a molecular weight distribution, the weight average molecular weight (Mw) is at least 500, and preferably at least 550. There are no particular limitations on the upper limit of Mw, but it is preferably at most 5000, and more preferably at most 2500. The Mw of the component (A2-3) can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0121] Furthermore, for the component (A2-3), the functional group equivalent of the maleimide group 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.

[0122] The component (A2-3) may be a maleimide compound having a structure represented by the following formula (A2-3-4).

[0123] [ka]

[0124] In the formula (A2-3-4), nB21 is as explained above.

[0125] An example of a commercially available maleimide compound having the structure represented by formula (A2-3-4) is "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. As the component (A2-3), "BMI-4000" manufactured by Daiwa Kasei Co., Ltd., "BMI-80" manufactured by Keiai Kasei Co., Ltd., and the like may also be used as the compound represented by formula (A2-3-1).

[0126] The content of the (A-2) component in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, 2% by mass or more, 3% by mass or more, or 4% by mass or more, when the total of the non-volatile components in the resin composition is 100% by mass. The upper limit of the maleimide resin content is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, 20% by mass or less, or 15% by mass or less.

[0127] (Styryl resin) The styryl resin has one or more groups selected from a styryl group and a vinylphenyl group in the molecule, and preferably has a vinylphenyl group. The vinylphenyl group is a group having the structure shown below. [ka]

[0128] From the viewpoint of obtaining a cured product with a low dielectric tangent, the styryl resin more preferably has two or more vinylphenyl groups.

[0129] The styryl resin preferably has a cyclic structure from the viewpoint of obtaining a cured product with a low dielectric tangent. The cyclic structure is preferably a divalent cyclic group. The divalent cyclic group may be any of a cyclic group containing a non-aromatic ring, such as an alicyclic structure, and a cyclic group containing an aromatic ring structure. In addition, the styryl resin may have a plurality of divalent cyclic groups.

[0130] From the viewpoint of significantly obtaining the intended effect of the present invention, the divalent cyclic group is preferably a 3-membered or more ring, more preferably a 4-membered or more ring, and even more preferably a 5-membered or more ring, and is preferably a 20-membered or less ring, more preferably a 15-membered or less ring, and even more preferably a 10-membered or less ring. In addition, the divalent cyclic group may be a monocyclic structure or a polycyclic structure.

[0131] The ring in the divalent cyclic group may have a ring skeleton constituted by a heteroatom other than carbon atoms. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom, and an oxygen atom is preferred. The ring may have one or more heteroatoms.

[0132] Specific examples of the divalent cyclic group include the following divalent groups (xii) and (xiii). [ka] (In the divalent groups (xii) and (xiii), R 51 , R 52 , R 55 , R 56 , R 57 , R 61 , and R 62 each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; R 53 , R 54 , R 58 , R 59 , and R 60 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.

[0133] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alkyl groups having 6 or less carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups, with methyl being preferred. 51 , R 52 , R 55 , R 56 , R 57 , R 61 , and R62 R preferably represents a methyl group. 53 , R 54 , R 58 , R 59 , and R 60 is preferably a hydrogen atom or a methyl group.

[0134] In addition, the divalent cyclic group may be a combination of a plurality of divalent cyclic groups. Specific examples of the combination of divalent cyclic groups include the divalent cyclic group represented by the following formula (A2-d) (divalent group (a)). [ka] (In formula (A2-d), R 71 , R 72 , R 75 , R 76 , R 77 , R 81 , R 82 , R 85 and R 86 each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; R 73 , R 74 , R 78 , R 79 , R 80 , R 83 and R 84 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. d1 and d2 each represent an integer of 0 to 300, except for the case where one of d1 and d2 is 0.

[0135] R 71 , R 72 , R 85 and R 86 R in formula (xii) 51 is the same as R 73 , R 74 , R 83 and R 84 R in formula (xii) 53 is the same as R 75 , R 76 , R 77 , R 81 , and R82 R in formula (xiii) 55 is the same as R 78 , R 79 , and R 80 R in formula (xiii) 58 is the same as:

[0136] d1 and d2 represent an integer of 0 to 300, except when one of d1 and d2 is 0. d1 and d2 preferably represent an integer of 1 to 100, more preferably an integer of 1 to 50, and even more preferably an integer of 1 to 10. d1 and d2 may be the same or different.

[0137] The divalent cyclic group may have a substituent, such as a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, or an oxo group, and an alkyl group is preferred.

[0138] The vinylphenyl group may be directly bonded to the divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, and the like, and may be a group in which a plurality of these are combined. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear, branched, or cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene groups, and are preferably methylene, ethylene, or 1,1-dimethylethylene. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferred, an alkenylene group having 2 to 6 carbon atoms is more preferred, and an alkenylene group having 2 to 5 carbon atoms is even more preferred. As the arylene group or heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferred, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferred. As the divalent linking group, an alkylene group is preferred, and among them, a methylene group is preferred.

[0139] The styryl resin preferably contains a compound represented by the following formula (A2-10). [ka] (In formula (A2-10), R 91 and R 92 each independently represents a divalent linking group. Ring B1 represents a divalent cyclic group.

[0140] R 91 and R 92 each independently represents a divalent linking group. The divalent linking group is the same as the divalent linking group described above.

[0141] Ring B1 represents a divalent cyclic group. Ring B is the same as the above divalent cyclic group.

[0142] Ring B1 may have a substituent. The substituent is the same as the substituent that the above divalent cyclic group may have.

[0143] Specific examples of the styryl resin are shown below, but the present invention is not limited thereto. [ka] (q1 is the same as d1 in formula (A2-d), and q2 is the same as d2 in formula (A2-d).)

[0144] The styryl resin may be a commercially available product, such as "OPE-2St", "OPE-2St 1200", or "OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., Inc. One type of styryl resin may be used alone, or two or more types may be used in combination.

[0145] From the viewpoint of significantly obtaining the intended effects of the present invention, the number average molecular weight of the styryl resin is preferably 3000 or less, more preferably 2500 or less, even more preferably 2000 or less, or 1500 or less. The lower limit is preferably 100 or more, more preferably 300 or more, even more preferably 500 or more, or 1000 or more. The number average molecular weight is the number average molecular weight in terms of polystyrene measured using gel permeation chromatography (GPC).

[0146] ((Meth)acrylic resin) The (meth)acrylic resin includes a compound having an acryloyl group or a methacryloyl group in the molecule. From the viewpoint of significantly obtaining the intended effect of the present invention, the (meth)acrylic resin preferably includes a compound having two or more (meth)acryloyl groups per molecule. The term "(meth)acryloyl group" is a general term for an acryloyl group and a methacryloyl group.

[0147] The (meth)acrylic resin preferably has a cyclic structure from the viewpoint of significantly achieving the desired effects of the present invention. The cyclic structure is preferably a divalent cyclic group. The divalent cyclic group may be any of a cyclic group containing a non-aromatic ring, for example, an alicyclic structure, and a cyclic group containing an aromatic ring structure. Among them, from the viewpoint of significantly achieving the desired effects of the present invention, a cyclic group containing an alicyclic structure is preferable.

[0148] From the viewpoint of significantly obtaining the intended effect of the present invention, the divalent cyclic group is preferably a 3-membered or more ring, more preferably a 4-membered or more ring, and even more preferably a 5-membered or more ring, and is preferably a 20-membered or less ring, more preferably a 15-membered or less ring, and even more preferably a 10-membered or less ring. In addition, the divalent cyclic group may be a monocyclic structure or a polycyclic structure.

[0149] The ring in the divalent cyclic group may have a ring skeleton constituted by a heteroatom other than carbon atoms. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom, and an oxygen atom is preferred. The ring may have one or more heteroatoms.

[0150] Specific examples of the divalent cyclic group include the following divalent groups (i) to (xi). Among them, the divalent cyclic group is preferably (x) or (xi). [ka]

[0151] The divalent cyclic group may have a substituent, such as a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, or an oxo group, and an alkyl group is preferred.

[0152] The (meth)acryloyl group may be directly bonded to the divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, and the like, and may be a group in which a plurality of these are combined. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear, branched, or cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene groups, and are preferably methylene, ethylene, or 1,1-dimethylethylene. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferred, an alkenylene group having 2 to 6 carbon atoms is more preferred, and an alkenylene group having 2 to 5 carbon atoms is even more preferred. As the arylene group or heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferred, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferred. As the divalent linking group, an alkylene group is preferred, and among them, a methylene group or a 1,1-dimethylethylene group is preferred.

[0153] The (meth)acrylic resin preferably contains a compound represented by the following formula (A2-11). [ka] (In formula (A2-11), R 101 and R 104 each independently represents an acryloyl group or a methacryloyl group, R 102 and R 103 each independently represents a divalent linking group. Ring B2 represents a divalent cyclic group.

[0154] R 101 and R 104each independently represents an acryloyl group or a methacryloyl group, and an acryloyl group is preferred.

[0155] R 102 and R 103 each independently represents a divalent linking group. The divalent linking group is the same as the divalent linking group which may have a (meth)acryloyl group bonded thereto.

[0156] Ring B2 represents a divalent cyclic group. Ring B2 is the same as the divalent cyclic group. Ring B2 may have a substituent. The substituent is the same as the substituent that the divalent cyclic group may have.

[0157] Specific examples of the (meth)acrylic resin include the following, but the present invention is not limited thereto. [ka]

[0158] As the (meth)acrylic resin, commercially available products may be used, and examples thereof include "A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", and "DPHA" manufactured by Nippon Kayaku Co., Ltd., and "NK Ester DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.

[0159] From the viewpoint of significantly obtaining the intended effects of the present invention, the (meth)acryloyl group equivalent of the (meth)acrylic resin is preferably 30 g / eq. to 400 g / eq., more preferably 50 g / eq. to 300 g / eq., and further preferably 75 g / eq. to 200 g / eq. The (meth)acryloyl group equivalent is the mass of a compound containing one equivalent of a (meth)acryloyl group.

[0160] (Allyl resin) The allyl resin has at least one allyl group in the molecule. The allyl resin more preferably has two or more allyl groups in one molecule. The upper limit is not particularly limited, but is preferably 10 or less, more preferably 5 or less.

[0161] In order to remarkably obtain the intended effects of the present invention, the allyl resin preferably has, in addition to the allyl group, any one of a benzoxazine ring, a phenol ring, an isocyanuric ring, and a carboxylic acid derivative having a cyclic structure.

[0162] The allyl resin having a benzoxazine ring is preferably bonded to either the nitrogen atom of the benzoxazine ring or the benzene ring, and more preferably bonded to the nitrogen atom.

[0163] Examples of allyl resins having a phenol ring include cresol resins containing an allyl group, novolac-type phenol resins containing an allyl group, and cresol novolac resins containing an allyl group.

[0164] In the allyl resin having an isocyanuric structure, a nitrogen atom of the isocyanuric structure and an allyl group are preferably directly bonded to each other. Examples of the allyl resin having an isocyanuric structure include allyl isocyanurate, diallyl isocyanurate, and triallyl isocyanurate.

[0165] As the allyl resin having a carboxylic acid derivative having a cyclic structure, an allyl carboxylate having a cyclic structure is preferred. The cyclic structure may be any of a non-aromatic ring, for example, a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic ring structure. In addition, the cyclic group may have a ring skeleton formed by heteroatoms other than carbon atoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms, and nitrogen atoms are preferred. The ring may have one or more heteroatoms.

[0166] Examples of carboxylic acids having a cyclic structure include isocyanuric acid, diphenic acid, phthalic acid, cyclohexanedicarboxylic acid, etc. Examples of allyl resins having a carboxylic acid derivative having a cyclic structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl diphenate, allyl diphenate, ortho-diallyl phthalate, meth-diallyl phthalate, para-diallyl phthalate, allyl cyclohexanedicarboxylate, diallyl cyclohexanedicarboxylate, etc.

[0167] The allyl resin may be a commercially available product. Examples of commercially available products include "MEH-8000H" and "MEH-8005" (allyl resin having a phenol ring) manufactured by Meiwa Kasei Co., Ltd.; "ALP-d" (allyl resin having a benzoxazine ring) manufactured by Shikoku Kasei Kogyo Co., Ltd.; "L-DAIC" (allyl resin having an isocyanuric ring) manufactured by Shikoku Kasei Kogyo Co., Ltd.; "TAIC" (allyl resin having an isocyanuric ring (triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd.; "MDAC" (allyl resin having a cyclohexanedicarboxylic acid derivative) manufactured by Osaka Soda Co., Ltd.; "DAD" (diallyl diphenate) manufactured by Nissho Techno Fine Chemical Co., Ltd.; and "Daiso DAP Monomer" (ortho-diallyl phthalate) manufactured by Osaka Soda Co., Ltd.

[0168] From the viewpoint of significantly obtaining the intended effects of the present invention, the allyl group equivalent of the allyl resin is preferably 20 g / eq. to 1000 g / eq., more preferably 50 g / eq. to 500 g / eq., and further preferably 100 g / eq. to 300 g / eq. The allyl group equivalent is the mass of a compound containing one equivalent of an allyl group.

[0169] (Butadiene resin) The butadiene resin has a butadiene skeleton. The polybutadiene structure may be included in the main chain or in the side chain. The polybutadiene structure may be partially or entirely hydrogenated. The butadiene resin is preferably one or more resins selected from the group consisting of hydrogenated polybutadiene skeleton-containing resin, hydroxyl group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxyl group-containing butadiene resin, acid anhydride group-containing butadiene resin, isocyanate group-containing butadiene resin, and urethane group-containing butadiene resin.

[0170] Specific examples of butadiene resins include "JP-100" manufactured by Nippon Soda Co., Ltd., and "Ricon100", "Ricon150", "Ricon130MA8", "Ricon130MA13", "Ricon130MA20", "Ricon131MA5", "Ricon131MA10", "Ricon131MA17", "Ricon131MA20", and "Ricon 184MA6" manufactured by CRAY VALLEY Corporation.

[0171] The content of the (A-2) component is 0 mass% or more, and from the viewpoint of enhancing the intended effects of the present invention, particularly from the viewpoint of obtaining a cured product with a low dielectric tangent, when the non-volatile components in the resin composition are taken as 100 mass%, the content is preferably 0.5 mass% or more, more preferably 1 mass% or more, even more preferably 1.5 mass% or more, and is preferably 60 mass% or less, more preferably 50 mass% or less, even more preferably 40 mass% or less.

[0172] From the viewpoint of enhancing the intended effects of the present invention, particularly from the viewpoint of obtaining a cured product with a low dielectric tangent, the content of the (A-2) component, relative to 100 mass% of the resin component in the resin composition, is preferably 1 mass% or more, more preferably 2 mass% or more, and even more preferably 3 mass% or more, and is preferably 80 mass% or less, more preferably 70 mass% or less, and even more preferably 60 mass% or less.

[0173] When the component (A) contains both the component (A-1) and the component (A-2), the content (parts by mass) of the component (A-2) is, from the viewpoint of enhancing the intended effects of the present invention, in particular from the viewpoint of obtaining a cured product having a low dielectric tangent, 0.01 times or more, 0.05 times or more, or 0.1 times or more of the content of the component (A-1) relative to the content of the component (A-2), and while there is no upper limit, it can be, for example, 10 times or less, 7 times or less, or 5 times or less.

[0174] The content of the (A) curable resin is more than 0 mass%, and from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are taken as 100 mass%, the content is preferably 0.1 mass% or more, more preferably 1 mass% or more, even more preferably 3 mass% or more, and particularly preferably 5 mass% or more. The upper limit is not particularly limited, but can be, for example, 65 mass% or less, 45 mass% or less, 35 mass% or less, or 30 mass% or less.

[0175] The content of the (A) curable resin is preferably 0.2% by mass or more, more preferably 2% by mass or more, even more preferably 6% by mass or more, and particularly preferably 10% by mass or more, from the viewpoint of obtaining the effects of the present invention remarkably, when the resin component in the resin composition is taken as 100% by mass, and the upper limit is not particularly limited, but may be, for example, 85% by mass or less, 70% by mass or less, 60% by mass or less, or 55% by mass or less. The resin component refers to the non-volatile components in the resin composition excluding the (B) component.

[0176] <(B) Compounds Having a Heterocyclic Structure Containing Two or More Nitrogen Atoms and a Cage-Type Silsesquioxane Structure in the Molecule: Modified Cage-Type PSQ> The resin composition of the present invention contains, as component (B), a compound having a heterocyclic structure containing two or more nitrogen atoms (hereinafter also referred to as "N-rich heterocyclic structure") and a cage-type silsesquioxane structure (hereinafter also referred to as "cage-type PSQ structure") in the molecule. Such a compound is also referred to as "modified cage-type PSQ" below. The (B) modified cage-type PSQ may be used alone or in combination of two or more types. The resin composition of the present invention can achieve the desired effect by containing component (B) in combination with component (A). The (B) modified cage-type PSQ usually has a linking group (hereinafter also referred to as "main chain linking group") between the above-mentioned cage-type PSQ structure and the above-mentioned N-rich heterocyclic structure. The main chain linking group will be described later.

[0177] (Cage-type silsesquioxane structure: cage-type PSQ structure) In the (B) modified cage-type PSQ, a silsesquioxane compound (PSQ: polysilsesquioxane) that can be used as a precursor of the cage-type PSQ structure usually has a skeleton containing a siloxane bond, and is represented by the formula (RSiO 3 / 2 ) n In the silicon-containing skeleton, R represents an organic group such as a hydrocarbon group, and n represents an integer. Silsesquioxane compounds are known to have amorphous structures, ladder structures, incompletely condensed structures, and completely condensed structures. The modified cage PSQ contained in the resin composition of the present invention has a cage PSQ structure, as described above. The cage PSQ structure refers to a structure that contains a plurality of cyclic structures composed of a silicon-containing skeleton, and that forms a closed space or can form a closed space after reaction by using such a plurality of cyclic structures. The cage PSQ structure includes, for example, the cage structure of a T8 silsesquioxane compound, the cage structure of a double-decker silsesquioxane compound (hereinafter also referred to as "DDSQ"), and the cage structure of a T12 silsesquioxane, and may also include the cage structure of a T7 silsesquioxane compound that can form a closed space by reaction. On the other hand, the cage PSQ excludes PSQs that do not have a cage structure, such as PSQs that have a ladder structure or PSQs that have an amorphous structure.

[0178] From the viewpoint of enhancing the intended effects of the present invention, the cage-type PSQ structure is preferably the cage-type structure possessed by DDSQ.

[0179] The cage PSQ structure preferably includes a cage structure represented by the following formula (B1). [ka] [In the above formula (B1), X's are each independently a group selected from an alkyl group having 1 to 40 carbon atoms, whose hydrogen atom may be replaced by a halogen atom, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group, whose hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 20 carbon atoms, and an arylalkyl group in which an aryl group, whose hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 20 carbon atoms, is bonded to an alkylene group having 1 to 8 carbon atoms; Y's each independently represent an alkyl group having 1 to 40 carbon atoms, whose hydrogen atom may be replaced by a halogen atom, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group, whose hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group in which an aryl group, whose hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 20 carbon atoms, is bonded to an alkylene group having 1 to 8 carbon atoms; * is a bond; When X or Y is an alkyl group having 1 to 40 carbon atoms, -CH2- contained in the alkyl group may be replaced by -O- or -CH=CH-; When X or Y is an aryl group, and a hydrogen atom of the aryl group is replaced by an alkyl group having 1 to 20 carbon atoms, a hydrogen atom of the alkyl group having 1 to 20 carbon atoms may be replaced by a halogen atom, and -CH2- contained in the alkyl group having 1 to 20 carbon atoms may be replaced by -O- or -CH=CH-; When X or Y is an arylalkyl group, -CH2- contained in the arylalkyl group may be replaced by -O-.]

[0180] In X and Y, examples of the alkyl group include a methyl group, an ethyl group, a t-butyl group, an octyl group, and a decyl group. Examples of the alkyl group in which a hydrogen atom is replaced with a halogen atom include a 3,3,3-trifluoropropyl group and a tridecafluoro-1,1,2,2-tetrahydrooctyl group. Examples of the group in which -CH2- in the alkyl group is replaced with -O- include a 3-methoxypropyl group and a 3-heptafluoroisopropoxypropyl group. Examples of the group in which -CH2- in the alkyl group is replaced with -CH=CH- include an ethenyl group, a 3-butenyl group, and an allyloxyundecyl group.

[0181] In X and Y, examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a decalyl group.

[0182] In X and Y, examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a fluorenyl group. Examples of the aryl group in which a hydrogen atom is replaced by a halogen atom include a 4-fluorophenyl group, a 4-chlorophenyl group, and a 4-bromophenyl group. Examples of the aryl group in which a hydrogen atom is replaced by an alkyl group include a 4-methylphenyl group, a 4-ethylphenyl group, a 4-butylphenyl group, a 4-octylphenyl group, a 4-decylphenyl group, a 2,4-dimethylphenyl group, a 4-(1,1-dimethylethyl)phenyl group, and a 4-(2-ethylhexyl)phenyl group. Examples of the group in which a hydrogen atom of an aryl group is replaced by an alkyl group and -CH2- contained in the alkyl group is replaced by -O- include a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-butoxyphenyl group, a 4-heptyloxyphenyl group, and a methoxyethylphenyl group.

[0183] From the viewpoint of obtaining a cured product with a low dielectric tangent, preferably, in the cage structure shown in the above formula (B1), at least one of X and Y, more preferably both, contain a hydrophobic group. Examples of the hydrophobic group include a hydrocarbon group having 1 to 40 carbon atoms, preferably a hydrocarbon group having 1 to 20 carbon atoms. Such a hydrocarbon group may be linear, may contain a side chain, may contain an aliphatic ring, or may contain an aromatic ring. X preferably contains an aromatic ring, more preferably contains a substituted or unsubstituted aryl group, further preferably a substituted or unsubstituted aryl group, and particularly preferably an unsubstituted aryl group. Y is preferably a substituted or unsubstituted aliphatic hydrocarbon group, more preferably a substituted or unsubstituted alkyl group. In a preferred embodiment, in the cage structure shown in the above formula (B1), all of the multiple Xs are phenyl groups. In a more preferred embodiment, in the cage structure shown in the above formula (B1), all of the multiple Xs are phenyl groups, and all of the multiple Ys are alkyl groups, such as methyl groups.

[0184] (Heterocyclic structures containing two or more nitrogen atoms: N-rich heterocyclic structures) (B) In the modified cage PSQ, the N-rich heterocyclic structure is a ring structure containing two or more nitrogen atoms as skeletal atoms in a ring structure of three or more members. In one embodiment, the N-rich heterocyclic structure is a monocyclic structure (i.e., not a condensed ring structure). The N-rich heterocyclic structure usually has a bond at any position for bonding to a linking group that may be interposed between the N-rich heterocyclic structure and the cage PSQ structure. In one embodiment, such a bond is possessed by a skeletal atom (e.g., a carbon atom) other than a nitrogen atom among the skeletal atoms constituting the N-rich heterocyclic structure.

[0185] The number of skeletal atoms constituting the N-rich heterocyclic structure (number of ring members) is 3 or more, preferably 5 or more, more preferably 6 or more, and there is no upper limit as long as the heterocyclic structure is a single ring, but it may be, for example, 9 or less, 8 or less, or 7 or less. In a preferred embodiment, the number of skeletal atoms contained in the N-rich heterocyclic structure is either 5 (i.e., a 5-membered ring) or 6 (i.e., a 6-membered ring), and in a particularly preferred embodiment, it is 6 (i.e., a 6-membered ring).

[0186] The N-rich heterocyclic structure is preferably selected from the group consisting of an imidazolidine structure, an imidazole structure, a 1,2,3-triazole structure, a 1,2,4-triazole structure, a piperazine structure, a pyrazine structure, a pyrimidine structure, a pyridazine structure, a hexahydro-1,3,5-triazine structure, a 1,2,3-triazine structure, a 1,2,4-triazine structure, a 1,3,5-triazine structure, a 1,2,3,5-tetrazine structure, a 1,2,4,5-tetrazine structure, and a pentazine structure.

[0187] In the N-rich heterocyclic structure, from the viewpoint of obtaining a cured product having excellent copper foil adhesion, the number of nitrogen atoms constituting the skeleton atoms is preferably large, more preferably 3 or more. In one embodiment, the N-rich heterocyclic structure contains three nitrogen atoms. Therefore, suitable examples of the N-rich heterocyclic structure include a 1,2,3-triazole structure, a 1,2,4-triazole structure, a hexahydro-1,3,5-triazine structure, a 1,2,3-triazine structure, a 1,2,4-triazine structure, and a 1,3,5-triazine structure. In a specific embodiment, the N-rich heterocyclic structure is a 1,3,5-triazine structure. In another embodiment, instead of the N-rich heterocyclic structure, a ring structure of a monocyclic compound in which all of the skeleton atoms are composed of nitrogen atoms may be used.

[0188] In one embodiment, N-rich heterocyclic structure comprises three nitrogen atoms.Therefore, suitable examples of N-rich heterocyclic structure include 1,2,3-triazole structure, 1,2,4-triazole structure, hexahydro-1,3,5-triazine structure, 1,2,3-triazine structure, 1,2,4-triazine structure, and 1,3,5-triazine structure.From the viewpoint of obtaining a cured product with better copper foil adhesion, in a specific embodiment, N-rich heterocyclic structure is 1,3,5-triazine structure.

[0189] Any substituent (hereinafter also referred to as "heterocyclic bonded substituent") may be bonded to the N-rich heterocyclic structure. Such heterocyclic bonded substituent may be bonded to an atom (e.g., carbon atom) other than a nitrogen atom among the skeleton atoms constituting the N-rich heterocyclic structure, or may be bonded to a nitrogen atom, and in one embodiment, is bonded to an atom other than a nitrogen atom.

[0190] The heterocyclic bonded substituent may include one or more selected from an aliphatic structure which may be substituted with a secondary substituent, and an aromatic ring structure which may be substituted with a secondary substituent. Such an aliphatic structure or such an aromatic ring structure is bonded to the N-rich heterocyclic structure directly or via an arbitrary linking group (hereinafter also referred to as a "side chain linking group"). The aliphatic structure may be linear, branched, or may include a ring structure. The number of carbon atoms contained in the aliphatic structure is, for example, within the range of 1 to 20, preferably within the range of 1 to 6, and a typical example of the aliphatic structure is a linear, branched, or cyclic alkyl group. The number of carbon atoms in the aromatic ring structure is, for example, within the range of 6 to 14, preferably within the range of 6 to 10, and a typical example of the aromatic ring structure is a benzene ring structure or a naphthalene ring structure. Thus, in one embodiment, the modified cage PSQ includes an aromatic ring structure which may be substituted with a secondary substituent, such as a benzene ring structure, bonded to the N-rich heterocyclic structure via a side chain linking group. Examples of the secondary substituent include a halogen atom (e.g., a fluorine atom), an alkyl group having 1 to 3 carbon atoms, and a halogenated alkyl group having 1 to 3 carbon atoms (e.g., a fluoroalkyl group). In one embodiment, from the viewpoint of obtaining a cured product with excellent dielectric properties, a trifluoromethyl group is adopted as the secondary substituent.

[0191] The linking group in the side chain is not limited as long as it is any linking group having a valence of 2 or more, and examples thereof include -O-, -S-, -CO-, -NH-, -NR'-, and combinations thereof. Examples of R' in the linking group in the side chain include an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, which may have a substituent, and a halogenated alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, which may have a substituent. From the viewpoint of obtaining a cured product having excellent copper foil adhesion, the linking group in the side chain is preferably a group containing a nitrogen atom. In a preferred embodiment, the linking group in the side chain is selected from -NH-, -NR'-, -NH-CO-, -CO-NH-, -NR'-, -NR'-CO-, and -CO-NR'-, and is, for example, -NH-. Thus, in certain embodiments, the modified cage-type PSQ comprises an optionally substituted aromatic ring structure bonded to an N-rich heterocyclic structure via -NH- in the molecule, or comprises an optionally substituted aliphatic structure and an optionally substituted aromatic ring structure bonded to an N-rich heterocyclic structure via -NH- in the molecule.

[0192] (Connecting group in main chain) As mentioned above, the (B) modified cage PSQ usually has a linking group in the main chain between the cage PSQ structure and the N-rich heterocyclic structure. The linking group in the main chain is not limited as long as it can link the cage PSQ structure and the N-rich heterocyclic structure, but in one embodiment, the linking group in the main chain contains at least one selected from an imide bond and an ether bond, and preferably contains at least an imide bond from the viewpoint of obtaining a cured product having excellent heat resistance, and may contain both an imide bond and an ether bond. From the viewpoint of obtaining a cured product having excellent heat resistance, the linking group in the main chain preferably contains an aromatic ring structure. Examples of such aromatic ring structures include a benzene ring structure and a naphthalene ring structure.

[0193] Furthermore, the linking group in the main chain may include any of the structures represented by the following formulae as a structure including an imide bond: In the following formulae, * represents a bond. [ka]

[0194] Among the structures represented by the above formula, in one embodiment, the linking group in the main chain includes the following structure. When a cage PSQ compound having a corresponding acid anhydride group is used as a precursor compound (monomer) of the cage PSQ structure, the following structure can be generated by imidizing the cage PSQ compound. As such a cage PSQ compound, a commercially available product can be used. Examples of such a commercially available product include bifunctional double-decker silsesquioxane "alicyclic double-decker silsesquioxane-DDSQ-01" or "silsesquioxane alicyclic acid dianhydride DDSQ" (CAS number: 948849-07-8) manufactured by Japan Material Technology Co., Ltd., and "DDSQ-02" manufactured by Japan Material Technology Co., Ltd.

[0195] [ka]

[0196] When the linking group in the main chain contains a structure containing the above-mentioned imide bond, it may contain any of the structures represented by the following formulae as a structure containing an ether bond and the above-mentioned aromatic ring structure. *-L 1 -Ar-(L 2 ) n2 -O-* [In the above formula, Ar is an aromatic ring structure, and L 1 is a single bond or a divalent group not containing an aromatic ring structure, and L 2 is a divalent group not containing an aromatic ring structure, n2 is 0 or 1, and * represents a bond.

[0197] L in the structure represented by the above formula 1 One of the bonds of the ether bond in the structure represented by the above formula is preferably bonded to the N-rich heterocyclic structure directly or via an arbitrary linking group.

[0198] In one embodiment, in the above formula, Ar is a benzene ring structure and L1 is an ethylene group, and n2 is 0. The above structure can be obtained by using a cage PSQ compound having an acid anhydride group as the cage PSQ compound, and using a monoamine monohydroxy compound having an aromatic ring structure (e.g., tyramine) as a monomer for imidizing the cage PSQ compound.

[0199] In a specific embodiment, the modified cage PSQ is an imide compound having a plurality of linking structures in which the above-mentioned N-rich heterocyclic structure and the above-mentioned cage PSQ structure are linked to each other via the above-mentioned main chain linking group containing at least the imide bond, and is preferably a polyimide compound having a plurality of such linking structures. For example, when the cage PSQ structure is X, the N-rich heterocyclic structure is Y, the aromatic ring structure which may have a substituent is Z, the main chain linking group containing at least the imide bond is Lp, and the side chain linking group is Ls, the modified cage PSQ may contain a structure represented by the following formula as a linking structure (repeating unit).

[0200] [-Lp-X-Lp-Y(-Ls-Z)n-] In the formula, n is 0 or 1.

[0201] Although the number of repeating units is not limited, when such a polyimide compound is obtained by a polymerization reaction, it is preferable that the weight average molecular weight (Mw) of the obtained polymer is within the range described below.

[0202] (Other structures) As described above, the modified cage PSQ is not limited as long as it has a heterocyclic structure containing two or more nitrogen atoms and a cage PSQ structure, and may or may not have a reactive functional group. The reactive functional group may exhibit its reactivity upon heating or light irradiation. When the modified cage PSQ has a reactive functional group, it becomes possible to incorporate the component (B) into the crosslinked structure formed by the component (A). The number of reactive functional groups is one or more, preferably two or more, per molecule, and there is no upper limit as long as they can be introduced into the molecule.

[0203] Examples of reactive functional groups include acid anhydride groups, epoxy groups, oxetanyl groups, hydroxy groups, carboxy groups, amino groups, and vinyl groups, as well as groups containing one or more of these groups (e.g., allyl groups, acryloyl groups, and methacryloyl groups).Unless otherwise specified, the term "acid anhydride group" refers to a group containing -CO-O-CO-.

[0204] The reactive functional group may be a part of one or more structural moieties selected from the aforementioned N-rich heterocyclic structure, the linking group in the side chain, the cage structure, and the linking group in the main chain, or may be directly bonded to such a structural moiety or may be bonded via any linking group.

[0205] When the component (B) is obtained by polymerization, the weight average molecular weight (Mw) of the obtained polymer is preferably 3000 or more, more preferably 5000 or more, and even more preferably 7000 or more, and is preferably 50000 or less, more preferably 45000 or less, and even more preferably 40000 or less. The weight average molecular weight of the polymer can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0206] The content of the (B) component is more than 0 mass%, and from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are taken as 100 mass%, the content is preferably 0.01 mass% or more, more preferably 5 mass% or more, even more preferably 7 mass% or more, particularly preferably 10 mass% or more, and is preferably 60 mass% or less, more preferably 55 mass% or less, and even more preferably 50 mass% or less.

[0207] From the viewpoint of achieving a remarkable effect of the present invention, the content of the (B) component is preferably 10% by mass or more, more preferably 14% by mass or more, and even more preferably 20% by mass or more, and is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, based on 100% by mass of the resin component in the resin composition.

[0208] From the viewpoint of obtaining the effects of the present invention prominently, the total content of the (B) component and the (C) component described later is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 50% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass. The upper limit is not particularly limited, but may be, for example, 98% by mass or less, 97% by mass or less, 96% by mass or less, or 95% by mass or less.

[0209] <(C) Inorganic filler> The resin composition may contain an inorganic filler as component (C). By including the inorganic filler (C) in the resin composition, a cured product (insulating layer) having excellent mechanical properties can be obtained. Furthermore, by including the inorganic filler (C) in the resin composition, a cured product having a low linear thermal expansion coefficient can be obtained.

[0210] As the inorganic filler, an inorganic compound is used. Examples 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 tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as the silica, spherical silica is preferable. (C) The inorganic filler may be used alone or in combination of two or more types.

[0211] (C) Examples of commercially available inorganic fillers include "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Company, Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; and "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", and "SC-C2" manufactured by Admatechs Co., Ltd.

[0212] From the viewpoint of significantly obtaining the desired effects of the present invention, the average particle size of the (C) inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

[0213] (C) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering particle size distribution measuring device, and the median diameter is taken as the average particle size. The measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture by ultrasonic waves for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution measuring device with blue and red light wavelengths as the light source, and the volume-based particle size distribution of the inorganic filler is measured using a flow cell method, and the average particle size is calculated from the obtained particle size distribution as the median diameter. An example of a laser diffraction particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

[0214] The specific surface area of ​​the (C) inorganic filler is preferably 1 m or less from the viewpoint of significantly obtaining the desired effects of the present invention. 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 3m 2 / g or more. There is no particular upper limit, but it is preferably 60m 2 / g or less, 50m2 / g or less or 40m 2 The specific surface area is measured by using a BET fully automatic specific surface area measuring device (Mountec's "Macsorb HM-1210") to adsorb nitrogen gas onto the surface of the sample, and then calculating the specific surface area using the BET multipoint method to measure the specific surface area of ​​the inorganic filler.

[0215] (C) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane, an organosilazane compound, and a titanate coupling agent. The surface treatment agent may be used alone or in any combination of two or more.

[0216] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), and Shin-Etsu Chemical Co., Ltd.'s N-phenyl-8-aminooctyl-trimethoxysilane.

[0217] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of the surface treatment agent, more preferably 0.2 parts by mass to 3 parts by mass, and even more preferably 0.3 parts by mass to 2 parts by mass.

[0218] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is more preferable that the content is 1 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0219] (C) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent 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 solid content, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, the "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used.

[0220] The content of the (C) inorganic filler is more than 0% by mass. From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are taken as 100% by mass, the content is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit is not particularly limited, and can be, for example, 90% by mass or less, 85% by mass or less, or 80% by mass or less. From the viewpoint of at least one of obtaining a cured product with a low dielectric constant (Dk) and obtaining a cured product with excellent copper foil adhesion, the content may be 50% by mass or less, 45% by mass or less, or 40% by mass or less.

[0221] <(D) Hardener> The resin composition may contain a curing agent (D). As the component (D), a substance having a function of curing the component (A), particularly the component (A-1), can be used. However, the component (D) does not include those that correspond to the components (A) and (B). When the resin composition does not contain the component (A-1), it does not have to contain the component (D). When the resin composition contains the component (D) together with the component (A-1), a cured product with excellent heat resistance can be obtained.

[0222] (D) The curing agent may be one or more selected from active ester curing agents, phenolic curing agents, naphthol curing agents, carbodiimide curing agents, benzoxazine curing agents, acid anhydride curing agents, amine curing agents, and cyanate ester curing agents. From the viewpoint of obtaining a cured product with excellent plating adhesion, it is preferable to use an active ester curing agent. The curing agent may be used alone or in combination of two or more.

[0223] The active ester curing agent is not particularly limited, but generally, 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 preferably used. The active ester curing agent is preferably one 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. In particular, 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 the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, phenol novolac, etc. Here, the term "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0224] Specifically, active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, and active ester compounds containing a benzoylated product of phenol novolac are preferred, and among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0225] Commercially available active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB-9451", "EXB-9460", "EXB-9460S", "HPC-8000-65T", "HPC-8000H-65TM", and "HPC-8000L-65TM" (manufactured by DIC Corporation); active ester compounds containing a naphthalene structure, such as "EXB-9416-70BK", "EXB-8100L-65T", "EXB-8150-65T", "EXB-8150L-65T", "HPC-8150-60T", "HPC-8150-62T", and "HP-B-8151-62T" (manufactured by DIC Corporation); and phenol novolac. Examples of the active ester compound containing an acetylated product of phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester compound containing a benzoylated product of phenol novolac includes "YLH1026" (manufactured by Mitsubishi Chemical Corporation), an active ester curing agent which is an acetylated product of phenol novolac includes "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester curing agent which is a benzoylated product of phenol novolac includes "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and an active ester compound containing a styryl group includes "PC1300-02-65MA" (manufactured by Air Water Corporation).

[0226] As the phenol-based curing agent (excluding active ester compounds) and naphthol-based curing agent (excluding active ester compounds), from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure or a cresol novolac structure, or a naphthol-based curing agent having a novolac structure is preferred. Also, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent is more preferred.

[0227] Specific examples of phenol-based curing agents and naphthol-based curing agents include, for example, "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", and "SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", and "KA-1160" manufactured by DIC Corporation.

[0228] Specific examples of carbodiimide-based curing agents include "V-03", "V-05", "V-07", "V-09", and "Elastostab H01" manufactured by Nisshinbo Chemical Inc.

[0229] Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation, "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd. The benzoxazine-based curing agent is a compound having a benzoxazine structure. The benzoxazine structure refers to a substituted or unsubstituted benzoxazine ring (e.g., 1,2-benzoxazine ring, 1,3-benzoxazine ring), or a benzoxazine ring in which a part of the double bond is hydrogenated (e.g., 3,4-dihydro-2H-1,3-benzoxazine ring).

[0230] Examples of the acid anhydride curing agent include a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule is preferable. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride (e.g., 3,4,3',4'-biphenyl tetracarboxylic dianhydride ("BPDA"), naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride , 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resins in which styrene and maleic acid are copolymerized. Commercially available acid anhydride-based hardeners include the Rikacid series "BT-100", "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by New Japan Chemical Co., Ltd., "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Co., Ltd., and "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.

[0231] The amine-based curing agent may be a curing agent having one or more, preferably two or more, amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propanediamine, and the like. bis(4-aminophenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. The amine-based curing agent may be a commercially available product, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0232] Examples of the cyanate ester curing agent 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-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (phenol novolac type multifunctional cyanate ester resins), "ULL-950S" (multifunctional cyanate ester resin), "BA230", and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been converted to triazine to form a trimer), all of which are manufactured by Lonza Japan.

[0233] The ratio of the amount of the (A) component to the (D) component is preferably 1:0.01 to 1:20, more preferably 1:0.05 to 1:3, and even more preferably 1:0.1 to 1:1.5, in terms of the ratio of [total number of reactive groups in the (A) component]:[total number of reactive groups in the (D) component]. Here, the reactive groups in the (D) component are active ester groups, active hydroxyl groups, etc., and vary depending on the type of the (D) curing agent. The total number of reactive groups in the (D) component is the total value of the non-volatile mass of each of the (D) components divided by the reactive group equivalent, for all curing agents. The total number of reactive groups in the (A) component is the total value of the non-volatile mass of each of the (A) components divided by the reactive group equivalent, for all curing agents. By setting the ratio of the (A) component to the (D) component in such a range, the desired effect of the present invention can be enhanced.

[0234] The content of the (D) component is preferably determined so as to satisfy the range of the ratio of the (A) component to the (D) component described above. The content of the (D) component is 0% by mass or more, and from the viewpoint of enhancing the intended effects of the present invention, when the non-volatile content in the resin composition is taken as 100% by mass, the content may be 1% by mass or more, 2% by mass or more, 3% by mass or more, or 3.5% by mass or more, and 50% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, or 15% by mass or less.

[0235] <(E) Curing accelerator> The resin composition of the present invention may contain (E) a curing accelerator as an optional component. The (E) curing accelerator has a function of accelerating the curing reaction of the (A) component. However, the (E) curing accelerator excludes those corresponding to the (A) to (D) components. The (E) curing accelerator may be used alone or in combination of two or more.

[0236] Examples of the (E) curing accelerator include phosphorus-based curing accelerators, imidazole-based curing accelerators, amine-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, etc. Among these, as the (H) curing accelerator, from the viewpoint of achieving a higher light reflectance, phosphorus-based curing accelerators and imidazole-based curing accelerators are preferred, and phosphorus-based curing accelerators are more preferred.

[0237] From the viewpoint of achieving a higher light reflectance, the phosphorus-based curing accelerator preferably contains one or more members selected from the group consisting of phosphonium salts and phosphines.

[0238] Examples of the phosphonium salt include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, and the like. Examples of aromatic phosphonium salts include aromatic phosphonium salts such as phenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate.

[0239] Examples of phosphines include aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, and tris(2,5-dimethylphenyl)phosphine. tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2- Examples of aromatic phosphines include bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; and aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct.

[0240] As the phosphorus-based curing accelerator, commercially available products may be used, for example, "TBP-DA" manufactured by Hokko Chemical Industry Co., Ltd.

[0241] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-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 isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-furan Examples of the imidazole compounds include imidazole compounds such as 2-ethyl-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 and epoxy resins. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0242] As the imidazole-based curing accelerator, commercially available products may be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation, "1B2PZ" and "1B2PZ-10M" manufactured by Shikoku Kasei Co., Ltd.

[0243] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0244] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene. Examples of such biguanide include o-[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0245] Examples of metal-based curing 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 octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0246] The content of the (E) curing accelerator exceeds 0% by mass, and from the viewpoint of significantly obtaining the effects of the present invention or controlling the curing time, when the non-volatile components in the resin composition are taken as 100% by mass, the content is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, for example, preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more.

[0247] <(F) Polymerization initiator> In the present invention, the resin composition may further contain a polymerization initiator as the component (F). In one embodiment, the component (A) contains the component (A-2), and the resin composition contains the component (F). However, the polymerization initiator (F) excludes those corresponding to the components (A) to (E). The polymerization initiator (F) may be used alone or in combination of two or more kinds. A typical example of the polymerization initiator as the component (F) is a peroxide-based polymerization initiator.

[0248] Examples of component (F) include peroxides such as t-butylcumyl peroxide, t-butyl peroxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butyl peroxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butyl peroxybenzoate.

[0249] Commercially available products of component (F) include, for example, NOF Corporation's “Perbutyl (registered trademark) C”, “Perbutyl (registered trademark) A”, “Perbutyl (registered trademark) P”, “Perbutyl (registered trademark) L”, “Perbutyl (registered trademark) O”, “Perbutyl (registered trademark) ND”, “Perbutyl (registered trademark) Z”, “Perhexyl (registered trademark) D”, “Percumyl (registered trademark) P”, and “Percumyl (registered trademark) D”.

[0250] When the resin composition contains the (F) component, the content of the (F) component, relative to 100 mass% of the non-volatile components in the resin composition, is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, even more preferably 0.05 mass% or more, and is preferably 5 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less.

[0251] <(G) Other Additives> The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include phenoxy resin, polyvinyl acetal resin, acrylic resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetherimide resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. Among them, thermoplastic resins such as phenoxy resin, acrylic resin, and polyphenylene ether resin; organic fillers such as rubber particles; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; defoamers such as silicone-based defoamers, acrylic defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based defoamers, and the like. Examples of the additives include ultraviolet absorbers such as thiocyanate-based ultraviolet absorbers, adhesion improvers such as urea silane, antioxidants such as hindered phenol-based antioxidants, fluorescent brighteners such as stilbene derivatives, surfactants such as fluorine-based surfactants and silicone-based surfactants, flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide), and dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants, and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers. (G) Other additives may be used alone or in combination of two or more at any ratio. (G) The content of other additives can be appropriately determined by one skilled in the art.

[0252] <(H) Organic Solvent> The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the non-volatile components described above. As the (H) organic solvent, a known one may be appropriately used, and the type is not particularly limited. As the (H) organic solvent, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, etc.; alcohol-based solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate, etc. Examples of the organic solvent include ether ester solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The organic solvent (H) may be used alone or in combination of two or more in any ratio.

[0253] The content of the (H) organic solvent is not particularly limited, but when all components in the resin composition are taken as 100 mass%, it can be, for example, 60 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, 5 mass% or less, etc.

[0254] <Method of producing resin composition> In the present invention, the resin composition can be produced, for example, by adding and mixing the components (A) and (B), and also the components (C), (D), (E), (F), (G), and (H) as necessary, in any order and / or all at once in any preparation vessel. In addition, the temperature can be appropriately set during the process of adding and mixing each component, and heating and / or cooling can be performed temporarily or throughout. In addition, during or after the process of adding and mixing, the resin composition can be stirred or shaken using a stirring device or shaking device such as a mixer to disperse the resin composition uniformly. In addition, degassing can be performed under low pressure conditions such as under vacuum at the same time as stirring or shaking.

[0255] <Physical properties and applications of resin compositions> As described above, the resin composition of the present invention contains (A) a curable resin and (B) a compound having a heterocyclic structure containing two or more nitrogen atoms and a cage silsesquioxane structure in the molecule, and thereby can provide a cured product having excellent dielectric properties and copper foil adhesion.

[0256] The dielectric properties can be evaluated by the method described in the <Evaluation of Dielectric Properties (Dielectric Constant, Dielectric Loss Tangent)> section below. The resin composition of the present invention, for example, has a dielectric constant (Dk) of a cured product obtained by thermal curing at 200°C for 90 minutes, preferably less than 3.20, more preferably 3.15 or less, even more preferably 3.1 or less, and particularly preferably less than 3.1. The dielectric loss tangent (Df) of the cured product is preferably less than 0.0032, more preferably 0.0031 or less, and even more preferably less than 0.0031. In a preferred embodiment, the dielectric constant (Dk) of a cured product obtained by thermal curing at 200°C for 90 minutes is preferably less than 3.2, and the dielectric loss tangent (Df) is preferably less than 0.0032.

[0257] The copper foil adhesion can be evaluated by the method described in the section <Measurement of copper foil peel strength (copper foil adhesion)> below. The resin composition of the present invention preferably has a peel strength of 0.40 kgf / cm or more, more preferably 0.42 kgf / cm or more, even more preferably 0.44 kgf / cm or more, and particularly preferably 0.46 kgf / cm or more, when laminated to a cured product obtained by thermally curing the resin composition at 130°C for 30 minutes and then at 200°C for 90 minutes.

[0258] In addition, in one embodiment of the resin composition of the present invention, there is a tendency that a cured product in which warpage is suppressed can be obtained. The suppression of warpage (low warpage) can be evaluated by the method described in the <Evaluation of low warpage> section below. For example, the resin composition of the present invention is thermally cured at 200°C for 90 minutes, and the cured product obtained has a warpage of preferably less than 1.0 cm, more preferably less than 0.95 cm, and even more preferably 0.95 cm or less.

[0259] The resin composition of the present invention can provide a cured product having excellent dielectric properties and copper foil adhesion. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating layers of printed wiring boards, particularly for interlayer insulation. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an interlayer insulation layer. In addition, the resin composition of the present invention can be suitably used as a resin composition for insulating the solder resist layer of a printed wiring board (resin composition for forming a solder resist layer).

[0260] The resin composition can obtain a cured product having excellent dielectric properties and copper foil adhesion. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation purposes. Specifically, it can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer) for forming a conductor layer (including a rewiring layer) formed on an insulating layer.

[0261] In addition, in the multilayer printed wiring board described later, the resin composition can be suitably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board) and a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board). The resin composition of the present invention can also be suitably used as a resin composition for a rewiring forming layer (resin composition for forming a rewiring forming layer) as an insulating layer for forming a rewiring layer, and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). An example of a manufacturing process for a semiconductor chip package will be described later.

[0262] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed from the resin composition of the present invention provided on the support.

[0263] 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 making the printed wiring board thinner and being able to provide a cured product with excellent insulation 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.

[0264] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0265] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes 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, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0266] When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0267] The surface of the support to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0268] In addition, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the support with a release layer may be, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support with a release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Unipeel" manufactured by Unitika Limited, which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

[0269] 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 a support with a release layer is used, it is preferable that the total thickness of the support with a release layer is in the above range.

[0270] In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film equivalent to the support provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dirt and the like to the surface of the resin composition layer and scratches can be suppressed.

[0271] The resin sheet can be produced, for example, by preparing a resin varnish by dissolving a resin composition in an organic solvent, applying this resin varnish onto a support using a die coater or the like, and then drying the same to form a resin composition layer.

[0272] Drying may be performed by a known method such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is performed so that the content of organic solvent in the resin composition layer becomes 10 mass % or less, preferably 5 mass % or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30 mass % to 60 mass % of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0273] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0274] [Printed wiring board] The printed wiring board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention.

[0275] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate so that a resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of thermally curing the resin composition layer to form an insulating layer

[0276] The "inner layer substrate" used in step (I) is a member that becomes the substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be called an "inner layer circuit substrate". In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed during the manufacture of a printed wiring board is also included in the "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0277] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). It is preferable to press the thermocompression member not directly onto the resin sheet, but via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the inner layer substrate.

[0278] The lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably performed under reduced pressure conditions of 26.7hPa or less.

[0279] The lamination can be performed by a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch type vacuum pressure laminator.

[0280] After lamination, the laminated resin sheet may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. The lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0281] The support may be removed between step (I) and step (II) or after step (II).

[0282] In step (II), the resin composition layer is thermally cured to form an insulating layer. The conditions for thermally curing the resin composition layer are not particularly limited, and conditions that are usually employed when forming an insulating layer for a printed wiring board may be used.

[0283] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, etc., but the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0284] Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50° C. or more and less than 120° C. (preferably 60° C. or more and 115° C. or less, more preferably 70° C. or more and 110° C. or less) 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).

[0285] In manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art for use in manufacturing printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0286] Step (III) is a step of drilling holes in the insulating layer, which allows holes such as via holes and through holes to be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a 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 depending on the design of the printed wiring board.

[0287] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smears are also removed. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid used in the roughening treatment is not particularly limited, but includes an alkaline solution, a surfactant solution, and the like, and is preferably an alkaline solution, and as the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P", "Swelling Dip Securigans SBU", and "Swelling Dip Securigant P" manufactured by Atotech Japan. The swelling treatment using a swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 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 liquid at 40°C to 80°C for 5 to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product is, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan. Treatment with a neutralizing solution can be performed by immersing the surface that has been roughened with an oxidizing agent in the neutralizing solution at 30°C to 80°C for 1 to 30 minutes.From the viewpoint of workability etc., a method in which the object that has been subjected to roughening treatment with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 minutes to 20 minutes is preferred.

[0288] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. There is no particular limit to the lower limit, but it is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0289] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0290] The conductor layer may be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has 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 a nickel-chromium alloy.

[0291] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.

[0292] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of ease of production, it is preferable to form the conductor layer by the semi-additive method. An example of forming the conductor layer by the semi-additive method will be described below.

[0293] First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0294] [Semiconductor Devices] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention. The semiconductor device of the present invention may include an insulating layer containing a cured product of the resin composition layer of the present invention. Examples of such semiconductor devices include a printed wiring board itself, a semiconductor chip package, a multi-chip package, a package-on-package, a wafer-level package, a panel-level package, and a system-in-package.

[0295] The semiconductor chip package is manufactured, for example, through the following steps (1) to (6): When the semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer. (1) A step of laminating a temporary fixing film onto a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A process of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0296] Semiconductor devices are used in electrical appliances (eg, computers, mobile phones, digital cameras, and televisions) and vehicles (eg, motorcycles, automobiles, trains, ships, and aircraft).

[0297] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a portion of a printed wiring board that transmits an electric signal, and the portion may be either on the surface or embedded. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of semiconductor material.

[0298] The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specific examples include a wire bonding mounting method, a flip chip mounting method, a bumpless buildup layer (BBUL) mounting method, an anisotropic conductive film (ACF) mounting method, a non-conductive film (NCF) mounting method, etc. Here, the "bumpless buildup layer (BBUL) mounting method" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess in a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board." EXAMPLES

[0299] The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Unless otherwise specified, the temperature and pressure conditions are room temperature (25°C) and atmospheric pressure (1 atm).

[0300] --Examples 1 to 6 and Comparative Examples 1 to 2-- Examples and comparative examples of the resin composition containing a component selected from the components (A) and (B) are shown below.

[0301] [Synthesis Example 1: Synthesis of imide compound b] (Synthesis of dihydroxy compounds) Two molar equivalents of tyramine (4-hydroxyphenylethylamine) were added to one molar equivalent of a cage silsesquioxane compound represented by the following formula ("DDSQ-02" manufactured by Japan Materials Technology Co., Ltd.) in dimethylformamide (DMF), and the mixture was stirred at room temperature for two hours. [ka]

[0302] Next, toluene was added and the mixture was heated to reflux overnight. In this manner, the imidization reaction was carried out. Ethyl acetate and water were added to the obtained imidization reaction solution, and then the organic layer was extracted. The extracted organic layer was purified using a column. The obtained predetermined fraction was concentrated to dryness to obtain an imidization reaction product (hereinafter referred to as "diimide body"). From the reaction pathway, it was estimated that the diimide body had a structure represented by the following formula. [ka]

[0303] (Synthesis of dichloro compound) Cyanuric acid chloride having a heterocyclic structure (specifically, a triazine structure) containing three nitrogen atoms as an N-rich heterocyclic structure precursor was reacted with aniline having an aromatic ring structure by a conventional method, purified by a column, and then crystallized with hexane to obtain a dichloro compound represented by the following formula. As represented by the following formula, in this dichloro compound, the N-rich heterocyclic structure and the aromatic ring structure were bonded to each other via the linking group -NH-. [ka]

[0304] (Synthesis of target compound) 1.9 parts by mass (0.001 mol) of the diimide body obtained as described above and 0.24 parts by mass (0.001 mol) of the dichloro body were dissolved in acetone, and then an aqueous sodium hydroxide solution was added and stirred at room temperature overnight. In this way, a polycondensation reaction was performed. The organic layer of the obtained polycondensation reaction solution was extracted with ethyl acetate. Then, the extracted organic layer was concentrated and dried. In this way, the target compound, imide compound b, was obtained. The weight average molecular weight (Mw) of the obtained imide compound was measured by the same method as the above-mentioned method, and it was 11000. It was estimated from the reaction path that imide compound b was a compound having a structure represented by the following formula. That is, imide compound b was a compound having an N-rich heterocyclic structure and a cage-type PSQ structure in the molecule. [ka]

[0305] [Synthesis Example 2: Synthesis of imide compound b' as a comparative compound of imide compound b] A varnish containing imide compound b' as a comparative compound for imide compound b was prepared as follows.

[0306] A 500 mL separable flask equipped with a water content receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were added to the flask, and the mixture was stirred at 45°C for 2 hours under a nitrogen stream to carry out the reaction, thereby obtaining a reaction solution.

[0307] Next, the reaction solution was heated and maintained at about 160°C, while the condensed water was azeotropically removed with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the water content receiver and that no water was flowing out. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. Then, it was cooled. In this way, a varnish containing 20% ​​by mass of the imide compound b' was obtained.

[0308] The imide compound b' had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). The weight average molecular weight of the imide compound b' was measured by the same method as described above and was found to be 12000. From the reaction pathway, it was clear that the imide compound b' was a compound that did not have either an N-rich heterocyclic structure or a cage PSQ structure in the molecule, unlike the imide compound b.

[0309] [ka]

[0310] [ka]

[0311] [Example 1] (1) Preparation of Resin Varnish A 5 parts of epoxy resin a1a (biphenyl type epoxy resin "NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 271 g / eq.) as component (A-1) and 5 parts of epoxy resin a1b (naphthalene type epoxy resin "HP-4032SS" manufactured by DIC Corporation, epoxy equivalent: 144 g / eq.) as component (A-1) were dissolved in a mixed solvent (20 parts of solvent naphtha and 10 parts of cyclohexanone) with stirring. This resulted in an epoxy resin-containing solution.

[0312] In the epoxy resin-containing solution, an inorganic filler c as component (C) (spherical silica "SC-C2" manufactured by Admatechs Co., Ltd., surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., specific surface area: 5.9 m 2 175 parts of 100% 1 / g, average particle size: 0.77μm), 50 parts of imide compound b (imide compound obtained in Synthesis Example 1) as component (B), 8.1 parts (non-volatile components: 5 parts) of curing agent da (active ester curing agent "HPC-8150-62T" manufactured by DIC Corporation, active group equivalent: 229g / eq., toluene solution containing 62% non-volatile components) as component (D), and 2 parts (non-volatile components: 0.2 parts) of curing accelerator (10% non-volatile components of imidazole curing accelerator "1B2PZ" (1-benzyl-2-phenylimidazole) manufactured by Shikoku Kasei Co., Ltd.) as component (MEK solution) were added, mixed, and further dispersed uniformly with a high-speed rotating mixer. As a result, a dispersion was obtained.

[0313] As described above, a resin varnish of a resin composition containing at least the components (A) and (B) was prepared. Hereinafter, the resin varnish thus prepared is also referred to as "resin varnish A."

[0314] (2) Preparation of resin sheet B As a support, a PET film ("Lumirror R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130°C, hereinafter sometimes referred to as "release PET") that had been release-treated with an alkyd resin-based release agent ("AL-5" manufactured by Lintec Corporation) was prepared.

[0315] Resin varnish A was uniformly applied onto the release PET with a die coater so that the thickness of the resin composition layer after drying was 25 μm, and dried at 80 ° C for 1 minute to obtain a resin composition layer on the release PET. Next, a rough surface of a polypropylene film (Oji F-Tex Co., Ltd. "Alphan MA-411", thickness 15 μm) was laminated as a protective film on the surface of the resin composition layer that was not bonded to the support, so as to be bonded to the resin composition layer. This resulted in a resin sheet consisting of the release PET (support), the resin composition layer, and the protective film in this order. Hereinafter, the resin sheet produced in this manner is also referred to as "resin sheet B".

[0316] [Example 2] In Example 1, 8.1 parts (non-volatile components: 5 parts) of curing agent da ("HPC-8150-62T" (non-volatile components: 62% by mass) as component (D) was changed to 7.7 parts (non-volatile components: 5 parts) of curing agent db (active ester curing agent "HPC-8000-65T" manufactured by DIC Corporation, active group equivalent: 223 g / eq., toluene solution with 65% by mass of non-volatile components). Except for the above, resin varnish A was prepared and resin sheet B was produced in the same manner as in Example 1.

[0317] [Example 3] In Example 1, the amount of inorganic filler c ("SC-C2") blended as component (C) was changed from 175 parts to 220 parts, and further, 28.6 parts (non-volatile components: 20 parts) of a radically polymerizable compound a2a (biphenylaralkyl-type maleimide compound "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a MEK / toluene mixed solution with 70 mass % non-volatile components) as component (A-2) and 0.2 parts of a polymerization initiator ("Perhexyl (registered trademark) D" manufactured by NOF Corporation) as component (F) were blended into the epoxy resin-containing solution. Except for the above, resin varnish A was prepared and resin sheet B was produced in the same manner as in Example 1.

[0318] [Example 4] In Example 3, 28.6 parts (non-volatile components: 20 parts) of the radical polymerizable compound a2a ("MIR-3000-70MT" (non-volatile components: 70% by mass) as the component (A-2) was changed to 20 parts of a radical polymerizable compound a2b (maleimide compound "BMI-689" manufactured by Designer Molecules, Inc. (N-alkylbismaleimide having a skeleton derived from dimer diamine, solvent-free). Except for the above, resin varnish A was prepared and resin sheet B was produced in the same manner as in Example 3.

[0319] [Example 5] In Example 3, 28.6 parts (non-volatile components: 20 parts) of the radical polymerizable compound a2a ("MIR-3000-70MT" (non-volatile components: 70% by mass) as the component (A-2) was changed to 30.7 parts (non-volatile components: 20 parts) of the radical polymerizable compound a2c ((vinylbenzyl-modified polyphenylene ether "OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Company, Inc., a toluene solution containing 65% non-volatile components). Except for the above, resin varnish A was prepared and resin sheet B was produced in the same manner as in Example 3.

[0320] [Example 6] In Example 1, the amount of inorganic filler c ("SC-C2") as component (C) was changed from 175 parts to 35 parts, and the amount of curing accelerator ("1B2PZ" (non-volatile component: 10% by mass) as component (E) was changed from 2 parts (non-volatile component: 0.2 parts) to 1 part (non-volatile component: 0.1 parts). Except for the above, resin varnish A was prepared and resin sheet B was produced in the same manner as in Example 1.

[0321] [Comparative Example 1] In Example 1, instead of 50 parts of the imide compound b (imide compound obtained in Synthesis Example 1) as the component (B), 250 parts (non-volatile component: 50 parts) of the imide compound b'-containing varnish (the imide compound varnish obtained in Synthesis Example 2 (non-volatile component: 20% by mass)) as the component (B') was blended into the epoxy resin-containing solution. Except for the above, resin varnish A was prepared and resin sheet B was produced in the same manner as in Example 1.

[0322] [Comparative Example 2] In Example 3, instead of 50 parts of the imide compound b (imide compound obtained in Synthesis Example 1) as the component (B), 250 parts (non-volatile component: 50 parts) of the imide compound b'-containing varnish (varnish of the imide compound obtained in Synthesis Example 2 (non-volatile component: 20% by mass)) as the component (B') was blended into the epoxy resin-containing solution. Except for the above, resin varnish A was prepared and resin sheet B was produced in the same manner as in Example 3.

[0323] Next, various measurement and evaluation methods will be explained.

[0324] <Evaluation of low warpage> (1) Lamination of resin sheet Each resin sheet B produced in the examples and comparative examples was cut into a size of 9.5 cm square, the protective film was peeled off, and the resin sheet B was laminated onto the roughened surface of a copper foil "3EC-III (thickness 35 μm)" produced by Mitsui Mining & Smelting Co., Ltd., cut into a size of 10 cm square, using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700"). The lamination was carried out by reducing the pressure for 30 seconds to 13 hPa or less, and then pressing at 120°C for 30 seconds at a pressure of 0.74 MPa to produce a metal foil with a resin composition layer, and then peeling off the PET film as the support.

[0325] (2) Curing of the resin composition layer The four sides of the metal foil with the resin composition layer obtained in (1) above were attached to a 1 mm thick SUS plate with polyimide tape so that the resin composition layer was on the upper side, and the resin composition layer was cured under curing conditions of 200°C and 90 minutes.

[0326] (3) Measurement of warpage The polyimide tape was peeled off from three of the four sides of the metal foil with the resin composition layer obtained in (2) above, and the height of the highest point from the SUS plate was measured to determine the amount of warping, which was then evaluated according to the following criteria. ○: The amount of warping is less than 1 cm. ×: The amount of warping is 1 cm or more.

[0327] <Measurement of copper foil peel strength (copper foil adhesion)> (1) Copper foil preparation The shiny side of Mitsui Mining & Smelting Co., Ltd.'s "3EC-III" (electrolytic copper foil, 35 μm) was etched by 1 μm with a micro-etching agent (Mec Co., Ltd.'s "CZ8101") to roughen the copper surface, and then an anti-rust treatment (CL8300) was applied. Furthermore, it was heated in an oven at 130°C for 30 minutes. This copper foil is called CZ copper foil.

[0328] (2) Preparation of inner layer board Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") with an inner layer circuit formed were etched 1 μm with a microetching agent (Mec "CZ8101") to roughen the copper surface.

[0329] (3) Laminating copper foil and forming an insulating layer The protective film was peeled off from the prepared resin sheet B to expose the resin composition layer. Using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700"), the resin composition layer was laminated on both sides of the inner layer substrate so that it was in contact with the inner layer substrate. The lamination was performed by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then pressing at 120 ° C and a pressure of 0.74 MPa for 30 seconds. Then, a heat press was performed at 100 ° C and a pressure of 0.5 MPa for 60 seconds. The treated surface of the CZ copper foil was laminated on the resin composition layer under the same conditions as above. Then, the resin composition layer was cured under a curing condition of 200 ° C and 90 minutes to form an insulating layer, thereby preparing an evaluation substrate.

[0330] (4) Measurement of copper foil adhesion before reliability testing The prepared evaluation board was cut into small pieces of 150 x 30 mm. A cutter was used to make a 10 mm wide and 100 mm long cut in the copper foil part of the small piece, and one end of the copper foil was peeled off and gripped with a gripper. The load (kgf / cm) when 35 mm was peeled off vertically at a speed of 50 mm / min at room temperature was measured to determine the peel strength. A tensile tester (TSE "AC-50C-SL") was used for the measurement. The measurement was performed in accordance with the Japanese Industrial Standard (JIS C6481), and the copper foil adhesion before the reliability test was evaluated according to the following criteria. ○: Adhesion is 0.40kgf / cm or more ×: Adhesion is less than 0.40 kgf / cm

[0331] <Evaluation of dielectric properties (dielectric constant, dielectric tangent)> The protective film was peeled off from each resin sheet B produced in the examples and comparative examples, and the resin composition layer was thermally cured by heating at 200°C for 90 minutes, and then the support was peeled off. The obtained cured product was cut into a test piece having a width of 2 mm and a length of 80 mm. The dielectric constant (Dk) and dielectric loss tangent (Df) of the test piece were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by a cavity resonance perturbation method using an "HP8362B" manufactured by Agilent Technologies. Measurements were performed on three test pieces, and the average value was calculated.

[0332] The dielectric properties were evaluated according to the following criteria. ◯: Dielectric constant is less than 3.2 and dielectric tangent is less than 0.0032 ×: At least one of the dielectric constant being 3.2 or more and the dielectric tangent being 0.0032 or more is satisfied.

[0333] The results of Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 1.

[0334] [Table 1]

[0335] In Examples 1 to 6, even if the components (A-1) and (D) are not contained, when the curing system is different, for example, when the components (A-2) and (F) are contained, it has been confirmed that the results are similar to those of the above examples, although to a different extent.

Claims

1. (A) a curable resin, and (B) A compound having a heterocyclic structure containing two or more nitrogen atoms and a cage-type silsesquioxane structure in the molecule. A resin composition comprising: The component (A) contains an epoxy resin, the heterocyclic structure containing two or more nitrogen atoms in the component (B) is a triazine structure, In the component (B), an imide bond is present between the heterocyclic structure and the cage silsesquioxane structure, A resin composition, wherein the weight average molecular weight (Mw) of component (B) is 3,000 or more.

2. The resin composition according to claim 1 , wherein the component (B) contains, in the molecule, an aromatic ring structure which may have a substituent and is bonded to the heterocyclic structure via a linking group.

3. The resin composition according to claim 1 or 2, wherein the cage silsesquioxane structure is a double-decker silsesquioxane structure.

4. The resin composition according to any one of claims 1 to 3, wherein the cage silsesquioxane structure includes a cage structure represented by the following formula (B1): 【Chemistry 1】 [In the above formula (B1), X's are each independently a group selected from an alkyl group having 1 to 40 carbon atoms in which a hydrogen atom may be replaced by a halogen atom, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group in which a hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 20 carbon atoms, and an arylalkyl group in which an aryl group in which a hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 20 carbon atoms is bonded to an alkylene group having 1 to 8 carbon atoms; Each Y is independently a group selected from an alkyl group having 1 to 40 carbon atoms in which a hydrogen atom may be replaced by a halogen atom, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group in which a hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 20 carbon atoms, and an arylalkyl group in which an aryl group in which a hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 20 carbon atoms is bonded to an alkylene group having 1 to 8 carbon atoms; * is a bond; When X or Y is an alkyl group having 1 to 40 carbon atoms, the —CH ２ - may be replaced by -O- or -CH=CH-; When X or Y is an aryl group, and a hydrogen atom of the aryl group is replaced by an alkyl group having 1 to 20 carbon atoms, a hydrogen atom of the alkyl group having 1 to 20 carbon atoms may be replaced by a halogen atom, and —CH ２ - may be replaced by -O- or -CH=CH-; When X or Y is an arylalkyl group, the arylalkyl group contains —CH ２ - may be replaced by -O-.

5. The resin composition according to claim 4 , wherein each X is a phenyl group.

6. The resin composition according to any one of claims 1 to 5, further comprising (C) an inorganic filler.

7. The resin composition according to claim 6 , wherein the content of the component (C) is 10% by mass or more, based on 100% by mass of non-volatile components in the resin composition.

8. The resin composition according to claim 6 or 7, wherein the content of the component (C) is 90 mass% or less, based on 100 mass% of non-volatile components in the resin composition.

9. The resin composition according to any one of claims 6 to 8, wherein the content of the component (C) is 40 mass% or less, when the non-volatile components in the resin composition are 100 mass%.

10. The resin composition according to any one of claims 6 to 9, wherein the total content of the (B) component and the (C) component is 50 mass% or more, when the non-volatile components in the resin composition are 100 mass%.

11. The resin composition according to any one of claims 1 to 10, wherein the component (A) contains (A-2) a radical polymerizable resin.

12. The resin composition according to any one of claims 1 to 11, wherein the content of the component (B) is 0.01 mass% or more and 60 mass% or less, when the non-volatile components in the resin composition are 100 mass%.

13. The resin composition according to any one of claims 1 to 12, wherein the dielectric constant (Dk) of the cured product of the resin composition is less than 3.

2.

14. The resin composition according to any one of claims 1 to 13, wherein the cured product of the resin composition has a dielectric loss tangent (Df) value of less than 0.0032.

15. The resin composition according to any one of claims 1 to 14, which is for use in an insulating layer of a printed wiring board.

16. A cured product of the resin composition according to any one of claims 1 to 15.

17. A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 15 provided on the support.

18. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 15.

19. A semiconductor device comprising the printed wiring board according to claim 18.

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